Eth 22533 02

Diss.
ETH No 12380
Identification of the
Oxygen
Reduction
at Cathodes of Solid Oxide Fuel Cells
A dissertation submitted to the
SWISS FEDERAL INSTITUTE OF TECHNOLOGY

ZURICH
for the
degree
of
Doctor of Technical Sciences
presented by
Andreas Mitterdorfer
Dipl. Werkstoff-Ing. ETH born on February 19,1966 citizen of Wiesendangen, ZH
accepted
on
the recommendation of
examiner
Prof. Dr.
Dr. B.
L.J. Gauckler,
Elsener, co-examiner
1997
Diss. ETH No 12380
Identification of the
Oxygen
Reduction
at Cathodes of Solid Oxide Fuel Cells
A dissertation submitted to the SWISS FEDERAL INSTITUTE OF TECHNOLOGY
ZURICH
for the
degree
of
Doctor of Technical Sciences
presented by
Dipl. Werkstoff-Ing. ETH born on February 19,1966 citizen of Wiesendangen, ZH
accepted on the
Dr. B.
recommendation of
Prof. Dr. L.J. Gauckler, examiner
Elsener, co-examiner
1997
Date of oral examination: October 3,1997, 3 p.m.
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Acknowledgments
I wish to express my
deep gratitude
to
my advisor, Prof. Dr. L.J. Gauckler,
head of the chair of Nonmetallic Materials, for his
encouragement and sup

opportu
port, and for his willingness
to entrust
so
much of the advance of the
project nity
to
to
my
judgement.
In
particular,
I wish to thank him for the

over
present
as
my results at international conferences all well
the world.
I wish to thank Dr. B. Elsener from the Institute of Corrosion Science for
acting
giving
co-examiner of this thesis
as
as
Prof. Dr. D. Bonnell, of the
on
Sabbat
ical from
Pennsylvania University,
valuable comments, and
reading most parts improving the language.
for
manuscript,
I wish to thank the members of the SOFC group at the chair of Nonmetal
Christoph Kleinlogel for many helpful discussions and support as well as their company during confer ences; Julia Will for continuing the processing of ceramic foams; Anja Bieberle and Roger Stadler for carrying on state-space modelling of electrochemical systems and making the method more known to others; Wal ter Tobler for his contributions during his diploma work and his assistance after the diploma. colleagues at the chair of Nonmetallic Materials: Prof. Dr. G. Bayer for giving time and attention to my questions about crystallography and ceramics processing; Dr. Marco Cantoni for his support in HRTEM analysis and his excellent support in operating the AFM and SEM; Dr. P. Bohac for helpful scientific discussions; Peter Kocher for his
am
lic Materials: Dr. Martin Godickemeier and
further indebted to many
technical assistance, his PC cult times;
support, and his encouragement during the diffi

the
Bengt Hallstedt for sharing
job
of UNIX network management
and Frank Filser for
taking this job
from
me.
I also wish to thank the members of Sulzer Innotec in Winterthur and the
members of the Swiss Federal Institute of

in SOFC R&D for their
Technology
in Lausanne involved
support and
interest.
family, my family, and my friends for their support and encouragement during my education. I also wish to thank Daniel Jurt for his support in typographical questions. I finally wish to express my gratitude to Dr. Leo Dubai from the Swiss Federal Department of Transportation, Communications, and Energy for his
continual interest and financial
I wish to thank my wife Denise and her
support of the project.
November,
1997
IV
Table
of
Contents
Acknowledgments
Table of Contents
List of
iii
v
Figures
ix
xv
List of Tables
Summary
xvii
Zusammenfassung
xix
Part I
1
Front Matter
3
Introduction 1.1
Background
1.1.1
3
3 5 8
11
Solid State Ionics Electrochemical Devices
1.1.2 The
1.1.3 1.2 1.3
Origin of Potential Differences Oxygen Reduction
Aim of the Thesis
Structure of the Thesis
12 13
References
Part
2
II
Theoretical
Analysis
of the Pt,
Oz(g)
I YSZ
System
19
General 2.1 2.2
Framework, Modelling, and Structural Investigation
Introduction
20
24
General Framework
2.2.1 2.2.2
The Process of
Modelling Hypotheses
24
General Considerations and
25 28
2.2.3
Modelling
Reaction Mechanisms
2.3
Identifying G(s) with Electrochemical Quantities 2.2.5 Working with Frequency Responses 2.2.6 Identifiability of Linear Reaction Models Reaction Models of the Pt, 02(g) I YSZ System
2.2.4
30
35 37
38 38
2.3.1
Introduction
2.3.2 Basic
Equations
and
Assumptions
39
42 45
2.3.3 Electrode
2.3.4
Overpotential
Behaviour
. .
2.3.5
2.4
Properties of the Models Qualitative Analysis of Frequency Response

Structural
56 60 61 66
Conclusions
References
Appendix
2-A.l
2-A.2
3
Space Description of an Electrical Circuit Calculation of tpb length from microstructural data
and Validation
State
...
66 68
71
Computer Implementation, Simulation,

3.1
3.2
Introduction
Model
3.2.1 3.2.2
72
Implementation Computer Tools and General Procedure Heterogeneous Chemical and Electrochemical
Transport
73 73
Kinetics
74
77 81
3.2.3 Surface Mass 3.3
Simulation Procedures
3.3.1 3.3.2
Model Initialization and

Penetration
Sensitivity
81 82 86
3.3.3 3.3.4 3.4
The
Depth and tpb Width Double Layer Capacitance

Simulation and Numerical
Digital
Aspects
91
Simulation Results
92 92
.
3.5
Charge-Transfer Controlled Kinetics 3.4.2 Competition Between Surface Diffusion and Adsorption 3.4.3 Sensitivity Analysis and Practical Identifiability Summary and Conclusions
3.4.1
110
124
129
References
131
136 Reaction Model Constants and Parameters
Appendix
3-A.l
3-A.2
136
Determination of
Cd\ by Potential Step

137
3-A.3
3-A.4
Chronoamperometry Implementation and Simulations Implementation and Simulations
of Model Ml of Model M2
139 148
VI
Part
III
The Interface between
Lao 85Sr015MnyO3+s and

Oxygen
Reduction Kinetics
159
Yttria-Stabilized Zirconia
4
Lanthanum Zirconate Formation and

4.1
Introduction
4.1.1
160
General
160
4.1.2 Microstructure
and-Chemistry Properties Aims of the Study
161 163 165 166

166
4.1.3 Influence 4.1.4

4.2
on
Electrochemical
Open Questions and Experimental Procedures 4.2.1 Sample Preparation
4.2.2
4.2.3 4.3
Investigation of Surfaces and Interfaces Electrochemical Investigation
168
169 170
....
Results
4.3.1 4.3.2 4.3.3
Conductivity Interface Development During Sintering Electrochemical Properties LSMq 98 Cathodes

General
Cathode Microstructure and Electrical
170 172 190 197 197 198
4.4
Discussion 4.4.1 4.4.2

4.4.3
Lanthanum Zirconate Formation
Oxygen
Reduction Kinetics at
LSM0 93/YSZ Interfaces.
207 223
224
4.5
Conclusions
References
Part
5
IV
End Matter
233
Outlook
5.1 5.2 5.3 5.4 5.5
General
233 234 235 236
Identification of Reaction Mechanisms
Modelling
and Simulation
Materials and
Samples Electrochemical Investigation Techniques
236
239
Curriculum Vitae
vii
viii
List
of
Figures
Chapter 1
1.1
Schematics of
half cell with Pt and
an
ionic
7
conductor in contact
1.2
Interface between cathode and solid

Schematic
electrolyte surface
at
1.3
diagram of predominant reaction steps electrode/electrolyte interface
10
Chapter 2
2.1
Schematic view of the oxygen reduction process at interfaces between noble metals and solid oxide
ion-conducting electrolytes
2.2
25
Secondary
Pt
on a
Electron
(001) YSZ
Micrograph (SEM) of porous single crystal surface

response of first-order
26
2.3
General Faradaic
frequency
an
electrochemical systems
2.4
2.5
33
"Equivalent
circuit" of
noble
metal/electrolyte system
area near
36
41
Schematic view of the active electrode
the tpb
2.6
Schematics of
three-electrode cell with identical

43
porous Pt electrodes
2.7
Two-compartment model
for structural
investigation
53
in the
of reaction mechanism M2
2.8
Qualitative frequency response of Ml shown
complex plane
2.9
57
in

Bode
representation
58
2.10
2-A1.1
Frequency
responses of Ml in Bode
representation
59 66
RC electrical circuit
2-A2.1
Simplified morphology
interface
of noble
metal/electrolyte
68
Chapter 3
3.1
electrode geometry and one-dimensional finite element model
Simplified
78 83
3.2
Temperature dependence
Electrical
of 0)max for
3.3
3.4
equivalent circuits partial

pressure
the
fitting experimental
EIS data
89
Relation between the

the oxygen
exchange current density i0 charge

at
and
94
3.5 3.6
Dependence of i0
on
transfer coefficient S
95
Isobaric Arrhenius
plot of /0
different oxygen
partial
98 1123 K 100 101 102
pressures
3.7 3.8 3.9 3.10
Steady-state /f(tj)
Deviation of Simulated
behaviour of Model M2 at T
/F(r|)
from theoretical Tafel behaviour
/f(t))
behaviour and Tafel
analysis
i0 values
Comparison
atr
=
of theoretical and estimated
1123K
103
3.11 3.12
Simulated
Z(j(o)
of M2 shown in the
complex plane
on
105
Influence of double
of
layer capacitance
appearance
106 107
Z(jco) spectra
3.13 3.14 3.15
Complex plane plot of simulated impedance data

Determination of Determination of
ZF(j(o)
from simulated
noisy Z(jco)
data
108 109
Rp and Rt after subtraction of CdJ

as a
3.16
Electrode conductivities and oxygen
function of
temperature
Ill
partial
pressure
3.17
Oxygen partial pressure dependence of electrode

conductivities of model M2
112
3.18
Isobaric Arrhenius
plots
of electrode
conductivity
115
3.19
Simulated temperature dependence of the oxygen partial pressure where the maximum of the electrode
conductivity occurs
3.20
116
Simulated
partial
3.21 3.22
under different oxygen pressure conditions at 973 K (700C)
/F(r|) relationships
118 120
Simulated cathodic
limiting-current behaviour
=
of M2
Simulated
impedances at T different overpotentials T|

Simulated
973 K
(700C)
at
121
=
3.23
impedances at T 973 K (700C) and different cathodic overpotentials

Sensitivity
of
123
3.24
IZFI
IZFI
with
respect
to the unknown
parameters
3.25
124 with
Sensitivity
of
respect
area
to the
length of the tpb

125
and the width of the active

3.26
Sensitivity of IZFI with respect to condition w-lc const

=
with under the

127
128
3.27
3.28
Correlation between
and
klc
with respect to the activation energy of the surface diffusion of Oad
Sensitivity
of
IZFI
129
3-A2.1
Comparison of potential step

circuits
responses of
equivalent
139
3-A3.1
Simulink block
diagram
for the
adsorption/desorption
140
....
dynamics
3-A3.2
3-A3.3
Simulation results for model Ml at reference conditions
141
Simulink block
diagram of Ml
in order to extract
linearized state-space models

3-A3.4
143
diagram of Ml current-voltage behaviour

Simulink block Simulink block
for simulation of 147
3-A4.1
diagram diagram
for the tpb
compartment of
M2
....
152
3-A4.2
3-A4.3
Simulink block
Simulink block
M2
of M2 with four
for
compartments
two of
....
152
diagram (subsystem)
compartment
153
xi
Chapter 4
4.1
4.2
SEM of sintered
LSMj 02 cathode
on
YSZ
single crystal
170
4-probe electrical conductivity

in air
of LSM
cathode
layers
171
on
4.3
XPS sputter depth YSZ single crystal TEM

on a
profile
of
La-rich surface
layer
173
4.4
images
(001)
a
of lanthanum zirconate islands grown YSZ single crystal surface
174
4.5
AFM of
lanthanum zirconate surface
layer covering a
YSZ
176
single crystal
4.6
AFM
with
4.7
images of a (001) YSZ single crystal surface covered cube-shaped islands of lanthanum zirconate
178
LZO island and YSZ
growth kinetics
at 1373 K between
LSMq 98
180 182 183
4.8 4.9 4.10
Bright
field TEM of LZO island
on
(001)
YSZ surface
HRTEM of LZO island surface
images of (001) YSZ surface La0.85Sr0 isMn! 02O3 cathode

AFM
after
sintering with
184
4.11
Density sliced sintering
AFM
image
of YSZ surface after
long-term
186 187
4.12 4.13
Plan-view TEM of YSZ surface
Bright-field TEM of cross ring-shaped island
section of
188
4.14
Typical complex plane plot of the electrochemical impedance of a LSM0.981 YSZ interface during heat
treatment in air
190
4.15
Bode
plots
of
LSMg 98
cathodes
on
YSZ
during heat
192
treatment
4.16
4.17
Arrhenius
plot of conductivity ae
of
LSMq 98
cathode
193
Oxygen partial pressure dependence conductivity of LSM0 98 cathode
of electrode
194
4.18
Oxygen partial pressure dependence impedance of LSMq 98 cathodes
of the electrochemical
195
xii
4.19
Schematic view of the LZO of
layer formation at the
interface
199
LSMq 95
and YSZ
4.20
Schematic view of LZO island formation and the interface between
growth
growth
at
LSMq 98 LSMj 02
and YSZ
at
202
4.21
Schematic view of LZO island formation and

the interface between
and YSZ
205
4.22
"Equivalent circuit" of an electrode/solid electrolyte system and corresponding frequency responses

Complex plane plot of Impedance Z and Faradaic impedance ZF of unsintered LSMq 981 YSZ interface
at873K(600C)
210
4.23
211
4.24
Frequency dependencies of IZI and IZFI LSMq.98 I YSZ interface at 873 K (600C)
of the unsintered
213
4.25
Complex plane plot of Impedance Z and Faradaic impedance ZF of the unsintered LSMq 981 YSZ interface
'
at 1123 K
(850C)
214
4.26
Complex plane plot of Impedance Z of sintered LSMq.98 I YSZ interface at 1223 K (950C) and low oxygen partial pressures Complex plane plot of Impedance Z and Faradaic impedance ZF of the sintered LSMq 981 YSZ interface
at 893 K
216
4.27
(620C)
in oxygen
217
4.28
Frequency dependence of IZI and IZFI of the sintered LSMo981YSZ interface at 893 K (620C) at different oxygen partial pressures
Model of the oxygen reduction at unsintered and sintered LSMq 98/YSZ interfaces
218
4.29
220
xiii
xiv
List
of
Tables
Table 3.1
Parameters and Constants used in Model Ml and M2

136
Table 4.1
Characteristics of the
used in this
screen-printing pastes
167
study
Leer
Vide
Empty
xvi
Summary
The
high temperature
reduction of oxygen at interfaces between solid oxide
oxygen ion conductors and

consists of
a
electronically conducting
cathode materials
number of
elementary steps: transport

on
of oxygen in the porous
cathode network,
adsorption of oxygen
the cathode, and electrochemical

measure
and chemical interfacial reactions.

ments and electrochemical
Steady-state current-voltage
are
impedance spectroscopy
the main electro
chemical
investigation techniques employed improve
for electrode characterization.
In order to be able to
the electrochemical
performance
of cathodes
the reaction mechanisms and the associated kinetic rate constants must be known. The purpose of the present the identification of
study
is to
provide a general
method for
heterogeneous
electrode reaction mechanism. The
application of this
A method is
method is demonstrated with two different systems.
developed
for
dealing
with micro-kinetic models. This
methods allows for model
performing
mathematical and
analysis
of the
equations,
implementation, steady-state
dynamic simulations,
a
and parame
ter estimation
(numerical optimization) within
single
framework. The
from
models
are
described
by time-independent state-space equations
which the Faradaic admittance transfer function is obtained. The Pt,
02(g) I Zr02 system

for its
is considered
as
model system and is
investigated
identifiability
of unknown parameters.
Oxygen adsorp-
tion
on
Pt, surface diffusion of atomic oxygen, and the electrochemical reduc
tion of adsorbed oxygen at the
three-phase boundary
is considered. It is
can
shown that the unknown rate constants and parameters estimated from
a
be
accurately
combination of mathematical
analysis,
electrochemical
surface
meas
measurements, and numerical data diffusion coefficients

can
analysis. Coverage dependent
be estimated from
impedance spectroscopy
can
urements. The method of
working
demonstrated
be well
applied
to other
metal electrode/solid
electrolyte systems.
La0 8sSr015Mn03, 02(g) I Zr02 system
are
The relevant reaction steps in the discriminated from electrochemical

an
experimental study, comprising

The
microstructural and
characterizations.
formation
of
the
foreign phase
means
La2Zr207
at the
cathode/electrolyte
interface is
investigated by
of
high
resolution transmission electron
microscopy
and atomic force micros
copy. The manganese concentration in the

nucleation and the
perovskite
A-site
affects the onset of

in the per
growth
rate of
La2Zr207.
deficiency
ovskite may prevent the interfaces

are
La2Zr207
formation. The electrochemical
properties
of
strongly
influenced
by La2Zr207
islands at the
three-phase
boundary. Charge transfer,
dissociation of adsorbed molecular oxygen ions,

are
and surface diffusion of atomic oxygen
discriminated from electrochemi
cal
impedance investigations.
xviii
ZUSAMMENFASSUNG
Die
Hochtemperatur-Reduktion Festelektrolyten
von
Sauerstoff
an
Grenzflachen zwischen
oxidischen
aus
und elektronisch leitenden Kathoden setzt sich

zusammen:
verschiedenen Teilschritten
dem
Transport
von
gasformi-
gen Sauerstoff im
Porensystem
der Kathode, der
Adsorption von Sauerstoff
auf der Kathodenoberflache, sowie elektrochemischen und chemischen
Grenzflachenreaktionen.
Statische
zu
Strom-Spannungs-Messungen
am
und
Impedanzmessungen
mischen
ten
zahlen
den
meisten verwendeten elektroche
Untersuchungsmethoden.
Kathoden verbessern
Um die elektrochemischen
zu
Eigenschafder
von
konnen,
ist
die
Kenntnis
Reaktionsmechanismen sowie die der relevanten kinetischen Parameter
notwendig.
tifikation
Das Ziel dieser Studie ist es, eine
allgemeine Methode
zur
Iden-
von
Reaktionsmechanismen
heterogener
Elektrodenreaktionen
bereitzustellen und deren
Anwendung
anhand zweier unterschiedlicher
Systeme
zu
demonstrieren.
zur
Es wird eine Methode
Behandlung
von
mikro-kinetischen Modellen
entwickelt. Diese Methode
ermoglicht
die mathematische
Behandlung
der
Bilanzgleichungen, die Computer-Implementierung der Modelle, die Simula

tion
vom
statischen und
dynamischen Verhalten,
sowie Parameter-Schatzun-
gen mit ein und demselben Formalismus. Die Modelle werden dabei mittels
zeitunabhangiger Zustandsgleichungen beschrieben,
woraus
die Ubertra-
gungsfunktion der Faraday-Admittanz erhalten werden kann.
Als wird
Modell-System
wird das Pt,
02(g) I c-Zr02-System
von
betrachtet. Dieses
beziiglich
der Identifizierbarkeit
unbekannten Parametern unterauf Pt, die Oberflachendiffusion
sucht. Es werden die

von
Sauerstoffadsorption
atomarem Sauerstoff auf Pt und die

an
elektrochemische Reduktion
von
adsorbiertem Sauerstoff
der
Dreiphasengrenze miteinbezogen.
Es wird
aus
gezeigt,
einer
dass die unbekannten kinetischen Konstanten und Parameter

von
Kombination
mathematischer
Behandlung,
elektrochemischen
Messungen
und numerischer
vom
Datenanalyse mit grosser Genauigkeit ermittelt

Diffusionskoeffizient
werden konnen. Der

von
Bedeckungsgrad abhangige
aus
atomarem Sauerstoff auf Pt kann
elektrochemischen
Impedanzmes-
sungen bestimmt werden. Die

andere
vorgestellte
Methodik kann ohne weiteres auf
Metall/Festelektrolyt-Systeme iibertragen werden.

an
Der Mechanismus der Sauerstoffreduktion
Grenzflachen zwischen
und elektrochemi
an
La0 85Sr015Mn03
und
c-Zr02
wird mit
mikroskopischen
der
schen Methoden charakterisiert. Die
Bildung
Fremdphase La2Zr207
der Grenzflache zwischen der porosen Kathode und dem wird mittels hochauflosender
Festelektrolyten
und
Transmissions-Elektronenmikroskopie
Der
Atomkraftmikroskopie
beeinflusst
untersucht.
Mangan-Gehalt
auch die
vom
Perowskit der
sowohl
den
Zeitpunkt
als
Geschwindigkeit
La2Zr207-Bildung.
werden durch
Die elektrochemischen
an
Eigenschaften
der Grenzflache
betrachtlich
von
ver-
La2Zr207-Inseln
der
Dreiphasengrenze
die Dissoziation
schlechtert. Der
Ladungstransfer-Schritt,
adsorbierten
atomarem
molekularen Sauerstoffionen und die Oberflachendiffusion Sauerstoff werden als relevante Reaktionsschritte bestimmt.
aus
von
Impedanzmessungen
xx
Parti
Front Matter
Chapter
Introduction
Abstract
The reader is introduced into the

state
operating principles
and
into
of solid
ionics
electrochemical devices
electrochemical
kinetics. The differences between Solid Oxide Fuel Cells
(SOFC),
oxygen sensors, oxygen pumps, and oxygen

branes
ous
are
presented.
that
is
Some
occur
emphasis
at
is
separation mem given on the heterogene

interfaces.
The
term
processes
materials
"overpotential"
explained.
The present status of
knowledge
given.
It
are
about the oxygen reduction kinetics at SOFC cathodes is
References to the most relevant literature in the field
given.
is assumed that the reader is familiar with most of the micro
scopic
and
spectroscopic techniques employed
in this thesis.
1.1
1.1.1
Background
Solid State Ionics Electrochemical Devices
Solid state ionics electrochemical devices consist of two
ducting electrodes which are separated by a gas Y203-stabilized Zr02 (YSZ) has been employed by far conducting electrolyte
for its
electronically con tight solid electrolyte.

most
as
oxygen ion
relatively high ionic conductivity at high tem peratures, its structural stability in both oxidizing and reducing atmospheres, its capability of being easily produced, and its relatively low price [1]. A number of other ionic conductors, such as doped Ce02 [2], 8-Bi203 [3], or per-
Introduction
ovskite-type LaGa03 [4]
have been
investigated
for
use as
solid oxygen ion
conductors. Neither of these materials has reached the role of YSZ up to the present time. The reader interested in new ceramic oxygen conductors is
referred to recent literature
(see e.g. [5, 6],
and references
therein).
A pro
found review
can
on
the science and
technology
of solid oxide fuel cells
(SOFC)
be found in the article and book of Minh

case
[7,8].
current-producing device, such as a SOFC, the electrodes are exposed to atmospheres of different oxygen partial pressures. The electromo tive force (emf) which develops across the cell under equilibrium conditions, i. e. if no current is flowing through the device, is given by the Nernst equa
a
In the
of
tion
emf
Po,
=
4f
low
(1.1)
j
vPo2
partial
an
where
p08
anc^
Vo*
are me
oxygen
pressures at the cathode and at
the anode,
respectively,
is
F is the
Faraday
at
constant, T is the absolute tempera

ideal oxygen ion conductor is
con
ture, R is the gas constant, and where
Oxygen incorporated into

tion
sidered.
reduced
the solid
cathode/electrolyte interface and electrolyte according to the stoichiometric equa
the
io2(g)
where
2e-
O2electrolyte,
and
e
(1.2)
O
2_
denotes oxygen vacancies in the solid
denotes
occupied
oxygen lattice sites in the solid
electrolyte,
denotes electrons
equilibrium the rate of the forward and backward reac tion in Eq. (1.2) are equally fast. At the anode, oxygen ions are oxidized to form either oxygen molecules (backward reaction of Eq. (1.2)) or a different reaction product in the presence of a fuel gas, e.g. H20 in the presence of
from the electrode. In
hydrogen or C02 in the presence of CO. The cell potential generally decreases when the cell produces a current. The deviation of the cell potential from the Nernst potential depends on the cur rent and the internal resistance of the cell. This behaviour is typical for any
*)
Note that in
electrochemistry the
term
"potential"
is
usually
used to ascribe
"potential
difference".
1.1
Background
galvanic cells. The internal resistances are due to the ohmic resistance of the electrolyte and electronic conductors, as well as due to interfacial resistances (generally non-ohmic). The understanding of these interfacial resistances has been a driving force for
current-producing
electrochemical device, i.e. the science of electrochemical kinetics.
By contrast,
current-driven devices, such

are
as
oxygen pumps
or
oxygen separa
operated by imposing an external load. This can either be accomplished by applying a constant current (galvanostatic mode) or by applying a constant potential (potentiostatic mode) across the cell. In the first case, a potential difference develops across the cell which is proportional to the cell conductivity, whereas in the second case, the current through the cell is proportional to the cell resistance (inverse conductivity). Accordingly, low cell resistances are desired to keep internal losses low.
tion membranes, The third type of solid state electrochemical devices, oxygen ther
sensors, are
nei
producing a current nor are they driven by a current. Their purpose is to probe an oxygen partial pressure of interest (cf. Eq. (1.1)). One might there
fore believe that the internal resistance of
cern. an
oxygen
a
sensor
is of minor
con
change in the oxygen partial pressure must be fast, low electrode resistances are required. So far we have briefly summarized the operating principles of solid state electrochemical devices from a macroscopic point of view. We have seen that internal cell resistances influence the properties of these cells. In the follow ing we consider the interfacial processes in more detail. The reader is also
However, if the response of
Eemf
upon
referred to standard textbooks about electrochemical kinetics and electro

chemical methods
(see Chapters
8 and 9 of
[9]
as a
starting point,
as
well
as
Refs
[10-14]).
1.1.2
The
Origin
a
of Potential Differences
If two materials and YSZ

two
and
(5
are
brought
into contact, in
our case a
noble metal
(Fig. 1.1), the electrochemical potential of the electrons within these p." jig. Note that phases will generally not be the same, i.e. aA e
=
-
YSZ is not
pure oxygen ion conductor but that
small electronic
(or hole)
conductivity is always present [15]. As a consequence, elections from one phase will flow to the other phase, leaving a positively charged phase behind. Accordingly, a potential difference develops between these phases, the equilibrium potential difference, Eeq. It is a fundamental property of materi-
Introduction
als interfaces that their
equilibrium potential differences can not be measured

we can
(see e.g. [9], p. 845). However,

between
T|
=
measure
an
the
an
interface
.
apart from equilibrium and

n
potential difference interface at equilibrium,

and
The
quantity
is termed
overpotential
plays
fundament
electrochemistry. This situation is accomplished by measuring the potential difference between two identical electrode/electrolyte interfaces,
where
one
role in
interface is at rest and the other distorted
by
not
an
electrical current.
that
are no
As known from chemical kinetics,
equilibrium does
mean
flow of
electrons occurs, but that the forward and backward currents
equilibrium current is Obviously, i0 reflects the

thus
case
equal. This designated equilibrium exchange-current density i0.

kinetic
properties
one
of the considered interface and

to another. As in the
are
can
be rather different from the
type of interface
of
Eeq,
quantity i0
can
not be
directly
and
measured. However, there
different
possibilities
a
to determine
i0,
some
methods
(and
its
limitations)
will be discussed.
We
can
obtain
net current
density
i if the forward and backward currents,
if
and ib, become different in
magnitude
i
=
if-ib.
potential
(1-3)
It is easy to
see
that this
implies
=
that the interfacial
difference must
depart
Let
us
from
Eeq.
The difference between the actual interfacial

T| E
-
potential
and
Eeq is the overpotential
as
introduced above.
briefly consider a platinum oxygen electrode to understand the physi cal significance of overpotentials (Fig. 1.1). The half-cell reaction is written as
02-(P)|02,Pt(oc)
where the notations determined
(1.4)
in
by the
correspond to those given following reaction
Fig.
1.1. The
potential
is
^02
because the electrons
are
2e"^02",
(1.5)
only charge-carriers that can exist in both phases. Note that the activity of electrons e~ in the electrolyte is related with 02~(B) through the reaction O2" (B) O(B) + 2e~(B). Similarly, the activity of oxygen at the interface between Pt and YSZ, aQ, is determined by the oxy
the
=
gen
partial
pressure.
Accordingly,
the oxygen
partial
pressure pQ
deter-
1.1
Background
potential of the oxygen ions in the YSZ, ji 2_(B), and therefore the equilibrium potential. Note that in equilibrium all activities of the species involved in the overall reaction exhibit its equilibrium value.
mines the electrochemical As
soon as a
current flows
through
an
external circuit, oxygen is removed

current is
so
from the cathode side
(the direction of the
that oxygen ions

is
migrate
from the cathode side to the
anode). On the anode side hydrogen
consumed and water is
produced. Thus, the activities of oxygen aQ on both electrode sides change near the tpb (cf. Fig. 1.1). This change of a0 with respect to the equilibrium value, a0(Eec), *s me origin of n. If the supply of atomic oxygen on the cathode side was infinitely fast, the interface would remain at equilibrium even if a large net currents flows. However, there are
two fundamental barriers for this not to
occur:
(i)
Molecular oxygen from the gas

reaction
phase
must
pass with
number of
steps until
it arrives
as
atomic oxygen
near
the
tpb.
Because every
elementary
reaction
proceeds
finite rate,
the concentrations of the
species
involved in the reaction
Pt
e~
Pore
<
o2(g)
O(ad)
YSZ
02"(P)
O(p)
2e"
Fig.
a
1.1
Schematics of
half cell with Pt and
an
ionic conductor in contact.
denotes the Pt
phase
and B denotes the solid oxide ion conductor. Electrons may exist
in the Pt and the ion conductor. Gaseous oxygen is contained within the gas
phase.
Note
that
In
02(g)
may
undergo heterogeneous
chemical reactions with the Pt and YSZ surface.
addition, adsorbed atomic oxygen may be incorporated in the electrolyte. In equilib rium, all elementary reactions are equally fast. The triple phase boundary (tpb) is the
line where YSZ, Pt, and the gas
phase
are
in contact.
Introduction
mechanism will deviate from its The term concentration
equilibrium concentrations. overpotential, nc, is used to ascribe for
phenomena. Furthermore, it is clear from the above that nc may be further split into contributions from the elementary reactions, e.g. gas phase diffusion, adsorption, dissociation,
and surface diffusion.
these
(ii)
Once the atomic oxygen arrived at the

nated and
tpb
it must be electroan
incorporated into
the solid
electrolyte. Certainly,
an
activation energy is necessary to into the YSZ lattice. In
incorporate
oxygen ion
act
on
addition, electrostatic forces

overcome.
the
oxygen ion which must be
The term
charge-transfer
differ
(or activation) overpotential, nct,
is used to ascribe for these

an
phenomena.
ence
It is
readily
seen
that
applied potential
influences the rate of oxygen transfer, because the oxy

are
gen
species
negatively charged.
1.1.3
Oxygen
shows The
a
Reduction
Fig. 1.2 trolyte.

tivity
typical interface between a porous cathode and a solid porosity of the cathode is in the order of 45% and the mean
a
elec
pore
size is ~1 (im. The cathode material should exhibit

at
good
electronic conduc
conditions.
as
high temperatures
or
and it must be stable under

as
oxidizing
Therefore, noble metals, such
Pt, Au,
or
Ag,
and oxide materials, such
Sr-doped LaMn03
Eq. (1.2).
of them
LaCo03,
have been considered
(see e.g. [7,16-19]).
The overall reaction of the oxygen reduction at SOFC cathodes is This reaction is made up of
a
given by
occur on
face between the ary
elementary reactions, some the surface of the cathodes, others take place near the inter cathode and the electrolyte, i. e. at the triple-phase bound
Which processes in detail
occur
couple
of
(tpb) (cf. Fig. 1.2).
depends
on
the
type of
electrolyte material considered. We start our considera tions at the tpb and work along the cathode surface. Three main types of het erogeneous elementary reactions can be distinguished (Fig. 1.3):
(i)
cathode material and
Charge
transfer of electrons from the metal to adsorbed
atomic oxygen
species
near
and the
gen ions into YSZ
subsequent incorporation of oxy tpb. This reaction is certainly con-
1.1
Background
fined to the
vicinity
of the
tpb [17, 20, 21].
An almost linear
dependence of the electrode resistance with the length of the tpb is generally found [22, 23]. In contrast, there is no experi
mental evidence about the actual mechanism of electron
are
transfer. Two one-electron transfer steps to atomic oxygen

more
probable
than
addition, there is also
single two-electron transfer step. In relatively little known about the actual
species.
either of two processes:
charge
of any adsorbed oxygen
The atomic oxygen is
supplied by
of
atomic
adsorption
or
and
subsequent
dissociation of oxygen molecules
surface
diffusion
oxygen.
Note
that
the
are
charge-transfer
process and the
supply
of atomic oxygen
series processes. Therefore the slower of the processes will
control the electrode behaviour.
Fig.
was
1.2
Interface between cathode and solid of porous
electrolyte surface.Secondary
cathode
on
Electron
Micrograph (SEM)
gen
La0 8sSr015Mn03
and
YSZ
polycrystal.
The cathode
in air.
subsequent sintering applied by screen-printing molecules may diffuse through the porous network
i.e. are
at 1373 K
(1100C)
Oxy
towards the
triple phase
and the gas
boundary (tpb), phase
the location where the cathode, the solid
electrolyte,
in contact.
Introduction
(ii)
Adsorption of oxygen on the cathode surface. This may either occur dissociatively (such as on Pt [24]), or associatively (such as on Au [25] or Sr-doped LaMn03 [16]). However, it is of fundamental difference whether the bonding of the oxygen molecule is broken upon adsorption or not and the overall behaviour of the electrode is expected to be different. Obvi ously, the adsorption/dissociation process occurs on the entire cathode surface. It can be taken as a general rule that, at least for Pt and Sr-doped LaMn03 cathodes, the supply rate of adsorption/dissociation is too low to account for the rela tively high current-densities measured. A further process must therefore be responsible for the supply of atomic oxy
gen.
Fig. 1.3 Schematic diagram of predominant reaction steps at electrode/electrolyte interface.(1) 02(g) is supplied by gas phase diffusion through the pores of the cath
ode.
(2)
The oxygen molecules may adsorb

can
on
the entire cathode surface.

can
(3)
the
tion process
be
accompanied by
(5)
an
electron transfer and it
be followed
are
adsorp by an
is
immediate dissociation of the molecule.
(4)
Atomic oxygen
species
considered to
diffuse
along
the cathode surface.
The final
charge
transfer and
incorporation step
are
believed to take
YSZ and
place
at the
tpb,
where
Oq
denotes
occupied
on
oxygen lattice sites in

not
denotes oxygen vacancies. Similar processes
the YSZ surface
believed to be of
comparable
relevance.
10
1.2
Aim
of the
Thesis
(iii) Diffusion of atomic oxygen

ess
on
the cathode surface. This proc
generally deliver atomic oxygen towards the tpb with a high transport rate. Because the adsorption/dissociation reaction and surface diffusion occur in parallel on the cathode surface, the faster process will control the electrode behav iour*. At temperatures above ~500C this is usually the sur
may
face diffusion process
(see e.g. [26-29]).
Obviously,
gen
further processes may be the gas
important,
such
as
the diffusion of oxy
phase, or the interaction of oxygen with the YSZ surface. However, it is generally accepted that these types of interactions can be neglected under most operating conditions. Although there is general agreement about the reaction pathway of oxygen at interfaces between electronically conducting cathodes and YSZ, there is still through
little known about the reaction mechanisms. Even less is known about the
kinetic constants of the
elementary
reactions involved in the overall kinetics.
There
are
are
two main reason
for this. First,
interpret and the mean large. Furthermore, rarely an operating condition of the cell is found where the mechanism is dominated by a single step. Second, the reaction mecha nisms are relatively complicated and, therefore, they are difficult to treat mathematically in analytical form. However, it is not always necessary to run through all the mathematics, and a combination of both analytical analysis and numerical simulation may help to solve a particular problem.
difficult to
experimental electrochemical results variation of the results is generally
1.2
Aim of the Thesis provide

general
method for the identification of
The aim of this thesis is to
heterogeneous
cation
on
reaction mechanisms at solid state oxygen electrodes. Identifi
the
on
one
hand includes the discrimination of the relevant reaction
steps, and
the other hand the
quantitative
estimation of
(electro-)
kinetic
parameters.
*)
It is worth to think about this statement and the
corresponding
statement in
(i).
11
Introduction
The
following sub-goals will be

(i)
followed:
development of a general framework for modelling, struc tural investigation, and implementation of reaction mecha
nisms;
(ii)
exemplary validation Pt, 02(g) I YSZ system;

of
of the
proposed
method
with
the
(iii) discrimination
the
relevant
on
reaction
steps
of
La0 85Sr015Mny03
tial; proposal
cathodes
YSZ
near
equilibrium poten
of reaction mechanism;
(iv)
assessment of the
Matlab/ Simulink programming environ
ment for the numerical treatment of models of reaction mech
anisms.
1.3
Structure of the Thesis

by
a
The main part of the thesis is enclosed outlook
an
introductory chapter
our
and the conclu
chapter.
we
In the outlook
some
we
give
concise summary of
sions and
give
ideas for further studies in the field of
ture electrode reaction kinetics. The main
part
consists of three
or
high tempera chapters, each

similar form.
of them intended for
publication
in the
present form
with
an
in
They
an
are
organized
an
in the usual way,
starting
abstiact, followed by
experimental section, a results section, a discussion sec tion, and the corresponding list of references. Nevertheless, redundancy an repetition are kept to a minimum. Following, a brief summary of the contents of the three main chapters:
introduction,
Chapter 2.
tion" and
The
general
framework for
modelling
and structural identifica
tion of reaction mechanisms is
developed.
are
The terms "structural identifica
"state-space modelling"
a
explained.
of
a
The theoretical concepts
are
exemplified by
thorough
treatment
kinetic model
describing
the
Pt, 02(g) I YSZ system.
12
1.3
Structure
of the
Thesis
Chapter 3.
tions for the
The system
explored
in
Chapter 2
are
is
implemented
in the
in Matlab
and Simulink.
Step-by-step
instructions
given
appendix.
are
Simula fre
steady-state current-voltage
behaviour
are
behaviour and the
small-signal
quency
dependent
to
obtained. The results
discussed with for the
respect
reported experimental
and simulated data. A

in the model is
procedure
identification of unknown
parameters
proposed.
Chapter 4.
YSZ
The interface between porous
La0.8sSr015Mny03
a
cathodes and
tech
single crystal
and
surfaces is
investigated by
number of
microscopic
is
niques
by electrochemical impedance spectroscopy.

between YSZ and
The formation of the
foreign phase La2Zr207

on
La0 85Sr015Mny03
investigated
at the inter
the sub-micron to nanometer scale. The influence of
La2Zr207
face upon the electrochemical
properties
is clarified. The relevant reaction

are
steps
in the overall process of oxygen reduction
discriminated.
References
[1]
B. C. E. Steele.
Oxygen
ion conductors. In T.
Takahashi, editor, High Conductivity

1989. World Scientific.
Solid Ionic Conductors, pages 402-446,
Singapore,
[2]
M. Godickemeier. Mixed Ionic Electronic Conductors for Solid Oxide Fuel Cells. PhD
thesis No. 11348, ETH Zurich,
Department of Materials, Switzerland,

Properties of Stabilized
of Twente, Holland, 1991.
1996.
[3]
I. C. Vinke. Electrochemical and Electrode
Bismuth Oxide Ceram
ics. PhD thesis, Technical
University
[4]
Matsuda, and Y. Takita. Doped PrMn03 perovskite oxide temperature operation. /. Electrochem. Soc, 142:1519-1524,1995.
as a new
T. Ishihara, T. Kudo, H.
cathode of solid oxide fuel cells for low
[5]
B. C. E. Steele, editor. Ceramic
Oxygen
Ion conductors, British Ceramic
Proceedings,
London, 1996. The Institute of Materials, The Institute of Materials.
[6]
H. U.
Anderson,
A. C.
on
national.
trochemical
Symposium Society.
Khandkar, and M. Liu, editors. Proceedings of the First Inter Ceramic Membranes, Pennington, NJ, 1997. 95-24, The Elec
[7] [8]
N.
Q. Minh. Ceramic fuel cells. /. Am. Ceram. Soc, 76:563-588,1993.
N. G. Minh and T. Takahashi. Science and
Technology of Ceramic
Fuel Cells. Elsevier
Science B. V.,
Amsterdam, The Netherlands, 1995.
13
Introduction
[9]
J. O. Bockris and A. K. N. Reddy. Modern Electrochemistry, volume London, 1970.

K.
2. Plenum Press,
[10] [11]
J. Vetter. Electrochemical Kinetics. Academic Press, New York, 1967. J. Bard and
L. R. Faulkner. Electrochemical Methods: Fundamentals and &
A.
Applica
2 edi
tions.
John Wiley
Sons, New York, 1980.
[12]
J. S. Newman. Electrochemical Systems. Prentice Hall, Englewood Cliffs, NJ,

tion, 1991.
[13]
C. Gabrielli. Identification of electrochemical processes
by frequency
response
1984.
analysis.
[14]
1987.
Technical
Report 004/83,
Solartron Instruments,
Farnborough,
J. R. Macdonald, editor. Impedance Spectroscopy. J. Wiley-lnterscience,
New
York,
[15]
J.-H. Park and
R. N. Blumenthal. Electronic
transport in 8 mole percent Y203-Zr02.
/. Electrochem. Soc, 136:2867-2876,1989. [16]

Y. Takeda, R. Kanno, M. Noda, Y. Tomida, and O. Yamamoto. Cathodic tion
polariza
/. Electro
phenomena
of
perovskite
oxide electrodes with stabilized zirconia.
chem. Soc, 134:2656-2661,1987.
[17]
M. Kleitz, T.
Kloidt, and L. Dessemond. Conventional oxygen electrode reaction:
Facts and models. In
moxed ConductorsProc
de, Denmark, 1993.
High Temperature Electrochemical Behaviour of Fast Ion and Miof the 14th Ris0 Int. Symp. on Mat. Set, pages 89-116, RoskilRiso National Laboratory.
on
[18]
S. C.
Fuel
Singhal, editor. Proceedings of the First International Symposium Cells, Pennington, NJ, 1989. The Electrochemical Society, Inc.
Solid Oxide
[19]
F.
ond International
Grosz, P. Zegers, S. C. Singhal, and O. Yamamoto, editors. Proceedings of the Sec Symposium on Solid Oxide Fuel Cells; Held from 2 to 5 July in Athens,
Greece, Luxembourg, 1991. Commission of the European Communities.
[20]
J. Mizusaki,
K. Amano, S.
tion of zirconia oxygen gas
Yamauchi, and K. Fueki. Response and electrode reac sensor. In T. Seiyama, K. Fueki, J. Shiokawa, and
S. Suzuki, editors, Chemical Sensors, volume 17 of Analytical Chemistry
Symposia Se
ries, pages 279-284, Amsterdam, 1983. Elsevier.
[21]
F. H.
van
Heuveln, H. J. M. Bouwmeester, and F. P. F.
van
Berkel. Electrode prop
erties of Sr-doped
ary
area.
LaMn03 on yttria stabilized zirconia. Part I: Three-phase bound /. Electrochem. Soc, 1997. to be published.
[22]
J. Mizusaki, K. Amano, S. Yamauchi, and K. Fueki. Electrode reaction and re Soc. Jpn, 6:1160-1166, sponse characteristics of zirconia oxygen gas sensors. /. Chem.
1985.
[23]
Fukunaga, M. Ihara, K. Sakai, and K. Yamada. The relationship between overpotential and the three phase boundary length. Solid State Ionics, 86-88:1179-1185,
H. 1996.
14
References
[24]
J.
L.
Gland, B.
face.
Surf.
Sexton, and G. B. Fisher. Oxygen interactions with the Pt(l 11) Sci., 95:587-602,1980.
A.
sur
[25]
B. Hammer and
J.
K. Norskov.
Why gold
is the noblest of all the metals. Nature,
376:238-240,1995.
[26]
J. Sasaki, H. Mizusaki, S. Yamauchi, and

of stabilized zirconia cells
K. Fueki. Studies
by
the
complex impedance
A.
on electrode processes method. Solid State Ionics,
3/4:531-535,1981.
[27]
M.
J. Verkerk, M.
W.
J. Hammink, and
J. Burggraaf. Oxygen transfer
on
substi
re
tuted
sistance
Zr02, Bi203, and Ce02 electrolytes with platinum electrodes. by D-C polarization. /. Electrochem. Soc, 130:70-77,1983.
K. Amano,
I. electrode
[28]
J. Mizusaki,
Pt,
S.
Yamauchi,
and
K. Fueki.
Electrode
reaction
at
Oz(g)/stabilized
zirconia interfaces. Part I: theoretical consideration of reaction
model. Solid State Ionics, 22:313-322,1987.
[29]
J. Mizusaki, H. Tagawa,
K.
Tsuneyoshi,
and A. Sawata. Reaction kinetics and
microstructure of the solid oxide fuel cells air electrode
Lao6Ca04Mn03/YSZ.
/. Electrochem. Soc, 138:1867-1873,1991.
15
Introduction
16
Part
II
Theoretical
Analysis
I YSZ
of
the Pt,
02(g)
System
18
Chapter
General Framework,
Modelling,
and
Structural
Investigation
Abstract
study aims to provide a general framework for modelling and structurally investigating complex heterogeneous electrode reaction mechanisms. The necessary theory is derived from classi cal systems and control theory. Relationships between abstract expressions and measurable electrochemical quantities are estab lished. The procedure is illustrated by means of the oxygen reduc tion the interface between at platinum electrodes and yttria-stabilized zirconia solid electrolytes. Dissociative adsorp
This
tion of oxygen
on
the
a
platinum surface,
surface diffusion of
near
atomic oxygen, and
two-electron transfer step
the
triple
phase boundary are considered. The first model includes the adsorption/desorption step and the electron transfer step,
whereas the second model also The finite-difference
incorporates
surface diffusion.
mass
approach
is used for
modelling
trans
are
port. The surface

considered
as
concentrations of adsorbed atomic oxygen
the time
dependent
state-variables within each ele-
*)
Submitted to
/. Electrochem. Soc.
General Framework, Modelling,
and
Structural Investigation
ment. The mass-balance
equations
are
obtained for the state-vari
ables. The reaction mechanisms

form and structural
is
are
formulated in state space
investigation
of the
resulting
is well
set of
equations
con some
performed
on
the
corresponding
transfer functions. The
cept of structural identifiability, which

domains of mathematical
sions
accepted
in
the
describing the frequency response

are
modelling, is demonstrated. Expres steady-state current-voltage behaviour and

behaviour
are
derived. It is shown that
globally structurally identifiable under the given assumptions. It is emphasized that modelling and testing model structures for identifiability must be accomplished prior to exper imental work. In combination with Part II of this publication, a complete tool for the identification of heterogeneous reaction mechanisms is provided.
Keywords.
Electrochemical kinetics, state space
both models
modelling;
structural
investigation;
elec
trochemical
impedance;
oxygen reduction; solid oxide fuel cell.
2.1
Introduction
play
an
Metal electrodes devices such

as
important
role in
high temperature
or
electrochemical
Ni in anodes of
a
Pt in oxygen
sensors or
oxygen pumps,
solid oxide fuel cells. The reduction of electrode resistances has been
major
driving force for the investigation of these interfaces during the past 25 years. The design of electrodes with desired properties necessitates knowledge about the micro-kinetics of the overall electrode process. Although this field has been extensively examined and general agreement exists on the reaction pathway of oxygen at noble metal electrodes, there remains little knowledge and uncertainty about the relevant elementary processes and their kinetic
parameters [2,3]. But,
makes
tions
a
it is this information about the micro-kinetics that
prediction
of electrode
properties
under different
operating
condi
possible. The reason for this situation is probably due to the interdisci plinary of high temperature electrochemistry, where a number of problems must be solved in depth individually, in order to be able to identify a particu lar reaction mechanism. First, models taking into account the relevant elec trode processes are mathematically difficult. Second, the characterization of high temperature electrodes with electrochemical methods needs experience
20
2.1
Introduction
special equipment. Finally, sample preparation and characterization requires knowledge about ceramic materials and its processing. However, modelling is often considered as the most difficult step and is, therefore, put at the end of an investigation. It is one aim of this study to make clear that modelling, structural investigation of the associated set of equations, and digital simulation should be accomplished prior to any experimental work. A large number of authors have studied the behaviour of the Pt, 02(g) I solid
and
electrolyte system. Generally, analyses include an experimental investigation combined with a certain extent of modelling. The methods of modelling have been strongly related to the experimental methods employed for studying this electrode system and can be grouped into (i) steady-state current-voltage investigations [4-12] and (ii) electrochemical impedance spectroscopy (EIS) investigations [11,13-18]. In addition, there are reports of transient-signal (small and large) analyses [19-22]. In all cases, the starting points of a model formulation are the mass and charge balances describing the dynamic prop erties of a proposed reaction mechanism. These equations are obtained from ordinary chemical kinetics considerations. Steady-state models relate a con stant overpotential as the input quantity to a constant current as the output quantity (potentiostatic mode). The equations then may be independent of time and therefore facilitating the mathematical treatment of the equations.
As
soon as
the reaction mechanism is assumed to consist of
more
than
sin
gle reaction step, it becomes difficult to find analytical solutions to the emerg ing system of equations. To circumvent these difficulties, simplifying assumptions are introduced. The most popular, introduced by Bockris and Reddy [23], assumes quasi-equilibrium for all steps except the rate determin ing one. With this method, Butler-Volmer type relations are obtained relating the current J to the overpotential n
I
ir
'Ct,,F
ocF
'o
[exp^-nj-exp^-n]
current
(2.1)
the apparent
where
i0
is the
exchange
[23],
from
density,
cca and ac
are
transfer coefficients
A is the active electrode area, and the
charge remaining
can
symbols
have their usual

a
meaning.
Tafel
If A is known,
i0,
ac, and aa
be
uniquely estimated
sible to include
most
plane plot (log(J)

in the
versus
n).
It is further pos
mass
transport processes
models, although only the
boundary conditions can be treated [7, 8,9,24, 25]. In addition, the steady-state method offers the possibility of predicting the qualitative dependence of the exchange current density, iQ, or the limiting
simple
situations and
21
and
partial pressure, tempera ture, or overpotential [8,10,14,15,25]. However, steady-state methods do not provide any information about the dynamic behaviour of electrode sys tems, and rarely give unique access to the kinetic constants of the elementary
current,
ij,
on
external parameters, such
as
oxygen
processes involved in the overall electrode reaction. For this purpose,
dynamic
methods
are
methods is limited to
i.e. where
one
indispensable. Furthermore, the use of steady-state investigation of relatively simple reaction mechanism,
step dominates the overall electrode behaviour.
reaction mechanisms at gas electrode of solids
a
reaction
Unfortunately, heterogeneous
state ionics devices involve
number of
dominating
Tafel
the overall characteristics.

an
elementary steps, neither of them Although the current-voltage charac

estimates of the
teristics may exhibit
apparent Tafel behaviour, numerical

contain
parameters (P, and iQ) may

to
large
errors.
Interpreting
these data
might lead
wrong conclusions (see also
[1,12,26,27]).
impedance spectroscopy (EIS) lies in the fact that it is a small-signal perturbation method which reveals both the relaxa tion times and the relaxation amplitudes of a system over a wide range of fre quencies [28]. EIS gives information about the static and dynamic properties of a system. However, the complexity in obtaining expressions describing the frequency response increases. This has led many researchers to interpret experimental data only in terms of circuits of electrical elements [cf. e.g. 16, 17,29]. Recently, a method developed by Gabrielli and coworkers [30] for dealing with aqueous electrochemical systems, was applied by van Hassel et
The power of electrochemical
al. to describe the Au,
anism
02(g)
I YSZ
system with
second-order reaction mech

used to model
on a
[12,31].
This
approach
has been
increasingly
compli
cated reaction mechanisms
[32, 33].
The method is based
Tailor series
expansion of the charge balance equation, from which the current modula tion and finally an expression for the impedance is obtained [30]. Recently, Gabrielli and coworkers provided a general framework for dealing with elec trochemical reaction kinetics of heterogeneous aqueous systems [34-36]. The method allows for the treatment of multi-step reaction mechanisms. But the multi-step
mass
treatment of the electrode reaction must be
abandoned,
as soon as
transport processes become relevant (see e.g. [12] and references therein). Furthermore, the fact that both type of processes (mass transport
heterogeneous reactions) occur in parallel on the electrode surface, dras tically increases the complexity to solve the equation system. It is, therefore, often assumed that only mass transport being relevant within a characteristic length (often over the Nernst diffusion layer length 5, or a multiple of 8; see
and
22
2.1
Introduction
quasi-equilibrium approach is employed for the treatment of the boundary concentrations at distances larger than 8. However, these simplifications may give different solutions for the frequency-dependent
e.g.
[12,16,25]).
behaviour,
as
well
as
for the
limiting
an
behaviour
(see e.g. [37] p. 73, for the

which
occurs
problem
of surface diffusion of
atomic
species
in
parallel
with dissociative
adsorption). We propose to employ numerical simulation techniques in combination with an analytical treatment to overcome the mentioned problems. The general
system behaviour
tions
our
is obtained from
analytical expressions. Approximate solu space"

has not been used in the electro
can
be obtained from simulations of state space models. To the best of

the notion "state
knowledge,
chemical literature. We
In Part I of this
give a brief description in appendix 2-A.l. paper we provide a general framework for modelling electro
and
chemical reaction mechanisms in state space form, which makes structural
investigation, simulation,
tion
state
parameter estimation of heterogeneous reac mechanism possible. First, some general theoretical background about
space
modelling
a
is
given,
and the link between the theoretical concepts

is
and electrochemical cedure
quantities
accomplished. Second, we illustrate the pro

(YSZ).
the
using
fairly
well known reaction mechanism that describes the oxy
gen reduction at interfaces between Pt and Yttria-Stabilized Zirconia

We
particularly investigate steady-state and the small-signal

consider dissociative
the
influence
of
surface
diffusion
on
electrode behaviour. In the first model
(Ml)
we
adsorption
of oxygen molecules and reduction of

area.
adsorbed atomic oxygen within the active electrode
In
second model
(M2), surface diffusion of atomic oxygen

Part II ious
we
on
the Pt surface is included. In
report the computer implementation of the equations, we give var simulation results, and we discuss the results with respect to some of the
experimental results from literature [1]. We have found that it is extremely helpful for a better understanding of a particular reaction mechanism, if time
and
frequency dependent
behaviour
be mentioned that the method
by simulation. It should of state space modelling is widely used in con

can
be studied
theory as well as in chemical engineering (see e.g. [38] or [39]). Nevertheless, we briefly present the necessary theoretical tools and we focus on the peculiarities of electrochemical modelling.
trol and systems
23
and
2.2
2.2.1
General Framework
The Process of
a
Modelling
basically determined by the purposes for which the micro-kinetic model is required. In kinetics three cate gories are generally distinguished for structure identification, parameter esti mation, and prediction purposes. Although there is general agreement about the reaction pathways at high temperature SOFC electrodes [2,3,40], we still have very little a priori knowledge of the actual electrode mechanism. Our interest has to be primarily focused on the identification of the overall proc ess structure; therefore we first need a of the over qualitative understanding all process and the corresponding elementary processes. Experimental results obtained from various electrochemical techniques provide such information. In addition, information is obtained from other physico-chemical investiga tions, in particular from surface science. From those, we develop a qualitative
picture
of the overall electrode reaction that considers the essential elemen
as
The form and detail of
mathematical model is
tary processes
ideas into
of
a
well
as
their interactions. Last,
we
translate the
qualitative
quantitative description of the model. Here three different types equations emerge: mass balance equations, physical relations, and equa
is obtained
describing the geometry. The final mathematical realization by casting the equations into a form suitable for further analysis
tions mentation in
a
and
imple
computer.
in the structure of the model and its
Often, uncertainties remain

Then simulation is
parameters.
only possible by assuming input/output data must be made. Exper iments must be designed in which the system is perturbed, thus providing input/output data. In some cases static analyses, such as current-voltage measurements, may be adequate. More often the dynamic response of the system is required that can be obtained from EIS measurements. The relation between the input /output data of the physical system are then compared with the corresponding input/output data from the model and the structure and/or parameters of the model are adjusted until a certain optimization cri
values for the parameters and the identification of the model from
teria is fulfilled.
At all levels within the
modelling
process, model validation should be

no
applied. Obviously
the model should contain
contradictions and the sim

to
ulation should be verified. In addition, simulations should

available data and the model should be
correspond consistent with accepted theories.
24
2.2
General Framework
2.2.2
General Considerations and
Hypotheses
general agreement
Electrode microstructure.
exists
on
For noble metal electrode
adsorption of oxygen molecules and surface diffu sion towards the triple-phase boundary (tpb) (cf. Fig. 2.1) [7,8,12]. The direct reaction of molecular oxygen from the gas phase with the electrolyte surface
the dissociative
(at least with YSZ)

trodes is
or
the solid state
tiansport of oxygen ions
in Pt
or
Au elec
generally ruled out [3, 41, 42]. For modelling purposes quantitative data for the tpb length l^ are needed. These values can vary over more than two orders of magnitude (0.1-10 urn/urn2), depending on the preparation procedure as well as on the operating conditions of the electrode. Although
estimates for
/^b
and the
mean
pore diameter
can
be obtained from micro
scopic data, modelling is complicated by the morphology of the porous elec trode and therefore simplified electrode geometries are employed (see
Fig.
2.1
Schematic view of the oxygen reduction process at interfaces between noble
ion-conducting electrolytes.The case of platinum is taken as an example. The oxygen molecules adsorb dissociatively (1) on the metal surface. Adsorbed atomic oxygen diffuses (2) towards the triple phase boundary (tpb). The electronation reaction (3) near the tpb may be considered as a single-step or a multi-step
metals and solid oxide
reaction. The concentrations of oxygen vacancies
e
,
as
well
as
the oxygen
partial
pressure pQ
V0, oxygen ions 00, facing the noble metal are
and elections considered to
be constant
over a
wide range of
operating
conditions.
25
and
appendix 2-A.l). Fig. 2.2 shows a SEM of a Pt electrode on a YSZ single crys tal surface. It is readily seen that a description of the microstructure can be accomplished with a few simple quantities (see appendix 2-A.2). However,
an
uncertainty
remains and
large
errors
may be introduced into
model
description. Moreover,
how
there is still little information about the
question
of
spatial extension of the tpb is. It is easy to demonstrate that there must be a spatial extension of the electrochemical active area around the tpb to accommodate the high current densities experimentally found (see
large
the
e.g. [2,40,
43]).
We will
give
more
account
on
this
question
below.
Adsorption.
tation, oxygen
The
adsorption
of oxygen is the first process
taking place
on
the noble metal surface.
Depending on adsorption is generally
the noble metal and its surface orien

an
activated process which
proceeds
through
mentary
The ele sequence of precursor states (see e.g. for Pt(lll): [44, 45]). steps of the oxygen adsorption and desorption are rather well dis-
Fig.
2.2
Secondary
with Pt
Electron
Micrograph (SEM)
was
of porous Pt
with Pt
on a
(001)
YSZ
single
crys
tal surface.The YSZ surface
dc-sputtered
area
during
10 min,
additionally
Esti
painted
mates
paste,
and
subsequently
tpb
fired in air at 1223 K and the
(950C)
area
for 4 h. The SEM
shows the
boundary
length
between the
sputtered
painted
(lower right).
of the
of the
and the pore sizes may be obtained from
quantitative
image analysis.
26
2.2
General Framework
criminated for
Pt(lll) surfaces [4447]. However,
care
is necessary when
employing
these data in simulations because
they
were
almost
exclusively
obtained from
single crystal
studies under low
partial
pressures and at rela
tively low temperatures. Real noble metal electrodes are polycrystalline and are operated at high temperatures under ambient pressures. Furthermore, it is well accepted that low amounts of impurities may drastically influence the
adsorption
behaviour of oxygen
on
metals
[48].
We should also be
aware
of
experimental data show some scatter and some param eters, such as most frequency factors, are even not known. Nevertheless, information about the adsorption and desorption of oxygen on noble metal surfaces constitutes basically the only a priori knowledge we have for model
the fact that available
ling
the oxygen
exchange reaction at noble metal/YSZ

are
interfaces.
types of diffusion which may be relevant when modelling high temperature oxygen electrodes. First, binary gas phase diffusion of the oxygen through the pore network of the cathode. Second,
Diffusion.
There
two different
surface diffusion of adsorbed oxygen intermediates. The first type of diffu

sion
can
generally
be ruled out in these systems at
high
to moderate oxygen
atm) because of the very high diffusivities partial pressures (pQ > 10 through the large pores even at high temperatures [14]. For modelling pur poses, the partial pressure of oxygen is therefore assumed to be uniform over space and time. However, at oxygen partial pressures below ~10-3 atm, gas phase diffusion may become apparent at porous SOFC cathodes at high tem
peratures [49].
In contiast, diffusion of adsorbed oxygen intermediates due to
a
gradient
of
potential along the metal surface can generally not be consid ered to be either infinitely fast or absent. It is important to recognize that these limiting cases result in completely different dynamic behaviour of the
the chemical
electrodes. In the first case, concentration

can
gradients are absent and

where different
the system
be modelled
using
one
single compartment
species
are
distributed
homogeneously.
The concentration of adsorbed
species
of the
would
remain constant with time and would further be
independent
applied
overpotential (i.e. the resulting current). Therefore, the overall electrode reac tion would be entirely charge-transfer controlled. In the second case, diffu
sive transfer of adsorbed oxygen
over
the electrode surface is absent and
therefore
only
the reaction
zone
must be considered
[12]. The rate-controlling
mechanisms may either be the

ess,
or a
adsorption
process, the
charge
to
transfer proc
combination of both. Both
types of problems lead
systems of ordi-
27
and
nary
first-order
differential
equations,
the
state
equations,
which
are
generally non-linear.
Electrochemical reactions. The rates of electron transfer processes
are
indi
rectly influenced by a change of the electrode stoichiometry or by a change of the electrochemical potential of the reacting species, whereas the rates are directly influenced by a change of the work function of the electrode mate rial. It is usually assumed that the rate constants of the election transfer reac tions depend exponentially on the applied potential [23,30,50].
2.2.3
Modelling Reaction Mechanisms

We consider the noble metal,
State space model. electrode form

as an
021
YSZ
can
high temperature
open time-invariant
system [38]
which
be described in the
(see also appendix 2-A.l)
x(t,p)
f[x(t,p),u(t),t;p]
(2.2)
subject
to the initial conditions
x(0,p)
In
x0(p).
state variables of the
e
(2.3)
model,
Eq. (2.2)
or
the vector x(t)
represents the
usually
variable
the concentrations of adsorbed
species; u(t)
the
is
some
external
input
that
can
be varied
or
during
experiment,
e.g. the
potential
difference the temperature
the pressure; p is the vector of the unknown the model consists of the observation
parameters.
In addition to the differential
Eqs. (2.2),
functions
y(t,p)
where
g[x(t,p);p],
is referred to
(2.4)
as
y(t)
Rp denotes the observed quantities and

or
the that
model output the
response function
are a
(most often the current). We

and that
assume
parameters
priori independent
or
and g
are
(generally
non-linear) real analytic functions for all possible

It is
sets of
parameters.
analytical solutions of this set of differential equations, that would describe the large-signal dynamic behaviour. Although non-linear studies are more general and yield more information, small signal methods are more often employed for they rely on a generally
difficult
impossible
to obtain
28
2.2
General Framework
linearisation of the model around
some
steady-state operating point
that is
associated with constant external variables. This mathematical treatment much easier.
Linearized state space model.
Linearisation of
procedures
makes further
Eqs. (2.2)
and
(2.4) yields (2.5) (2.6)
5x(t, p)
A(p)bx(t, p) C(p)Sx(t, p)
system
B(p)5u(t) D(p)bu(t) describing

the
Sy(t, p)
where A, B, C, and D,
ties
are
the
are
matrices
system proper
entirely.
The matrices
given as
R
nxn
A-*/
A"
dx
(2.7)
_d/
=
du
nxm
(2.8)
dx
pxn
(2.9)
du
pxn
(2.10)
particular operating point. The intrinsic dynamic behaviour of a system is given by the eigenvalues of matrix A. For intrinsi cally linear systems, 5x and 8w are replaced by x and u. However, in elec trochemistry we are dealing with intrinsically non-linear systems due to the exponential dependence of the electrochemical rate constants on the overpo tential [23]. In the following we will write x and u instead of dx and Sw, keep ing in mind that we only mean small deviations around an operating point.
(*) denotes
a
where the star
Transfer function ized state space
description. An equivalent representation of the linear description can be obtained by Laplacian transforms of
with
Eqs. (2.5)
and
(2.6)
x0
0:
Y(s,p)
where
G(s,p)U(s)
(2.11)
29
and
G(s,p)
LZ(s) and Y(s,p)
nal y;
This
are
C(sI-A)_1B
D.
(2.12)
the
Laplace
transforms of the
G(s,p)
is the transfer function and I
description
is
is either called "transfer
input u and the output sig is the appropriate identity matrix. function description" or "Laplace
description". G(s,p) generally a three-dimensional matrix in case of a multi-input multi-output (MIMO) system. In case of single-input multi-output systems
(SIMO), G(s,p)
reduces to
a
transform
two-dimensional matrix, and in
case
of
sin
gle-input single-output (SISO) systems system, G(s,p) results in a fraction. In this case, G(s, p) can be easily obtained by means of Eq. (2.12) or by Laplace transforming, in the linear (or linearized) case, the input and output
Y(c n\
=
bts
Jfc
G(s,p)
^^=
U(S)
k
n
+bk
+ans
Jfc-2
,s x +
...
b-,s
-
bn
k~l
(k<n)
(2.13)
+...
+bls
a0
are
where
is the
Laplace
variable and
b{(p) and a{(p)
constant coefficients
of the transfer function.
systems and control

similar
Eqs. (2.12) and (2.13) are fundamental results from theory (see e.g. [38]). Gabrielli and Tribollet first used a
description
as
presented
above for the treatment of aqueous electro
chemical systems
The state space
[35].
is the most reliable linear
representation
use
time-independent
(LTI)
model to
for computer
analysis.
Stable computer
the eigenvalues, frequency response, time response, and other (A, B, C, D) quadruple are known [51]. Transfer function models are numeri cally more difficult to handle, and tend to be inherently ill-conditioned. Nev ertheless, this representation is often used for testing the identifiability of
algorithms properties of
for
low-order LTI systems
(see e.g. [52,53] and references therein).
2.2.4
Identifying G(s)
with Electrochemical
Classical
Quantities
deals electrochemistry with electrochemical systems as SISO systems. Specifically, in potentiostatic mode Ip(t,p) u(t), where ZF is the Faradaic current y(t,p) and r\(t) and the overpotential r\ E- E is defined as the deviation of the potential E from the equilibrium potential E We would like to point out that this approach is by no means limited to the treatment of SISO systems, but that it
Faradaic admittance and
impedance.
=
30
2.2
General Framework
is
applicable
to the treatment of SIMO
systems
as
in much the
same
way
(cf. [36,54]).
The linearized state space
description is
=
obtained
x(t)
Ax(0 Cx(t)
Bn(f)
(2.14) (2.15)
IF(f)
where D has become
a
Dr\(t)
In accordance with
scalar
quantity.
Eq. (2.11)
and
(2.12)
we
further obtain
h(s,p) YF(s)
which is
we
=
Y(s,p)T\(s)
+
(2.16) (2.17)
C(sI-A)_1B
obviously
the Faradaic admittance transfer function.
Accordingly,
find for the Faradaic
impedance
transfer function
ZF(s,
Frequency
^.
[30]
(2.18)
response.
imposes
impedance spectroscopy harmonically oscillating overpotential with frequency

at
Electrochemical
(EIS)
a)
and
amplitude fj
the
input
of the system
r|(0
It
can
f\cos((ot).
[38] that the output signal
(2.19)
in time
be shown for stable LTI systems
domain is
given by
y(t)
=
ycos(cof
(p)
(2.20)
where
|
The
|YF(;co)|
andcp
Zy-Zn
arg{YF(/co)}.
(2.21)
complex function YF(jco) is known as the frequency response, |YF(jco)| as the magnitude and arg{YF(jco)} as the phase of YF(jco), i.e. we have a relationship between the measurable frequency response and the model in a
state
space
use
or
transfer function
ral to
the admittance data
description. Note that it would be more natu than the impedance data because EIS is nor-
31
and
mally carried out by imposing an alternating voltage across the interface, thereby measuring the admittance rather than the impedance. We must also keep in mind that the method relies on the linearisation of the equation system and on small-signal excitation. If the non-linear physical system is excited with large input signals, the output might contain frequen cies other than the input frequency and the output magnitude might be dependent on the input magnitude. This can easily be checked with EIS by exciting a sample with increasing input amplitudes. The validity of linearity prevails as long as |YF(jo))| and arg{YF(jco)} do not depend on the input amplitude. Additionally, the system matrices should not be used to calculate any large-signal response since the non-linear model equations must be employed for these purposes. Let us identify some useful quantities that can be generally obtained from the state-space description of an electrochemical
system.
Charge
transfer resistance.
The
charge
transfer resistance
Rt
is defined
by
1/Rt
which becomes with
(2.22)
Eq. (2.15)
1/Rt
i.e.
lim
co-*
YF(jco),
on
(2.23)
the real axis at
Rt
is
scalar
quantity
which
can
be found
=
high
fre
complex plane plot of ZF(jco) 1/YF(jco) (cf. Fig. 2.3). Accordingly, 1/D is the most general description for Rt taking the non-reversibility of the elementary reactions into account. Note that only in the case where the concept of the rate determining step applies, we obtain
quencies
of the from
Eq. (2.1)
R"1
where
i0
[expj^n]- expj^n)]
at the
(2.24)
At
zero
f|
is the
overpotential
corresponding operating point.
overpotential we find
the well known result
Kt1
hd^rY, + c> o*f(.oaTv.c'-'o^r>

=
(2-25)
32
2.2
General Framework
ZgCjO))
ioo
316
L.
316/
N
3kZ
\#32
10k/*
i
100k/
*t
%
*c
i
-2
-
a)
10
15
20
Re(Zp/Q)
20
11 ii
11 r
20
CJ
-fc10
N
oo
10
1=^
*
'
ii
'
'
''
'
b)
10
101
102
103
-h
f/(2n*-1)
104
105
Fig.
()
2.3
General Faradaic
frequency
of
response
ZF(j(o)
of first-order electrochemical Bode
systems.(a) Complex plane plot

denotes
ZF(jco)
were
data and
(b)
plot
of the
same
data.
|ZF|
and
(- -) denotes the phase <p. The numbers

in Hz. The data
in the
complex plane plot
denote the
frequencies
obtained from
simulation of model M2
(fully
ance,
described in Part II of the present paper
[1]).
=
denotes the
-
polarization
resist
Rt
is the transfer resistance, and
resistance.
Ze(jco)
denotes the
R Rc Re Rt denotes the concentration frequency dependent part of the Faradaic impedance

=
ZF(jco).
33
and
where
is the number of electrons which
were
transferred in the rate-deter
mining step,
is of
and
v as
is the stoichiometric number

it
(see [23], p. 1006). Eq. (2.25)
importance
can
gives
relation between the
iQ/
which
be obtained from
can
exchange-current density steady-state current-voltage measurements,

(see below).
output
to
and
Rt,
which
be obtained from EIS measurements

The dc
Polarization resistance.
its
gain
s
of
system
=
is the ratio of the
(constant) input after all
transients have
=
decayed.
0 in
To find the dc
gain of an
asymptotically stable system we put the polarization resistance R
jco
Eq. (2.17)
and obtain for
^-
YF(0)
D-CA_1B.
(2.26)
Obviously, Rp depends also on f\ at the operating point as well as on the experimental parameters (T,pQ). R is also a scalar quantity which can be found on the real axis at low frequencies of a complex plane plot of ZF(j(o) (see Fig. 2.3).
Concentration admittance.
write the Faradaic For
reasons
which will become clear later,
we
impedance ZF(s) as the sum of the charge transfer ance Rt and the concentration impedance Ze(s), an impedance due time dependence of the concentrations of the adsorbed species ZF(s)
=
resist
to the
Rt + Ze(jco)
(2.27)
From
Eq. (2.17)
we
obtain
yF(s)
and from
d^ ^si-a^b]
+
(2.28)
ZF(s)
-i,
=
YF (s)
we
further have
ZF(s)
D
=
D-(D
D
C(sI-A)
-l,
B)
B
-i, D + C(sl-A) B_
C(sl-A)
-l,
(2.29)
From
Eq. (2.29)
we
obtain
ZF(s)
C(sl-A)
D
+
C(sI-A)_1B.
(2.30)
34
2.2
General Framework
which is
equivalent
to
YF(s)-D
ZpW-V*.-^By comparing Eqs. (2.27)

and
<2-31>
(2.31)
we
finally
obtain
ZQ(s)
and
-Rt
-^H-r-
YF(s)-D
Yv(s)
(2.32)
by definition (cf. Fig. 2.3)

1/Rn-1/Rf
Ze(0)
Eqs. (2.23) quencies and by
From
Re
-Rt
^
that
'
Rp Rt
-
(2-33)
ZF(jo)) is limited by Rt at high fre R at low frequencies. The frequency response ZF(jco) in between these limits is described by the concentration impedance Zq(jco) (Eq. (2.32)). Note that the concentration resistance Re not simply depends linearly on the charge transfer resistance Rt, but that a rather complicated relationship exists. Thus, it is expected that the dependence of Re (or of R if R_ Rt) on temperature and on oxygen partial pressure shows a rather complicated behaviour.
and
(2.26)
we see
2.2.5
Bode
Working with Frequency Responses

plots.
If linear
time-independent systems are put in series, the fre quency response of the new system is simply the product of the individual frequency responses, the magnitude is the product of the individual magni tudes, and the phase is the sum of the individual phases. It is therefore con venient to draw the magnitude in a logarithmic plot and the phase in a linear plot. Together, these two curves comprise a Bode plane plot of the system. There are some important quantities that can be directly obtained from the Bode plot (or from the Nyquist plot) of a system. It is important to be able to hand-plot frequency responses for several rea sons: simple problems can be dealt with directly and computer results for more complicated cases can be checked. Hand-plotting is especially useful in interpreting frequency response data that have been obtained experimentally.
35
and
We will illustrate this

common
procedure later. The interested reader textbook about control theory (see e.g. [38,39]).
vs.
is referred to
Admittance
Faradaic admittance.
It is
emphasized
that
ZF
describes
yield the total impedance Z, i.e. ZF obscured by a double layer capacitance Cdl. A rig orous treatment of the electrode impedance must include coupling between Faradaic processes and the charging of the double layer. If, and only if, the origin of Cdl can be attributed to a space charge at the interface between the noble metal grains and the YSZ [12,50,55], can it be assumed that Cdl is associated in parallel with ZF and therefore:
dynamics.
In contrast, EIS measurements
the intrinsic electrode
Z(ja
' Zp(jco)
=
.
l+]CoCdlZF(]to)
(2.34)
un-compensated electrolyte resistance Re present. Therefore, the total electrode system can be represented by the "equivalent circuit" shown in Fig. 2.4.
is
In
addition, there
always
finite
C<11
*e *t
-
zeGco)
ZpXJG))
Fig.
2.4
"Equivalent circuit"
=
impedance Zp(s) function: Cdl(s) ZF(j(B) comprises a series combination of the transfer resistance Rt and the concentra tion impedance Ze(jco). Note that the (measurable) frequency response Z(jco) depends on ZF(j(o), Cdl, and Re and that the intrinsic dynamic behaviour of the electrochemical interface is exclusively described by its Faradaic frequency response ZF(joo) (not directly
is obscured
Faradaic metal/electrolyte system.The by an layer capacitance Cdj (transfer in parallel and an electrolyte resistance Re in series. l/(sCdl))
an
of
noble
electrical double
measurable).
36
2.2
General Framework
The various
possible frequency
as
cal reaction mechanism
responses depend on the actual electrochemi well as upon the values of Cdi and Re. We will
we
expand
this
is
point
in
part
II. However,
on our
would like to
ZF(j(o)
entirely dependent
with EIS
kinetic model and
point out here that that Re and Cdj are

can
(measurable!) external quantities. It
is well known that
Re
be determined
experimentally
[56]
or
can
with the current be almost
interruption technique [57].
equally well determined from EIS data, if the general "equivalent circuit" of Fig. 2.4 applies, even without mak ing any assumptions on the Faradaic impedance [58]. There are examples in literature where values for Cdl are reported from equivalent circuit analyses ([17,18,59] and references therein). Always, an a priori choice of an equiva lent circuit was made. Obviously, the values determined for Cdi from fitting impedance data to equivalent circuits largely depend on the choice of the cir
Cdl
cuit. We believe that the
But it is less known that
interpretation
of these data is doubtful.
2.2.6
Identifiability
of Linear Reaction Models
Testing model structures a well accepted practice

notion of
for
identifiability
and
distinguishability has become

systems [60, 61]. The
in identification of metabolic is most
identifiability
lems often encountered in
easily understood by considering the prob equivalent circuit fitting. There, identical simula
parameters for the
or
tion results may be either obtained with different sets of

same
same
equivalent
the
same
circuit
(problem
of structural
global identifiability),
same
the
simulation results may be obtained with different model structures

number and type of electrical
(with
tural
elements) but the
set
of
parameters (problem of structural model distinguishability). Note that
struc
global identifiability is a property of the model itself that is assessed. It has nothing to do with the accuracy of measurements and data. There are currently many methods available for analysing the identifiability of LTI sys
tems. In
contrast, efficient methods to
analyse
the
identifiability of non-linear
is
systems have only recently been introduced [62, 63]. The interested reader
referred to the cited literature and references therein.
It is
only recently that the concepts of model identifiability and model distin guishability have been introduced in the field of aqueous electrochemistry
[64, 65].
It is not
our
intention to present the
substantial, although mostly concerned

mechanical systems
theory, for the literature on it is with pharmaceutical kinetics [61] or
[62].
A reaction mechanism is said to be
globally
p
can
struc
turally
identifiable if, and
only if,
unique
set of
parameters
be deter-
37
and
mined for
given input. The finite (and hopefully small)

a
mechanism is said to be number of
locally
identifiable if
parameter
sets is
estimated from
equivalent circuit fitting). Non-identifiable mechanisms give identical outputs for a given input for any set of parameters. We will encounter all three situation while investigating our proposed models of the Pt, 02(g) I YSZ system. experimental
data
(very
often encountered in
2.3
2.3.1
The
Reaction Models of the Pt,

Introduction
with the
use
02(g)
I YSZ
System
problem associated
of numerical methods may, in
our
opin
ion, best be elucidated using simple

idea
examples.
This section illustrates this
by considering a simple reaction mechanism of the Pt, 02(g) I YSZ sys tem, which is by far the most thoroughly studied electrode system in high temperature electrochemistry (see e.g. [5,11,13, 66]). Dissociative adsorption
of oxygen
on
Pt, surface diffusion of atomic oxygen, and electrochemical

a
reduction of adsorbed oxygen in

is considered In
our
two-electron transfer step
near
the
tpb
line
[25,66]. (Ml),
mass
first model
and
charge
balances
are
formulated and the

surface dif transfer of
complete model structure is developed. For illustration purposes, fusion is first neglected, i.e. we assume that any diffusive
adsorbed atomic oxygen is slow
~723 K
(which
is the
case
for temperatures below direct
(~450C) [11])
and therefore the oxygen is
only delivered by the
adsorption process near the tpb. The model Ml is tested for structural identi fiability in the steady-state as well as for electrochemical impedance spectros
copy.
In
our
second
model
is
(M2)
we
include
surface
diffusion.
The
finite-difference
approach
employed
for the treatment of surface diffusion.
Considering one-dimensional,
solution.
are
first-order
finite-difference method is the most
coupled differential equations, the straightforward method of numerical 021

YSZ
Computer implementation
part
II
and simulation results of both models
illustrated in
[1].
more
realistic model of the Pt,
system
(M3), accounting
for the
Pt surfaces, will be the
step-wise adsorption/desorption dynamics subject of a forthcoming publication [67].
of
02
on
38
2.3
Reaction Models
of the
Pt, 02(g) I YSZ System
2.3.2
Model
Basic
Equations
and
Assumptions
exchange
of oxygen at
equations.
We consider the electrochemical
the Pt/YSZ interface which is described
by
=
the overall reaction
^02
represents occupied
the electrons within the Pt.
V0 + 2e"
00
(2.35)
where, in Kroger-Vink notation, V0 represents the oxygen vacancies,

oxygen lattice sites in the
00
electrolyte,
and e~
represents
The overall reaction is considered to consist of several
elementary reactions [5,8J. Oxygen adsorbs dissociatively on the Pt surface, diffuses linearly in the direction perpendicular to the electrode surface, and is electionated and incorporated near the tbp in the active area of width w (cf. Fig. 2.1 and
Fig. 2.5):
2(g) + 2s 2ad
des
(2.36)
Tt
EMD
+
C237,
ad
Vb
2e
<00 +
1
(2.38)
where
kad and fcdes are the rates for adsorption and desorption of oxygen on polycrystalline Pt; c is the surface concentration of Oad; D(c) is the chemi cal diffusion coefficient of Oad on the Pt surface; kt and k- are the electro
chemical rate constants; and [s] is the concentration of vacant surface sites.
Assumptions.
(i)
The
We will base Ml
on
the
following assumptions: dissociatively

and
adsorption of oxygen Langmuir isotherm;

be
occurs
obeys
(ii)
The maximum number of surface sites per unit

can
area
which
occupied by Oad
is characterized
by N0;
39
and
(iii) The
rate of
adsorption /cad
Vq
and
are
desorption kdes
are
independ
ent of surface
coverage and
known from the literature;

in the YSZ surface
are con
(iv) The
concentrations of
and
00
stant;
(v)
The electrochemical rate constants

ent
on
are
exponentially depend
the
potential
=
difference
*!
A-
klc(T)exp[-n$cFE/(RT)]
fcic(T) exp[npaF/(RD]
(239)
where
klc(T)
and k- (T)
are
potential independent
n
chemical
rate constants;
Pc
and
(3a
are
the cathodic and anodic transfer

is the number of
our case n
=
coefficients of the electrochemical reaction;

electrons transferred in the reaction step
(in
2);
n
T| where
eq
is the
equilibrium potential
and
is
the For M2
we
overpotential.
assumption:
on
make the additional
(i)
Surface diffusion
depends only
concentration
gradients.
No interaction of adsorbed
species
is
considered;
(ii)
The surface diffusion coefficient D is known from literature
data;
(iii)
Mass and
D is
independent of the
local surface concentration.

and
charge balances.
=
For Ml
mass
charge balance give

(2.40)
^[Oad] 2fcadp02[s]2
2fcdes[Oad]2
+
-MOadHVol
fcjtsHCk]
(2.41)
from the
IF
where
2EAa[fci[s][Oj] -fc1[Oad][Vol]
is the
area
Aa
tpb
x w
of the active
region extending
tpb
electrolyte grains, and/or along the electrolyte surface. For the moment we make no speculations as to the physical basis of this extension. From the modelling point of view, the active region is simply regarded as a
line under the
40
2.3
Reaction Models
of the
Fig.
2.5
Schematic view of the active electrode
area near
the
physical extension of the active area around the tpb ,w, from only the electron transfer rate in the active area Aa, and not the location of the reaction, determines the electrochemical properties of the interface. Accordingly, we can Aa con
sider to extend from the
tpb.Regardless of the a conceptual point of view
tpb
towards the Pt electrode.
strip extending from the tpb line along the noble metal surface towards the electrode (cf. Fig. 2.5). We assume for the moment that Aa is a priori known.
For M2
a
further term must be added to
Eq. (2.40) accounting for
the surface
diffusion.
Complete
malized
model structure.
The mathematical model should first be

its numerical
nor
or
scaled to
improve
plished by replacing the surface N0 coverage. By expressing [Oad]

=
conditioning. This concentration by its fraction
is
accom
of surface
and [s]
N0(l-6) Eqs. (2.40)
and
(2.41)
are
rewritten
/i=
dt
2*adPo N0 (i
e)2 ^desN0 e2
-
(2.42)
*i-[Vo]-e
*r[C&]-(l-6)
41
and
gl:
IF
2N0FAax kv [00] (1 -0)-^ [V0]

(2.43)
which is
simply
representation
of
Eqs. (2.2)
and
(2.4)
with the state vector
x(t,p),
the
input
scalar u(t), and the
output scalar y(t):

=
Q(t,p)
x(t,p),n(t)
u(t), and I(t,p)

is
y(t,p).
(2.44)
The vector with the unknown
parameters
given by
(2.45)
reac
[fclc(T),Pc,fcIc(T),PJ.
Eqs. (2.42)
To
and
(2.43) generally describe the dynamic behaviour of the
tion mechanism Ml.
complete Ml, we have to consider all additional and independent alge braic equality or inequality constraints relating 9, n, and p or any combina tion of these, known a priori. The relationships are generally written as
/j[9(f,p),n(f),p]<0.
The
(2.46)
equation system of Eqs. (2.42) to (2.46) is defined as the constrained structure, which completely describes our model structure Ml. In our partic ular case we have the two following equality constraints (cf. e.g. [23]).
Pa
The number of
Pc"1
Oand/F(eq)
0.
(2.47)
independent parameters is therefore reduced by the number of equality constraints. Accordingly, the number of parameters to be deter mined in Eq. (2.45) is reduced to one rate constant and one transfer coeffi cient, e.g. p [klc(T), f5c]. In the following we will simply write P instead
=
ofp.
2.3.3
Let
us
Electrode
consider
are
a
Overpotential
type shown
in in
a
cell of the
ments
performed
same
three-terminal
Fig. 2.6. Electrochemical measure configuration where the working

counter electrode
aware
electiode
(WE), reference electrode (RE), and
(CE)
a
are
exposed
ence
to the
atmosphere.
We should be
of how
polarisation
refer
device interacts with the electrochemical cell. In
potentiostatic
mode
potential
difference between the WE and CE is set
by
the
experimenter.
42
2.3
Reaction Models
of the
Negative feedback of the actual potential difference ensures control of the ref erence potential. A polarisation is imposed on the CE side. As a consequence, the electrode reaction on the CE departs from its equilibrium point and the electrochemical potential of oxygen ions, ji 2-(P"), in the surface of the solid
electrolyte
fore,
a
is altered. This
causes a
current
through
the
electiolyte and,
there
net current
flows
through
the WE. If the electrode reaction is not infi
nitely fast, ji 2-(P') deviates from its equilibrium value, whereas jio2-(P) remains at its equilibrium value, ji 2.(P') is somehow related to the oxygen partial pressure and the current. The question which emerges is the follow ing: what is the physical significance of the potential difference between WE
and CE that
can
be measured?
We therefore consider the
following half-cell
reaction
02_(P)|02,Pt(a)
where
(2.48)
Pt
P denotes the solid electiolyte and where the electrode material

seems
(phase a)
not to be
involved in the electrochemical reaction. The poten
tial is determined
by
the
following reaction
k>2
i.e. the electrons
are
2e~>02~,
(2.49)
common
the
phase
and
p.
For the
only charge carrying species which are equilibrium of reaction Eq. (2.49) we have
in
WE
Pt
RE
'.
.'
YSZ
Pt"
P'
3"
,
CE
Fig.
2.6
Schematics of
three-electrode cell with identical porous Pt electrodes.The

are
notations used in subsection 2.3.3
indicated.
43
and
^
jL(y)
=
2^(00
ji02-(P).
potential
of
(2.50)
With the definition of the electrochemical
species
i in
phase
y,
ziFcp(y), and the definition of the chemical potential, p..(y) + RTlnfl t(y) where flj(y) is the activity and m(y) is the stand p:.(y) ard chemical potential of species i, we can calculate the equilibrium potential difference (Galvani potential) between the metal and the solid electrolyte at
(i^y)
+
=
the reference electrode
as
follows
eq4
Acp
,a.
u(cx)-u(P)
=
RT
cp(a)-cp(p)
lnfle(p).
(2.51)
where
we
used
can
lyte, fle(P),
involved
1. The activity of the elections in the solid electio ae(a) be expressed in terms of the equilibrium in which they are
=
K(0\02
(2.52)
o(P)-WP)r
phase (g)
=
At the reference electiode, the gas
is in
equilibrium
=
with the solid
electrolyte
surface
=
(P), thus ApG

where
Mo^-lk^P)
conveniently
we
anc^
a0(P)
fl0(g)
JPo /*/p~
we
set
1 atm.
this result and
solving Eq. (2.52)
for
ae(P)
obtain for the
accordingly Using equilibrium
potential
difference
Acpeq
where
we
Acp
=
ln(^) ||ln[flo2.(P)]
-
(2.53)
used
Acp
Au
RT
+
ln[K(02IO )]
2-
for the concentration inde
pendent terms. The overpotential n
is defined
as
the deviation of the interfacial
potential dif
=
Acp- Acpeq. equilibrium potential difference A(peq, T| If a current flows through the interface between the electrode (a') and the solid electrolyte (P'), the equilibrium situation no longer prevails for polarizable electrodes. Analogous to the derivation of Acpeq we obtain for the non-equilibrium potential difference
ference Acp from the
Acp
A9
|ln[ao(P0]-f^m[ao2_(P')].
44
(2.54)
2.3
Reaction Models
of the
With the definition of the electrochemical
potential for
2-
we
obtain
gln[flo2.(P')] ^[ii02-(P')-lio2-(P')-lio2-0]+<P(P')
=
(2-55)
and jj,
similar
=
result
we
for
2-(P)
by
replacing
P'
with
p.
With
2-(P)
M^n2-(P')
obtain for the
overpotential
Acp-Acpeq
|[|io2_(P)
+
jio2_(P')]
[<P(P)
cp(P')]
(2-56)
RT,
MP')
2Tln
-fa-
Eq. (2.56)
the
the
overpotential is attributed to the ohmic drop due to ionic current in the solid electrolyte (first term: ohmic potential drop), to (ohmic) potential drop due to charge transfer (second term: charge-trans
shows that the
and to the deviation of
fer
overpotential),
fl0(P)
frm
me
equilibrium value
overpo
at the
electrode/solid electrolyte interface (third

can
term: concentration
tential). Accordingly, Eq. (2.56)
be used to validate simulation results.
2.3.4
Structural
Properties
of the Models
Model Identification. the structure of

a
Identification is concerned both with
determining
physical process
of
a
and with
estimating
the unknown parame
ters. The structure
mathematical model is reflected in its set of

The
(coupled)
question
differential of whether
equations. it is possible
on
question
a
of identification addresses the
to obtain
unique
solution for the unknown param

a
eters of interest
the basis of data collected in

as
question
If the
is often referred to
that of
can
particular experiment. This theoretical or structural identifiability.
theoretically identified uniquely, the parameters estimation problem is theoretically well posed and the actual experiment can be carried out to provide real data for parameter estimation. This assumes, however, that the experimental test data used for identification are noise-free and that the structure of the proposed model is not in error (question of practical identifiability). Indeed, the second assumption is often not fulfilled and therefore postulating a false of (partly) inappropriate model
parameters of
Ml and M2
be
structure constitutes
an
important
source
of
error.
45
and
Equilibrium potential Eeq.
We first show that the unknown parameters p

can
of the model structures Ml and M2
be
overpotential measurements. We first describing the steady-state IF(n) behaviour. Starting from this result we prove in a second step the global structural identifiability of the mechanisms in the steady-state. Under steady state the condition dQ/dt 0 must apply. By solving 0/we obtain for the equilibrium potential Eq. (2.43) for IF(E )
=
=
uniquely obtained from currentrigorously develop the expression
eq
,Po>)
2/'
ta[*ic<T)'[o^'l-VT,p0z)J
in this way E
(2.57)
where
F/(RT). Note that

well
as
(T, pQ ) depends
on
the tem
perature
as
on
the oxygen
partial
equilibrium
surface concentration of
Oad
pQ ) denotes the which is obtained from the mass

pressure.
Q0(T,
action relation
(Eq. (2.36))
%(T, Pp2)
l-%(T,Po)
with the
K(T)
fc
(2.58)
equilibrium
in
constant
K(T)
Jkad(T)/kdes(T). By putting
Eq. (2.58)
Eq. (2.57)
we
obtain
,T
,
2
eq
2/
r^(T) [v] [k-lc(T) [0x^j

=
K(T)
^ln(p02)
=
(2.59)
and, accordingly,
eq(T, pQi)
eq(T) + eq(p02).
=
Eq. (2.59) is simply an expression of the Nernst form. We arbitrarily set the T and pQ equilibrium potential which evolves at T equal to p0 zero. In this way the electrode potential, and therefore also the electrochemi
cal rate constants,

For the
are
defined relative to this reference state.
temperatures
not too far
from T
we
make the
following
formulation for
temperature dependence of the chemical
rate constants:
klc(T)
*lc.exp[-El/(RT)]
k-lc-exp[-El/(RT)]
46
k-lc(T)
(2.60)
2.3
Reaction Models
of the
where
the_pre-exponential factors, klc and k- and the activation energies, a and a, are assumed to be temperature independent. Accordingly, we find in the reference state
,
V3
57-hl
fclc
we
fcic [V0]
*lc
=
[Oq]
and
+tf
kl(
=
hl<^5)
(2-61)
where, by definition,
With
fclc(T)
p020
1 atm
find
k-lc
at T
from.CEq. (2.61)
fcIc(T).
as
[V0]
[Oq]
The values for the forward and backward electrochemical rate constants at
equilibrium, kx(T,pQ ) and k-(T,p0), are finally obtained from Eq. (2.39) by use of Eqs. (2.59) to (2.62). In principle, we are free to choose the reference state. For obvious reasons, it is advantageous to take it at 1 atm. The reference temperature can be pQ taken anywhere, but once this temperature is fixed, the chemical rate con stants must be described by Eq. (2.60) and (2.62). For simulation purposes we need to assign the activation energies a and Ea some (reasonable) values. In principal, it is possible to determine these values experimentally. We will return to this point below. Finally, it is important to recognize that by defin ing the equilibrium potential in this way, a change in the oxygen partial pres sure influences both the forward and backward rate constant through the in change eq.
following we derive the expressions for the steady-state IpOl) behaviour and the exchange current density as a function of pQi at T. By substituting Eqs. (2.39), (2.60) and (2.62) in the expression for the Faradaic current (Eq. (2.43)) we obtain
Steady-state IpCn)
behaviour.
In the
Mm, T, p0)
2N0FAaklc[Vo]
x
(2.63)
K(T) (i -fi)
i.e. the
.e2<l-W<*i>_. f*f<****r
surface coverage of the
where 9
steady-state corresponding operating point. Eq. (2.63) is

=
8(n, pQ^, T),
Oad general description
at the
of the
47
and
current-voltage behaviour of the proposed reaction mechanism (valid for Ml and M2). As long as 0 is independent of n, either because the adsorption flux or the surface diffusion flux is much larger compared to the electrochemical reaction step, we simply have to deal with a charge transfer-controlled reaction and 9 is obtained from Eq. (2.58) steady
state
K(T)- jpZ
6
=
%(T, Po) 2
exchange
2LEL.
l
+
K(T).Jp^2
are
(2.64)
The anodic and cathodic
currents densities
therefore
given
as
i0
i0a
2N0Fklc[Vo]K(T) (1 -90) i0c
e2(1_P)/eq
and
(2.65)
i0
2N0Ffclc[Vo] 90 <f 2P/eo.

(2.66)
for the
By taking the product of Eqs. (2.65) and (2.66) we obtain current density (note that we do not (!) assume that p 0.5)
=
exchange
i0
2N0Ffclc[Vo]-[90(l-90)]1/2-7K(7^j-e(1"2P)/e<'
and
(2.67)
with
By using Eq. (2.64) for expressing 90 1/(2/) ln(Jp^),we finally obtain
by replacing
(T,p0 )
i0(T, POi)
With
2N0F*lc[Vo]
*<^>
and Pq
Po2(1"P)/2
(2-68)
dependence of i0 is obtained at low and high oxygen partial pressures, respectively [8, 68]. This behaviour is generally explained with the Langmuir adsorption of oxygen (Eq. (2.58)). Our result is more general.
P
=
1/2, the well known pQ
The oxygen
partial
pressure where the maximum of
i0(T,po)
occurs
is
given by
Po2*(T)
The
Jjl2PPL
P2-[K(T)r
(2.69)
expression
for the
gen
partial
pressures
exchange current at arbitrary temperatures can be similarly calculated and is given by
and oxy
48
2.3
Reaction Models
of the
i0(T,Po2)
2N0Ffclc[Vo]
lVA + (AHad)/2 J+ lr R -2KfWX:
n|a
tj
(i
x
aH2
(2.70)
JK(T)K(T)
:=
1+K(T)-Jp^2
where
=
Po,
(i-P)/2
adsorption enthalpy, and where A a a. It is seen that the temperature dependence of i0 at a fixed oxy gen partial pressures shows a rather complicated behaviour and no straight line can be expected in an Arrhenius plot of i0. Let us finally note that Eq. (2.69) is generally valid for arbitrary temperatures and not only for
we
=
us_ed AHad
ad
des
for the
rp
By use of Eq. (2.70), Eq. (2.63) simplifies equation
to the well known Butler-Volmer
Un.T.PoJ-UT.fo,).A.-le^-M-e-**}
As
soon as
(2.71)
an
9 deviates from its
equilibrium value 9q (due
to
applied
over-
Ip(T|) will deviate from the ideal Butler-Volmer behaviour described by Eq. (2.71) and the reaction can not be considered as charge-transfer controlled. The actual behaviour depends on the relative magnitudes of the electrochemical rate constants to the rate constants of the
source
potential),
then
terms of
Oad (adsorption and

steady-state.
surface
diffusion).
use
Identifiability
give
an
in the
We
now
the result of
Eq. (2.71)
to
intelligible
are
and M2
said
identifiability. The mechanisms Ml to be globally structurally identifiable from steady-state /F(n)

n
prove of structural
measurements
when for all
hip)
It is
l-pip*),
if and
only
if p
p*
controlled
current
(2.72)
reactions
are
well-known
that
two
described
by only
purely charge-transfer parametersthe exchange

a
apparent transfer coefficient
(note that
we
density i0 and the deliberately use the symbol a
49
and
instead of
p,
which
we use
for
elementary reactions)which
vs.
can
be
uniquely
in
determined
our
by
Tafel-analysis (log(ip)
n) (see
e.g.
[23], p. 888). Thus,
fclc and P can be uniquely determined if the reaction is entirely charge-transfer controlled. It is rather troublesome to show analytically that Ml is globally structurally identifiable in the general case, because the (non-linear) analytical expression for 9(T), p0 T) (which is obtained by solving d9/df 0) must be substituted in Eq. (2.63). For the case where Tafel behaviour should prevail (|r|| RT/(2F)) the problem reduces to show that the following must hold
case,
=
,
for all
Q(p)
It
can
Q(p*),
if and
of
a
only if
p*.
(2.73)
program such
as
be shown,
or
by
means
symbolic computer
Mathematica
is
MAPLE, that Eq. (2.73) holds and that therefore the
problem
uniquely identifiable in the steady-state, even if the reaction is not charge-transfer-controlled. (We do not give these results because they can be easily reproduced on the computer and it takes some space to present them.) Keep in mind that in this case the unknown parameters can not be estimated from a Tafel analysis, but can be obtained from a least-square fit of Eq. (2.63) to the experimental data. A Tafel-analysis of experimental data would give
incorrect values for the unknown
parameters.
M2. We
in
We
can
use
these results to infer the

that M2
is
expect
identifiability of reaction mechanism also globally structurally identifiable

are
the
steady-state,
Therefore,
because the model structures of Ml and M2
similar. In addi
tion, the surface diffusion coefficient of

we
Oad
on
Pt
was
assumed to be known.
into the
have not introduced any
new
parameter
problem.
is
Note that the
steady-state strongly influenced by the surface

as
concentration of
Oad
near
the
tpb line, 9,
to
diffusion of adsorbed
species.
We therefore
expect this
This
means
concentration to remain
in the
an case
approximately
is
constant up
much
higher overpotentials
where surface diffusion is absent much

more
(Ml).
a
that such
electrode
likely
to
exhibit
charge-transfer dominated behaviour, fromanfp(n) analysis.

Linearized state space
state space model from constants from
which allows for parameter estimation
description.
We
will
first
rewrite
the
non-linear
rate
Eqs. (2.42)
and
and
(2.43) using the definitions of the
Eqs. (2.39)
(2.60). With the abbreviations
50
2.3
Reaction Models
of the
keq
*
e_*/(RT) e"2P/eq
k-
.fE^RT\e2^-^fE^
(2.74)
we
obtain
fi-
^(t,p)
2fcadPo2No
[1
8(f,
p)f
2kdesNQ 9(f, p)2
(2.75)
[00].[l-9(f,p)].)cf-e2(1-pW)
[-
gl:
IF
2N0FAa
[VG] 9(f, p) fceq e~imt)
(2.76)
[oJ]-[i-eaP)].]fc?c'-e2(1-p)^)]
expressed through k^. The linearized state space description of Ml is obtained by linearisation of Eqs. (2.75) and (2.76), using for the rate constants, k\ the steady state values k^(E, T) and k-(E, T), and the surface coverage, 9 9(p, T, p0 ), at the correspond fcj
Note that
A^q
must be
ing operating point.
We obtain
5/i
=
39
a(p)
*kadpoN0 (1
9)
4kdesN0
(2.77)
[VG] h
[00] k-x
d/i
=
3t1
b(p)
[V0]-2B/fci-9
+
(2.78)
[00]-2(l-P)/fcr(l-9)
39
c(p)
-2N0FAa
[[00] k-x
[VQ] fci]
(2.79)
51
and
dn
d(p)
2N0FAax[[Oo]-2(l-P)/-r(l-8) +
[VQ] 2P/ h 9]

(2.80)
which
finally
may be written
compactly
a(p)Q(t,p) c(p)Q(t,p)
+
9(f,p)
b(p)r\(t)
I(t,p)
where
we are
we
d(p)x](t),
(2.81)
to denote that
used lowercase letters for the
(A, B, C, D) quadruple
dealing with scalars (first-order SISO system) instead of matrices. Following the procedure described in subsection 2.2.4 we obtain the Faradaic impedance ZF(s, p) in transfer function representation (cf. Eq. (2.30)):
Z(s,p)
Rt
1s +
-([00]fcT
[V0]fci)
+
4kadN0po-(l-Q)
4kdesNQ-Q
(2.82)
l/d(p) by definition (cf. Eq. (2.23)). It can be shown that the Rt(p) result for Rt(p) and the expression for the exchange current density i0 (Eq. (2.68) or (2.70)), satisfy relation (2.25).
where
=
Identifiability with
structure is
electrochemical
impedance spectroscopy.
if the
This
model
globally identifiable at p* equivalence ZF(s, p) Z(s, p*) Vs determined by seeking solutions of

=
equations
in p that arise from the

=
have the the
p*. This is only solution p following system of equations for
any :
Rt
R*
[oD] fca
[vQ] h

[oG]
T*
[vG] i*
(2.83)
âdôPo,
Keep
be
at T
(1
8)
4fcdesN0
=
4kadN0pO7
=
(1
9*) + 4fcdesN0 9H
in mind that 9
9(p, T, pQ ), k\
pQ . We obtain
k\c(r\, T,pQ), and that fcj should

is solved for illustiation purposes
expressed
=
in terms of
=
k\. The problem
T and pQ
constant and with
(by substituting the 0) for the second relation in Eq. (2.83)
backward rate
52
2.3
Reaction Models
of the
[K(T)
a
1]
(fclc)*[K(T)
l]
(2.84)
P
can now
which has
obviously
single
solution for
fclc.
The value for
be
uniquely obtained from the first relation. Accordingly, Ml is globally struc turally identifiable by impedance spectroscopy at least under equilibrium conditions, i.e. we could estimate a unique set of parameters from EIS data obtained at the reference condition and zero overpotential. Obviously, it becomes much more difficult to prove the structural identifiability of Ml
apart from
the reference state
or
for
n *
0 and
we
do not indent to do
so ana
lytically.
Let
us now
consider M2.
We
first-order process
constant
(Fig. 2.7) and (boundary condition).
approximate the surface diffusion by a 8 as keep the surface concentration at z

=
We obtain for the surface diffusion flux
(cf. Fig. 2.7)
%
1
CO
=
J\
-
h
-
e(t)
t=i
YSZ
tpb
investigation
of reaction mechanism
=
Fig. 2.7
Two-compartment
model for structural
M2.The electrochemical reaction takes
place
in the
tpb compartment (i
1). The
con
centration of adsorbed atomic oxygen is considered to be
partment.
At
distance
z >
8,
is considered to be
diffusion flux is
proportional
to the
homogeneous time-independent. concentration gradient.
within
a com
The surface
53
and
/i(0
"e0-e(o"
"9
and/'^f)
(f)-90-
(2.85)
The
mass
balance for the
tpb compartment is
=
obtained from
('tpb8)-^(*)
which results in
(>Wi>-ztpb
(2.86)
24.Jr9(r)
where
90-9(f)
(2.87)
Td
(8
8 /(2D) is the time constant of the considered surface diffusion
process
tration
is often called the average diffusion
depth [7]).
We include this term in the The result is
length of Oad [25] or the pene mass balance of Eq. (2.75) and
re-evaluate
ZF(s,p).
given by
ZF(s,p)
Rt
1s +
-([Ool-fci
T+
tVolfci)
-
(2.88)
9
AKdN0Po7
(1
8)
4kdesN0
no
which
means
that the existence of surface diffusion has
negative
influence
identifiability of M2. Furthermore, we can expect to estimate Td from an impedance analysis under the experimental conditions where the simplifications are justified (at high cathodic overpotential and low oxygen partial pressure, i.e. under limiting current conditions). From these examples it might seem that the proof of unique identifiability is mathematically straightforward. But the mathematical effort necessary to test for identifiability increases with model complexity and the problem of Vs implies that p whether ZF(s, p) p* is generally a diffi ZF(s,p*) cult one. Berthier and coworkers [58, 64, 65] have proven the identifiability for a number of reaction mechanisms under different experimental condi tions. The reader interested in more elaborated examples is referred to their work and the references therein. Fortunately, computer implementations of efficient algorithms for testing structural identifiability are becoming increas ingly available [62], and the field is growing rapidly.
upon the
= =
54
2.3
Reaction Models
of the
Vagueness
upon the
width that
w
of wits consequences to
our
identifiability.
we
In the
following
we
will address
attention to the
or
question,
what consequences will it have
identifiability of Ml of the tpb is known,

no
M2, when
skip
our
assumption
w
that the
i.e. when
we assume
that
is unknown and
as men
we
would like it to estimate it from
experimental
data. Indeed,
plausible argument to assume that the width of the tpb can be considered as a known quantity. Let us first consider the simplest case of a charge-transfer controlled reaction under steady-state investigation. The IF(T|) behaviour is given by Eq. (2.71) where we put Aa lt b w. Thus, from a Tafel-analysis, P and the parameter product klc w are uniquely identifiable, but klc and w are not individu [P, k^0,w] is un-identifiable in the ally identifiable. Thus, Ml with p steady-state.
tioned before, there is
=
An
important point
n
to note is
that, for
+
classical EIS
experiment
on a
system
with
is
states, there are, at most, 2n
equations
in the
parameters. This fact
easily seen by looking at a complex plane plot where every loop provides two quantities: one time constant and one resistance. The number of states n determines, at most, the number of loops. The additional equation is given by the expression for the charge transfer resistance (cf. Eq. (2.83)). Thus, we could expect that EIS might be capable to give us unique estimates of P, kx
andu;.
Tafel-analysis, estimates for P and fcj0 w can be obtained. Obviously, fcj can still be uniquely determined from an impedance analysis. Accordingly, all parameters can be obtained uniquely from a combined analysis. Note that an impedance analysis alone can not solve the problem, because the last expression in Eq. (2.83) does not
We
answer our
conjecture
as
follows: From
Rt *q and R^k^, w, P), we are left with similar problems as in the steady-state. We see from this example that it is important to have as much as possible a priori knowledge of a system available at an early stage of experimental design. Let us close this section by touching on a problem which occurs in practical parameter estimation. A reliable quality measure of an obtained parameter
contain any unknown
parameter (at least
at
0).
Because
estimate is
sary
prerequisite for any reasonable use of the results. It is also neces for experimental design, in particular for determination of optimal input
a
signals.
that the
To obtain accurate
parameter estimates, it is
sensitive
as
necessary
requirement
object
function is
highly
on
the individual parameters. This
requirement
two
or more
is not
sufficient, however,
the
sensitivity
of
combination of
sensitivi-
parameters may be much smaller than the individual
55
and
ties,
indicating point
high
part
correlation between the

II.
parameters [69].
We will illus
trate this
in
2.3.5
Qualitative Analysis of Frequency Response Behaviour

The
s
Nyquist plot properties.
expression
for
ZF(s,p)
(Eq. (2.82))
is
first-order rational fraction in
'
ZF(s,p)
which
be
Rt(p)
general
s +
1-
bp(P)
s +
a0(p) Eq. (2.13):
(2.89)
can
rearranged
to
the
form of
ZF(s)
where
on
Rt
(a0-b0j
s + a
(2.90)
we
actually
mean
that
Zp, Rt,
and the
polynomial
coefficients
depend
the set of parameters p. The
polarization resistance
b0 Rt-Rt =
is found to be
fUjco)
We also
lim
JO)
ZF(jco)
(flo"&o)
(2.91)
immediately see by comparing Eq. (2.32) Ze(s)

=
and
Eq. (2.89)
that
-Rt
'o
s + a,
(2.92)
o
which is the transfer function of

and
a
an
electrical circuit made up of

= =
resistance R
parallel where R -Rtb0/a0 and C l/fl0. The frequency response ZF(ju), p) shown in the Nyquist plane is a semicircle in the fourth quadrant ("capacitive" behaviour) (Fig. 2.8) with the high fre the angular fre quency intercept at Rt, the low frequency intercept at R
capacitance
C in
,
quency of the apex at go0 denominator in Eq. (2.82)

i.e. if the
ao
>
ana<
^p
^t
ê
can
furmer
see
that if the
(or Eq. (2.88))
is much
larger
than the numerator,

is much
adsorption
and
desorption
process
(or surface diffusion)
faster than the electrochemical reaction step, then this second term will
almost
disappear
and the overall reaction is
charge-transfer
controlled with
56
2.3
Reaction Models
of the
-0.2
0 0.2
0.4
0.6
0.8
1.2
Re(Zp//c)
Fig.
2.8

data
are
in the
complex plane
R )
.The The
num
impedance
witch
standardized with denote the
Rp(a0,b0).
We have
(Rt <
V(jco).
bers within the
figure
frequencies
Rt
are
in Hz. The simulations
were
obtained
increasing
so
values for the forward electrochemical rate constant. Note that
doing
the values of
b0
as
well
as
influenced. With
increasing
values for
by fcj, Rt
decreases and
|b0|
increases.
Rt (curve (1) in Fig. 2.8). In the limiting case the frequency Z(jco) would exhibit as a single point on the real axis at R Rt.
R
=
response
Bode
plot behaviour.
co2
=
x2
a0 in the
introducing expression of ZF(jco) we

t7
By
-l
xx
coj
a0-b0
and
obtain
jou-, +1
(2.93)
which is
well known transfer function in control
theory [39].
We have for
the
phase ZZp(jco)
ZRt-
Z(jcoT1
as
l)-Z(jct)x2 + l)
(2.94)
and the
magnitude can be
written
57
and
log|ZF(JG))|
We
can
log
logClJcoT! +1|) log(|j(ox2 +1|).

-
(2.95)
of
identify
three kinds of terms, where the first term is
independent
the
frequency.
2.9.
The behaviour of the
frequency dependent ZZF( jcu)
terms is shown in
Fig. by
Note that the
frequency
where the maximum of
occurs
is not
given
is
the inverse relaxation time of the process, l/x*, but that this
frequency
inO
10
^^^^
--'"
,.-
N* 10-2
r
a)
in-4
/?t-T2/T, j(0X[ + 1 Qm2 + irl

' '
^_
-:
. .
'
10*
10J
0)/s
-l
1(T
103
100
'
'
-pit-'
"""*
"-r
*r
o
00
50-
~^^^"^ "Z^^^ ^^^

^^^
^^***"NW.
>w
^""""Sk. ^*s*sfc^
S
9I
0
""---....
-501-
"^-^
b)
-100
...
'
'
'
10J
10J
co/s
-l
10*
102
Fig.
2.9
in Bode
ZF(ja>). by adding the individual terms (curves (1), (2), and break frequencies 1/Xj and l/x2 are obtained where a phase (3)) in a Bode shift of 45 occurs. The phase peak is at a>0 Joiâ^ where a^ \/%x and 1/^2 Note that co0 does not correspond to the relaxation frequency of the overall co2
IZpl
scaled with
can
Rp
and
(b) phase
of
Note that the overall
representation.(a) magnitude and over
all
phase
be
simply plot. The
obtained
electrode reaction.
58
2.3
Reaction Models
of the
//(27C-S-1)
b)
Fig.
2.10
-h
//(27C-S"1)
Frequency
responses of Ml in Bode
phases
of
ZF(jco)
data with different ratios of

-1 if
representation.(a) Magnitudes and (b) aQ/bQ. Note that the slope of ZF(j<o) only by
about
one
emerges
clearly
as
o>1 and co2
are
different
order of
magnitude.
given by
tance,
J^
u)2 (cf.
Fig. 2.9).
The
imaginary part
of the Faradaic admit
Im[Yp(jco)],
has its maximum at the relaxation
all process. This fact must be data.
kept
in mind when
frequency of the over discussing experimental
plots by considering the high frequency behaviours of the terms in Eq. (2.95). The magnitudes of these terms approach an asymptote at frequencies (axi 1. The slope of these terms in a Bode plot is either +1 or -1, i.e. it is possible to get information about the order of an electrochemical process by examining the slope of the magnitude in the Bode plot. But at the same time we draw attention to the fact that the polynomial coefficients a0 and b0 have to be different by at least one order of magnitude (in our particular example). Otherwise, both curves will overlap and the slope of the total curve will always be flatter than minus
can see a
We
further
important property
of Bode
59
and
one.
Note that the ratio of the relaxation is
frequencies
These facts
as are
introduced in
in
Eq. (2.93), Fig.
given by tOj/o^
same
l-bQ/aQ.
Fig.
2.8
are
2.10 where the
data
as
in
given
in
envisaged Bode plot.
2.4
Conclusions
study, comprising of this and a second part, was undertaken to provide a tool to treat heterogeneous reaction mechanisms within a uniform framework. The concepts were presented by investigating the reaction mech anism of the rather well understood Pt, 02(g) I YSZ system. We showed that the electrochemical kinetics can be conveniently represented in (non-linear) state space models. In the cases where the reaction mechanisms are simple, analytical solutions for the steady-state and frequency response behaviours
The present
can
be obtained. Otherwise, numerical solutions which

we
can
be found for any II of this
study. Although state space models can accommodate any degree of complexity, the need for testing the structural properties demands rather simple equations. We showed how problems can be simplified without losing too much general validity. There is certainly a need for a widely available and easy-to-use method to carry out the task of testing model identifiability and model distin guishability and the lack of such a method is the reason why we feel some
input/output behaviour,
will
present
in
part
discomfort at the present time.
However, it is obvious that these problems

ments are
must be
tackled before
experi
carried out to make certain that the
most
possible information.
(and use)
as
experimental work gives the We have also shown that it is extiemely important
priori knowledge of a
reaction mechanism
as
to have
much
pos
sible to be able to estimate unknown kinetic parameters from measurements.
Despite
these difficulties, the power of the

can
proposed
method is the fact that
state space models
be treated
on
the computer
efficiently
and in
straightforward way.
Acknowledgments.
portation,
thank
sions. In
The financial
support from the Swiss Department of Energy, Trans
and Telecommunication is
gratefully acknowledged.
on
The authors wish to
present colleagues
in the Chair of Nonmetallic Materials for many useful discus
particular,
we are
indebted to Prof. Dr. D. Bonnell,

our
sabbatical from
Pennsyl
vania the
University,
and Dr. M. Godickemeier from
laboratory,
for
carefully reading
manuscript and giving valuable comments.
60
References
References
[I]
A. Mitterdorfer and L.
tem. Part II:
J. Gauckler. Theoretical analysis of the Pt, 02(g) I YSZ sys implementation, simulation, and validation. /. Electrochem. Soc, sub
of materials selection for ceramic fuel cells. Solid State Ionics,
mitted.
[2]
B. C. E. Steele.
Survey
86-88:1223-1234,1996.
[3]
M. Kleitz, T. Kloidt, and L. Dessemond. Conventional oxygen electrode reaction: Electrochemical Behaviour of Fast Ion and MiFacts and models. In
moxed ConductorsProc
de, Denmark, 1993.
High Temperature of the 14th Ris0 Int. Symp. on Mat. Set, pages 89-116, RoskilRise National Laboratory.
A.
[4]
H.
Yanagida, R. J. Brook, and F.
Kroger.
Direct
current-voltage characteristics of
electrodes. /. Electrochem. Soc,
calcia stabilized zirconia with porous
platinum
117:593-602,1970.
[5]
T. H. Etsell and S. N.
Flengas. Overpotential
behaviour of stabilized zirconia solid
electrolyte
[6]
fuel cells.
/. Electrochem. Soc, 118:1890-1900,1971.
S. Pizzini, M.
Bianchi, P. Colombo, and S. Torchio. On the influence of the anneal

on
ing temperature and heavy current treatments

electrodes and
on
the porous structure of platinum

at
the kinetic of the oxygen reaction
high temperatures. /. Appl.

substi
re
Electrochem., 3:153-159,1973.
[7]
M.
J. Verkerk, M.
W.
J. Hammink, and
A.
J. Burggraaf. Oxygen transfer
on
Zr02, Bi203, and CeOz electrolytes with platinum electrodes. sistance by D-C polarization. /. Electrochem. Soc, 130:70-77,1983.
tuted
I. electrode
[8]
Wang and A. S. Nowick. Cathodic and anodic polarization phenomena at platinum electrodes with doped Ce02 as electrolyte: I. steady-state overpotential.
D. Y.
/. Electrochem. Soc, 126:1155-1165,1979.
[9]
T. M. Giir, I. D. Raistrick, and R. A.
Huggins. Steady-state
D-C
polarization char
acteristics of the
Oz, Pt/stabilized
zirconia interface.
/. Electrochem. Soc, 127:2620-
2628,1980.
[10]
A.
J. A. Winnubst, A. H. A. Scharenborg, and A. J. Burggraaf. The electrode resist ance of Zr02-Y203(-Bi203) solid electrolytes with Pt electrodes. Solid State Ionics,
14:319-327,1984.
[II]
J. Mizusaki,
Pt,
K. Amano,
S. Yamauchi,
and
K. Fueki.
Electrode
reaction
at
02(g)/stabilized zirconia interfaces. Part II: analysis. Solid State Ionics, 22:323-330,1987.
[12]
B. A.
van
electrochemical
measurements and
Hassel, B. A. Boukamp, and A. J. Burggraaf. Electrode polarization

Ionics, 48:139-154,1991.
at the
Au,
02(g)/yttria
stabilized zirconia interface: Part I: Theoretical considerations of
reaction model. Solid State
61
and
[13]
Wang and A. S. Nowick. Cathodic and anodic polarization phenomena at platinum electrodes with doped Ce02 as electrolyte: II. transient overpotential and A-C impedance. /. Electrochem. Soc, 126:1166-1172,1979.
T. M.
D. Y.
[14]
Giir, I. D. Raistrick, and R. A. Huggins. AC admittance
measurements on sta
bilized zirconia with porous platinum electrodes. Solid State Ionics, 1:251-271,1980.
[15]
D.
at
Braunshtein, D. S. Tannhauser, and I. Riess. Diffusion-limited charge transport platinum electrodes on doped Ce02. /. Electrochem. Soc, 128:82-89,1981.
[16]
M.
J. Verkerk, M. W. J. Hammink, and A. J. Burggraaf. Oxygen transfer
on
substi
tuted
ance
Zr02, Bi203,
van
and
Ce02 electrolytes
with
platinum
electrodes. II. A-C
imped
study. /.
Electrochem. Soc, 130:70-77,1983.
[17]
B. A.
Hassel, B. A.
Boukamp, and A. J. Burggraaf.
Electrode
polarization at the
measure
Au,
02(g)/yttria
stabilized zirconia interface: Part II: Electrochemical Solid State Ionics, 48:155-171,1991.
ments and
analysis.
[18] [19]
O.
J. Velle, T. Norby, and P. Kofstad. The electrode system 02/Pt/ /Zr02:8Y203 vestigated by impedance spectroscopy. Solid State Ionics, 47:161-167,1991.
T.
in
reduction in
Kenjo, Y. Horiuchi, and S. Osawa. Determination of the rate constants of oxygen high-temperature air electrodes on solid oxide electrodes. /. Electro
Y.
chem. Soc, 137:2423-2431,1990.
[20]
T.
Kenjio,
Yamakoshi, and K. Wada. An estimation of the electrode-electrolyte
contact area
by linear sweep voltammetry in Pt/Zr02 oxygen electrodes. /.

Pacey.
Rate and mechanism of response of
Electro
chem. Soc, 140:2151-2157,1993.
[21]
A. Sharma and P. D.
sensor.
zirconia oxygen
/.
Electrochem. Soc, 140:2302-2309,1993.

and S. G.
[22]
C. G.
Vayenas
Controlled Promotion
Neophytides. Electrochemical Activation of Catalysis: In Situ of Catalyst Surfaces, volume 12, pages 199-253. The Chemical
N.
Society, London,
[23]
London, 1970.
1996.
J. O. Bockris and A. K.
Reddy. Modern Electrochemistry, volume 2. Plenum Press,

polarization of Pt, Ag,
Electrode
and Au
[24]
D. Y.
Wang and A.
K.
S. Nowick. Diffusion-controlled
ceria
electrodes with
doped
electrolytes. /. Electrochem. Soc, 128:55-63,1981.

Yamauchi,
and
K. Fueki.
[25]
J. Mizusaki,
Pt,
Amano,
S.
reaction
at
02(g)/stabilized zirconia interfaces. Part I:
theoretical consideration of reaction
[26]
A. M.
rous
Svennson, S. Sunde, and K. Nisancioglu. A mathematical model of the po SOFC cathodes. Solid State Ionics, 86-88:1211-1216,1996.
S. Primdahl. SOFC anode kinetics. In
[27]
M.
Mogensen, S. Sunde, and ture Electrochemistry: Ceramic
and MetalsProc
of the
17th Ris0 Int.
Sci., pages 77-100, Roskilde, Denmark, 1996. Riso National
High Tempera Symp. on Mat. Laboratory.
62
References
[28]
J. R. Macdonald, editor. Impedance Spectroscopy. J. Wiley-lnterscience, New York,

1987.
[29]
J. Van Herle,
A.
J. McEvoy,
and K. R.
Thampi. Oxygen
reduction at porous and
dense cathodes for solid oxide fuel cells. Electrochim. Acta, 39:1675-1680,1994.
[30]
C. Gabrielli. Identifiaction of electrochemical processes
analysis.
1984.
Technical
Report 004/83,
Solartron Instruments,
by frequency response Farnborough, 275-295,

Yttria Sta
[31]
B. A.
van
Hassel.
bilized Zirconia.
Transport and Oxygen Transfer Properties of Ion Implanted PhD thesis, University of Twente, 1990.
on
[32]
G. O. Lauvstad, S. Sunde, and R. Tunold. Oxidation of CO
Ni-point electrodes: Measurement and modelling of impedance. In High Temperature Electrochemistry: Ceramic and MetalsProc of the 17th Rise Int. Symp. on Mat. Sci., pages 339-344, Roskilde, Denmark, 1996. Rise National Laboratory.
kinetics of the oxygen reduction SOFC cathodes. In
[33]
J. Divisek, J. W. Erning, R. Jung, B. Steffen, U. Stimming, and K. Wippermann. The
High Temperature Electro chemistry: Ceramic and MetalsProc. of the 17th Rise Int. Symp. on Mat. Sci., pages 229-234, Roskilde, Denmark, 1996. Rise National Laboratory.
on
[34]
C. Gabrielli, M. Keddam, and H. Takanouti. New trends in the
electrochemical
impedance techniques:
Multi-transfer function
investigatino of analysis. Electro

elec
chim. Acta, 35:1553-1557,1990.
[35]
C. Gabrielli and B. Tribollet. A transfer function
approach
for
generalized
trochemical
impedance spectroscopy. /.
investigation
Electrochem. Soc, 141:1147,1994.
[36]
C. Gabrielli and M. Keddam. Contribution of electrochemical
impedance spectros
copy
to
the
of the electrochemical kinetics. Electrochimica Acta,
41:957-965,1996.
[37]
Phasengrenzreaktionen an Perowskitelektroden auf stabilisiertem Zr02: Implikationen fur die Abgassensorik. PhD thesis, Universitat Tubingen, 1994.
G. Reinhardt.
T. Kailath. Linear
[38]
Systems. Prentice-Hall,
New York, 1980.
[39]
J. D. Powell, and A. E. Naeini. Feedback Control of Dynamic Systems. Addison-Wesley, Reading, MA, 1994.
G. F. Franklin, H. Lauret and A. Hammou. Localization of oxygen cathodic reduction zone at lan thanum manganite/zirconia interface. /. Europ. Ceram. Soc, 16:447-451,1996.
L. R. Velho and R. W. Bartelett.
[40]
[41]
Diffusivity
and
solubility
of oxygen in
platinum
and Pt-Ni
alloys.
Met.
Trans., 3:65-72,1972.
on
[42]
N. L. Robertson and
zirconia cells:
J. N. Michaels. Oxygen exchange
platinum
/.
electrodes in
Location of electrochemical reaction sites.
Electrochem.
Soc,
137:129-135,1990.
63
and
[43]
E. Siebert, A. Hammouche, and M. Kleitz.
Impedance spectroscopy analysis

kinetics. Electrochim.
of
La^S^MnO^yttria-stabilized
40:1741-1753,1995.
zirconia
electrode
Acta,
[44]
J.
L.
face.
Gland, B. A. Sexton, and G. B. Fisher. Oxygen interactions with the Pt(lll) Surf. Sci., 95:587-602,1980.
sur
[45]
A. C. Luntz, M. D. Williams, and D. S. Bethune. The
sticking of 02 on a Pt(lll)
sur
face. /. Chem.
Phys., 89:4381^395,1988. Adsorption

of oxygen
on
[46]
R. Lewis and R. Gomer.

1968.
platinum. Surf. Sci., 12:157-176,
[47]
A. N. and
Artsyukhovich, V. A. Ukraintsev, and I. Harrison. Low temperature sticking desorption dynamics of oxygen on Pt(lll). Surf. Sci., 347:303-318,1996. Somorjai.
Introduction to
[48]
G. A.
Surface Chemistry
and
Catalysis. John Wiley
&
Sons,
Inc., New York, 1994.
[49]
J. Mizusaki and H. Tagawa. Microstructure and electrical property relationships

for
02 reduction in zirconia cells.
In
Proceedings on
Characterization, pages 91-6, The Electrochemical Society.
ture electrode Materials and
Symposium on High Tempera 75-87, Pennington, NJ, 1991. PV
the
[50]
C. G.
Vayenas,
S.
Bebelis, and I. V. Y. S. Neophytides. Non-faradaic electrochemi
cal modification of catalytic
activity:
The work function of metal electrodes in solid
electrolyte
[51]
cells. Solid State Ionics, 53-56:97-110,1992.
A. J. Laub. Numerical linear
algebra aspects
of control
design computations.
IEEE
Trans Autom. Control, AC-30:97-108,1985.
[52]
R. Bellman and K. J. Astrom. On structural

1970.
identifiability.
Math. Biosci., 7:313-328,
[53]
K. R.
Mathematical
Godefrey. The identifiability of parameters Modelling, 7:1195-1214,1986. technique

in
of models used in biomedicine.
[54]
C. Gabrielli, M. Keddam, and J. F. Lizee.

turbation
Frequency analysis
of
temperature per
electrochemistry. /.
Electroanal. Chem., 359:1-20,1993. Electroanal. Chem. and In
[55]
R. D.
Armstrong.
The metal-solid
electrolyte interphase.
terfacial Electrochem., 52:413-419,1974.

[56]
J. E. Bauerle. Study of solid electrolyte polarization by a complex admittance meth od. /. Phys. Chem. Solids, 30:2657-2670,1969.
N. Nardella, D. V. Ho, and S. P. S. Badwal. Galvanostatic current
[57]
interruption
technique
for
C. C. Sorell and B. Ben-Nissan, editors, Ceramic

rum, volume
investigating polarization phenomena electrolyte cells. In Developments; Materials Science Fo

in solid
34-36, pages 237-241,1988.
[58]
F. Berthier,
J.-P. Diard, B. Le Gorrec, and C. Montella. Method for determining the

of
an
faradaic
impedance
electrode reaction:
Application
to metal corrosion rate
measurements.
Corros., 51:105-115,1995.
64
References
[59]
J. N. Michaels. Double layer capacitance of porous platinum electrodes in zirconia electrochemical cells. /. Electrochem. Soc, 138:1494-1499,1991.
E. Walter.
N. L. Robertson and
[60] [61]
Identifiability of State Space Models. Springer-Verlag,
Berlin, 1982.
Cobelli, and L. Finkelstein. The Mathematical Modeling of Metabolic and Endocrine Systems. John Wiley & Sons, Inc., New York, 1983.
L.
E. R. Carson, C.
[62]
Ljung
and T. Glad. On
global identifiability
for
arbitrary
model
parametriza-
tions.
Automatica, 30:265-276,1994.
[63]
Berthier, J.-P. Diard, B. Le Gorrec, and C. Montella. Choice of experimental by structural properties of mechanisms. /. Electroanal. Chem., 399:1-6,1995.
F.
method induced
[64]
F.
Berthier, J.-P. Diard, C. Montella, L. Pronzato, and E. Walter. Sur ridentifiabilite
structurelle de la reaction de
volmer-heyrovsky. /.
Chim.
Phys., 90:2069-2081,1993.
[65]
Steady-state investigation and electro impedance spectroscopy: Identifiability and distinguishability of metal dissolution and passivation mechanisms. /. Electroanal. Chem., 362:13-20,1993.
chemical
K.
F.
Berthier, P. Landau, and C. Montella.
[66]
Sakurai, H. Nagamoto, and H. Inoue. Microstructure of Pt electrodes

and its effects
on
over
solid
electrolyte
1989.
interfacial
impedance.
Solid State Ionics, 35:405-410,
[67]
J. Gauckler. Reaction kinetics of the Pt, 02(g) I c-Zr02 sys tem: state and parameter estimation. To appear in Proceedings of the I lth Interna tional Conference on Solid State Ionics, Hawaii, 1997.
H.
[68]
Okamotoa, G. Kawamura, and
T. Kudo.
Study
a
num
through
observation of
exchange
current in
of oxygen adsorption on plati solid electrolyte concentration
cell. Electrochim. Acta, 28:379-382,1983.
[69]
M. Knudsen. A
tem
sensitivity approach for estimation of physical parameters. Identification, pages 533-538, Copenhagen, Denmark, 1994. IFAC.
In
Sys
65
and
Appendix
2-A.l
State
Space Description of an
space"
Electrical Circuit
by means of a simple example. Consider the electrical circuit shown in Fig. 2-Al.l. The circuit should be familiar to electiochemists. Let us derive the state space model for this partic ular circuit. In the appendix of Part II of this publication, a more complicated
system
The
is treated.
The notion "state
is best introduced
dynamic properties of this system are entirely described for times t > tQ, if the voltage U (t0) and the current I(t0), as well as the input voltage Uu(t) for t > tQ is known. From this information, I(t) and Uc(t) can be determined for t >t0. However, 7(f) and L7c(f) characterize the "state" of the electrical circuit and are therefore called state variables. From a node analysis for node 1
we
find
[Uu(t)
Ux(t)]
C
0
^[Uy(t)
Ux(t)}
(2-Al.l)
^[UyW-U^t)]
and
Kt)
^-[Llu(0-lli(0]-
(2-A1.2)
/(0
o o2
Rl
-O
R2
ua(t)
Uy(t)
-o
o-
Fig.
2-Al.l
RC electrical circuit.The notations
are
given
within the text.
66
Appendix
We
put
L7y(f)
(ground).
We solve
Eq. (2-Al.l)
for
L7a(f)
and sort the dif
ferent terms to obtain
î(')
and
4-(h^]-"i(^
C
Ul
R2
CRl
U(0
(2-A1.3)
similarly for Eq. (2-A1.2)

7(f)
=--.Ul(t)
Rl
Rl
rUu(t).
(2-A1.4)
Eq. (2-A1.3) is called state equation and Eq. (2-A1.4) is called output equation. Form Eq. (2-A1.4) it is clearly seen that 7(f) depends on the input 17U(0 and the present value of L71(t). Because the circuit is a linear and time independ ent system, we can easily write Eqs. (2-A1.3) and (2-A1.4) in matrix form as
x
=
Ax
Bu
(2-A1.5) (2-A1.6)
y
where
Cx
Du
we
used
(A, B,C,D)
are
7(f), u Lf1(f),y Uu(t), and the state space matrices obtained by comparing the coefficients of Eqs. (2-A1.3) to
=
(2-A1.6)
LCRlJ
(2-A1.7)
State-space systems are easily treated numerically (see Part II of this publica tion). The dynamic properties of a system are entirely described by the (A, B, C, D) quadruple and the starting conditions.
67
and
2-A.2
Calculation of
tpb length
from microstructural data

terms
We intend to describe the electrode
measurable microstructural data. coverage of the

can
morphology mathematically in From SEM images (see Fig. 2.2)

as
of
the total
electrolyte surface, Acov,

image analysis.
well
as
the average pore size, d
be obtained from
as a
We will express the
length
of the
tpb,
can
I tib, We
function of these two
parameters.
assume
that the electrode microstructure metal
facing
the solid
electrolyte
be
regarded as a mesh of /char, is introduced, which

A2.1. Let
us
strips (Fig. 2-A2.1).
A characteristic
as
length,
Fig.
2-
reflects the size of the unit cell

as
defined in
consider
Then
/char
we
constant for the moment and let
dp
be the
only
free
parameter.
obtain for the
length
of the
triple phase boundary
'tpb
4rfP T^
char
C-A2-1)
char
-4
-
Pt
tpb
Simplified morphology of noble metal/electrolyte interface.A mesh of noble metal strips is arranged in a regular lattice. The unit cell size is characterized by it characteristic length /char and d is the pore size. The length of the triple phase bound
ary is
Fig.
2-A2.1
parametrized
in terms of the surface coverage
Acov
of the solid
electrolyte
and the
characteristic
from SEM
length Zchar
Both
quantities
can
be estimated with
satisfactory
accuracy
image analysis.
68
Appendix
where
A,,,
is the
apparent
electrode
area.
With the definition of the surface

we
coverage
Acov
(/char
)/lchaT
which
solve for
dp we find
(Â2-2)
'tPb
4/-^VriA7,char
Typical values for noble metal electiodes are in the range of 2-10 pm for l^j. and in the range of 0.4-0.85 for the coverage A^ (cf. Fig. 2.2 and e.g. [7,10,17,
20]).
69
and
70
Chapter
Computer Implementation,
Simulation,
Abstract
In
and
Validation
part
I of this paper
nonlinear state-space model of the

was
Pt, 02(g) I yttria-stabilized zirconia system

structure of the
proposed
In this
and the
one
equations
was
investigated.
part
representation of the model is given. The computer implementation of the heterogeneous chemical and
electrochemical kinetics and the surface
mass
dimensional finite-element
transport
is devel
oped.
The
origin
of the double
upon the electrochemical

sion of the
layer capacitance and its influence impedance (EIS) is discussed. The prob
and numerical
lems of the space discretization of the electrode surface, the exten
triple phase boundary (tpb),
aspects
are
considered. The simulation method is described in detail. The
steady-state current-voltage
ance
behaviour and the Faradaic

K
imped
is simulated for
temperatures from 773

1
are
(900C), and oxygen partial pressures from

different
reaction
,
(500C) Pa to 105
to 1173 K
Pa. Three 1123 K
regimes
discriminated.
Above
overpotentials the reaction kinetics is essentially determined by the charge-transfer step. With increasing cathodic overpotentials, and/or decreasing pQ surface diffusion is in competition with charge-transfer. At tem-
(850C), high pQ
and low cathodic
*)
Submitted to
/. Electrochem. Soc.
Implementation, Simulation,
and
Validation
peratures between
dominated
773 K and 1073 K the reaction is
essentially
supply of atomic oxygen (Oad) via surface dif fusion and dissociative adsorption of 02(g) near the tpb. The charge-transfer coefficient, the electrochemical rate constants, and the activation enthalpy of the charge-transfer reaction can be uniquely estimated from EIS data. The activation enthalpy of the
by
the
dissociative oxygen
adsorption on Pt can be
on
estimated. With elec
trodes of well known geometry the surface diffusion coefficient of
chemisorbed atomic oxygen

ence can
Pt and its concentration
depend
a
be obtained. It is demonstrated that the simulation of

a
micro-kinetic models is
powerful technique
in order to obtain
deeper understanding
Keywords.
double
of reaction mechanism.
Reaction mechanism, electrochemical
impedance (EIS), state-space model,
layer capacitance, digital simulation, Matlab/Simulink.
3.1
In
Introduction
I of the
part
present paper
we
have
presented
general
framework for
modelling reaction mechanisms at noble metal electiodes in solid state elec trochemistry [1]. We illustrated the process of modelling and structural inves tigation by means of a well known reaction mechanism describing the Pt, 02(g) I Yttria-Stabilized Zirconia (YSZ) interface. In a first model (Ml), we considered the dissociative adsorption of oxygen on the Pt surface and the reduction of atomic oxygen near the triple phase boundary (tpb) line. In a sec
ond model included. Is
(M2), surface diffusion of

was
atomic oxygen
on
the Pt surface
was
only one electrochemical rate constant and one charge-transfer coefficient are unknown, whereas the remaining model parameters, such as activation energies or the rate of adsorption and desorp tion, were assumed to be a priori known. We investigated the structure of the
models in detail, showed the condition for their
a
assumed that
identifiability,
steady-state transfer controlled reaction. Expressions describing the behaviour as well as the small-signal frequency response behaviour were also given. However, we have not yet described how the theoretical results
rigorous
case
treatment of the
behaviour in the
presented a charge steady-state I(r\)

of
and
insight into the reaction kinetics of the Pt, 02(g) I YSZ system. In addition, the implementation and simulation procepart
I
can more
from
be used to obtain
72
3.2
Model Implementation
dure has not unknown

It is
one
yet been described and

can
it has not been demonstrated how the
parameters
be estimated from electrochemical measurements.
of the aims of this part to
present the computer implementation of

can
the model
equations
and to show how simulations
be obtained. We
use
high level programming environment of Matlab and Simulink [2], which is widely available for many computer hardware platforms. Detailed instruc tions for the implementation are given in the appendix, in order to facilitate the re-implementation of the models and to encourage the reader to use these computer tools for the investigation of reaction mechanisms. We introduce block diagrams for the description of dynamic electrochemical systems. The steady-state and dynamic behaviour of model M2 is simulated and the simu lation results are compared with experimental results from the literature. We further propose a procedure for the estimation of many of the parameters employed in M2. It is shown that almost any parameter can be estimated from a combination of different measurements and analyses. The difference between theoretical identifiability, as introduced in part I, and practical iden tifiability are enlightened. The limitations of M2 are discussed and improve ments are proposed.
the
3.2
3.2.1
Model
Implementation
Tools and General Procedure
Computer
We have chosen Matlab and Simulink

mentation and simulation of models
as
primary software
an
tools for the
imple
[2], instead using

an
ordinary
program
ming language,
with numerical
such
as
or
Fortran. Matlab is
efficient tool for
dealing
sci
analysis,
matrix
a
zation. Matlab has become

ence
computation, signal processing, widely used computer tool in engineering
and visuali
and is available
are
There
two
an
large number of computer hardware platforms. basically different approaches to implement the set of equa
on a
use
tions into
executable Matlab code. The first method makes
of the
graphical programming extension Simulink in Matlab [3], where the dynamic system is represented as a block diagram. Single Simulink models can be con verted to subsystems which can itself be further built to larger systems; a
property which
for
is
particularly
mass
useful when
treating
finite-difference models
Simulink
dealing
with
transport processes. From
function, the
73
and
Validation
dynamic
behaviour of
system
can
be
investigated
models
can
in time and
frequency
domain. Linear time invariant
(LTI)
be converted between
state-space and transfer function representations.
commonly used in ordinary programming languages, uses the system of equations directly. Explicit state-space descrip tions are obtained by linearization of the state equations as described in part I. Each methods offers specific advantages; in fact both approaches are useful and are best employed in conjunction. When dealing with small mod els (i.e. if the number of state variables is below -50), model implementation in Simulink is considerably faster and more intuitive. In addition, the loss in performance during simulation is negligible. We mainly use the graphical
The second
approach,
which is
programming
environment.
a
The overall strategy to solve
problem
can
be summarized
as
follows:
(i)
by building a block diagram Simulink or by writing ordinary (C like) Matlab functions. Implement
Make the
lab
the model either
in
(ii)
physical and kinetic constants available to the Mat workspace. Estimate some reasonable values for the
unknown parameters.
(iii)
Determine the
steady-state
=
values for the state variables from
the condition
dx(t)/dt
(initial conditions).
in
(iv)
Run
large-signal
simulations
the time domain of the
non-linear model
(Simulink
or
Matlab
function),
or
(v)
generate
nal time
(linearized) state-space model of the non-linear
model and compute the
frequency
response
or
the
small-sig
dependent
behaviour.
3.2.2
Heterogeneous
Chemical and Electrochemical Kinetics
The
primary objective
balance
concern care
of these
procedures
is to
implement
the
mass
and
is
charge
no
equations
into the
computer suitable for simulation. There
need to
about the time discretization of the
equations
for Matlab
the
takes
entirely
of that. It is, therefore, not necessary to know
precisely
74
3.2
nature
of the numerical
may be
helpful
in
integration techniques, although choosing the appropriate algorithms

can
or
basic
knowledge
for simulations in
time domain. Basic details
be found within the handbooks of the pro
gramming
environment
in textbooks about numerical mathematics
[3-5].
As it is the first time where electrochemical
systems
are
treated with this pro
gramming environment we put some emphasis on the actual implementation the model. Implemen process in order to facilitate the re-implementation of tation details specific for Matlab and Simulink will be given in the appendices
3-A.3 and 3-A.4.
We
use
the non-linear state-space model Ml

the
developed
in
part
I of this
cation
as
starting point
obtained
as
for the
implementation [1].
The
mass
and
publi charge
balances
were
h-
êC>P)
2kadpoN0-[l-Q(t,p)]2-2kdesN0-Q(t,p)2
(3.1)
-[Vol-^t.p).^.^^
+
[00]-[i-e(t,p)] fc!qe2(1-p)/n(0
gl:
IF
2N0FAax [- [V0] 9(f, p)
k? e~2mn
(3.2)
[00]-[l-e(i,p)].^-e2(1-p)/,1(f)]
unknown
with
the
vector
of
the
parameters
[klc, (3],
and
fclc exp[-Ea/RT] exp[-2(3/E symbols was explained in part I or can

=
fc^q
]; the definition of the remaining

be found in Table 3.1 of
u
A.l. Let
us
rewrite
=
Eq. (3.1)
with
Q(t, p) (state variable),
appendix 3i\(t) (input
quantity), kt
*
=
[Vq]
k\q, and kb
(1"
"
[00] ke-q

as
2kadPo2M0
*)2 2*:desN0 x2
+
(3.3)
-
-krx- exp[-2p/u]
kb (1 -x) exp[2(l
p)/w]
The first two terms
adsorption and desorption of oxygen on the platinum surface. These reactions takes place on the entire cathode surface and are not restricted to the tpb area as the electron transfer reaction is (terms three and four of Eq. (3.3)). The model Ml is completed by adding the equation for the charge balance. Using y lF(t,p) and the same abbrevia tions as in Eq. (3.3) we write
are
related with the
75
and
Validation
2N0FAa[-k(
(3.4)
can
<f2P/M + kh
(1 -x)
2(1-P)/m
(3.4)
implemented into a Matlab function or into a Simulink block diagram. Appendix 3-A.3 gives more detailed information about the Simulink implementation of model Ml and most of the Matlab commands used for simulation. The following gives an overview of the capa
Eqs. (3.3)
and be bilities of the method. The initial condition for the state variable,
x
=
x0, is obtained
by solving
only the first two terms must be taken into account and the well known analytical solution of the Langmuir equation is obtained (cf. 3-A.3). The time dependent behaviour of the system from any starting point towards the steady-state point can be followed by choosing an appropriate simulation algorithm and appropriate step sizes. Simulation results can either be followed directly within the Simulink envi ronment or by writing the simulation results into the Matlab workspace. Lin earized state-space descriptions of the models can be obtained by following either of two routes. First, analytical expressions for the state-space matrices A, B, C, and D can be obtained by linearization of Eqs. (3.3) and (3.4) as described in parti. This can be done for both Ml and M2, although it becomes tedious doing so for multi-compartment models. From linearized state-space models (SSM) the frequency response and the small-signal time dependent behaviour can be obtained at the corresponding operating point. Note that the linearized SSM can not be used to simulated the large-signal time dependent behaviour, such as potential-step responses or cyclic voltammetry. The second approach circumvents these limitations. The function "linEq. (3.3) numerically
x
=
for
0. If
0,
mod" from Simulink is used to extract numerical estimates of the state-space

matrices
from the
non-linear Simulink block
approach has the advantage that both small-signal behaviour of the model can be
and without the need to obtain
diagram (cf. 3-A.3). This the large-signal behaviour and analysed with one representation
(lengthy) analytical expressions for the state-space matrices. However, during the early implementation stage it is often useful to follow both routes simultaneously in order to validate the model implementation. In addition, Simulink offers the function "trim" which enables to determine steady-state equilibrium points from (non-linear) sys tems in block diagram representation (cf. 3-A.3). This is especially useful when the steady-state values for the state variables are needed under the con dition where an overpotential is applied, i.e. when a current flows. Under
76
3.2
these conditions it is
generally
as
not
possible
to solve
=
equations
or
systems of
equations
of the type such
Simulink block
diagram of Ml
0 analytically. Eq. (3.3) for x is given in appendix 3-A.3.
The
complete
3.2.3
Surface Mass
Transport
different methods to deal with
There
are
basically
two
partial
differential
equation (PDE) systems numerically.

The second method, which finite-difference
we use
The first is the collocation method
[6].
it
in this paper, is the method of the
approach [7].
Whereas the first
technique
is
more
elegant,
generally requires more mathematical treatment. We employ the simplified model of the electrode morphology developed in part I. The height of the Pt stiips is assumed to be equal to the thickness of the electrode layer (Fig. 3.1 a). The z axis is divided into compartments of increas ing size directed away from the tpb line (Fig. 3.1b). However, there is no need to discretizise the electrode surface over its entire thickness, but only to a cer tain extent which is in the order of the Nernst diffusion layer (see below). The concentration of Oad is considered to be homogeneous within the compart
ments.
For
digital simulation it is convenient to rewrite sion along the z -coordinate in the form [8]
Fick's second law for diffu
I ^35
In
D>S a-lH!i)2
"
D>8dz'
(3'5)
part
we
assumed that D does not
depend
on
the concentration. Accord

term.
treat
cen
ingly,
the first term in
However, it is
tral differences
and out of
a
Eq. (3.5) vanishes and we are left with the second obvious that Eq. (3.5) is the starting point for a refined
are
ment of surface diffusion. The space derivatives
approximated
with
(see e.g. [7]). The diffusional flow/ (mol/(ms)) of Oad

is obtained from
into
compartment
/i
1, i
DicrNA
N0
xi -1
Az;
xi
i-l
Az,
2 )
and/'i,i
DaT
v
xi
AZ:
xi +
AZ;
1
+
(3.6)
1
V 2
77
and
Validation
a)
h,3
>3,2
1
=
HO
h,3
ii
J3,2
i
=
HO
Jl,2
z
>1,2
b)
x,(0
YSZ
i=l
tpb
Fig. 3.1 Simplified electrode geometry and one-dimensional finite element model. (a) 3-dimensional view of porous Pt on solid electrolyte according to the 2-dimensional
developed in the appendix of part I. d is the pore diameter and Zchar is the char acteristic length. Gas mass transport is considered to be infinitely fast in the Pt pores, (b) The plane (ABCD) is discretizised in compartments of increasing size starting with the tpb compartment of width w (= Az{). Mass balances are formulated for every compart ment. In addition, for the tpb compartment the charge balance is formulated.
model
78
3.2
where Xj is the surface coverage of
of surface sites
on
Pt
Oad in compartment i, N0 is the number (atoms/m2), NA is the Avogadro constant (mol-1), and
mass
Azj
is the width of
compartment i (m). The

as
balance
(mol/s)
for
com
partment
i is obtained
Ai7n
dc-.
~
ldt
*'
Oi-l,l-/i,i l)
+
(3.7)
where
A{
is
Azf
xi
is the
area
of
compartment i,
of
mass
t is the width of the pore,
and
Cj
the
surface concentration
we
Oad
in
compartment
i. i
With
ci
N0/NA
dxi
finally
find for the
balance of
compartment
a Az-
D
=
dt
Az./2
(3.8)
x
Az;
*i-l"
+
i-l
Az
V
AZ:
i-l
AZ;
xi
+
1
/
Az
AZ:
AZ:
AZ;
or
in short form
Az;
dc-
1
~
dX:
rp
1
"
~2D~'Tt
where
rTt
i-l.iî-l 'fli,ij:i
ai,i + la:i + l
(3.9)
T{
Az{ /(2D)
is the time constant of the diffusion process in
com
partment /, and the ai are numerical factors which and the boundary conditions.
The
depend on the geometry
state-space model is realized by writing the mass and charge balance equation for every compartment using the following initial and boundary
conditions:
(i)
Initial conditions: the surface concentration of
Oad
is homo
geneous before
establishing an external disturbance.
79
and
Validation
(ii)
Boundary
conditions at
an
infinite distance
a
co
from the elec
sufficiently large distance from the interface the concentration of Oad is equal to the equilibrium surface concentration x0 determined by the an<^ adsorption/desorption equilibrium (c(o i xo 0). AZco i trode/electrolyte
interface: at
=
(iii) Boundary conditions
in the
tpb compartment:
the interface is
blocking for surface diffusion; the Faradaic current is equal to the charge balance; the electron transfer reaction can only take 0 and Azt b x oo. place in this compartment; i.e. ct b x
= =
_ _
boundary compartments can be conveniently obtained from the following argument: if the boundary is blocking we put either Azj _j or Az{ , depending on which boundary is blocking. +1 If the concentration of a neighbouring compartment is taken to be constant with time, we put Az{ 0. Starting from the tpb compartment we increase +1 the size of every successive compartment by a factor of q. Accordingly, we obtain an approximate state-space description of M2:
=
=
Note that the a{
of the
dx-.
2kadpoN0 (1
-krx1
dx{
Tt
+
xx)2
2kdesN0 x2
(3.10)
kh.(l-xl)
^-Tl-qx1 T]-qx2)
+
l:
2*adPo2No
(1
*i)2
+
2kdesN0 x2 +
(3.11)
TJ^Tq^-1
dx
co:
(0
~Xi
T7~qXi
-
l)
'
~di
2fcadPo2^0
1
(1
*o)2
+
2fcdes^0
+
(3-12)
q
+
TuKl
where denotes
q**-1
2q
_
l+qXa>
X> +
1)
co
=
the
outmost
compartment
facing
the
region
with
* +
xo-
80
3.3
The
by putting Eqs. (3.10) to (3.12) into a Simulink block diagram (see appendix 3-A.4). The implementation of the tpb compartment almost corresponds to the implementation of Ml with the dif ference that the terms for surface diffusion are included. The charge balance complete
model M2 is obtained
is still
The
and
xx. given by Eq. (3.4) where Aa must be replace with Azx t and x remaining compartments account for the adsorption/desorption process the surface mass transport. More details concerning the implementation
of
mass
transport
in Simulink
are
given
in
appendix 3-A.4.
3.3
3.3.1
Model Initialization and
Sensitivity
the numerical values of all constants
The models and
are
initialized
by making
parameters available to the Matlab workspace. The values for the parameters which are (assumed to be) a priori known are given in Table 3.1
(appendix 3-A.l).
These values
are
used for the simulations if not otherwise
stated. It should be mentioned that there is much information available in the literature about the faces
adsorption
and
desorption dynamics
of
02(g)
on
Pt
sur
(see model
M3 in
[33]). The
kinetic rate constants
were
chosen while
in
taking
into account most of this available information
(see references cited
Appendix 3-A.l). Note that the activation enthalpy of the electro chemical reaction is also reasonably known [9,10].
Table 3.1 of
run
simulations,
=
some
values must also be chosen for
[klc, (3]. Often one can obtain reasonable esti mates of unknown parameters by considering the static properties of the sys tem. This is exemplified in the following. Assume that we would like to 1 atm. Assume that Rt has obtain an estimate for k*{q at T 1000 K and pQ been determined experimentally as Rt 10 Qcm2 for an electrode of 1 cm2 of find From the relation we RT/(2F) l/iQ apparent area. Rt [ VQ] fcf x Using i'0 4.3 mA/cm2. This value should be close to 2N0FA the parameters given in Table 3.1 and with Aa w /^b, where w is the width of the tpb compartment and l^b is the length of the tiiple phase boundary, a numerical estimate of k\q is obtained if x is calculated for the
the unknown parameters p
= = =
temperature and pQ considered. Other

similar way.
reaction rates
can
be estimated in
81
and
Validation
Once the
estimates
priori
known
parameter values and the approximate parameter
are
made available to the Matlab
workspace,
simulations
can
be
goal of a study is to determine accurate estimates of unknown model parameters, it is generally not sufficient to test for (theoretical) identi fiability of the model (cf. [1]). Obviously, a further necessary condition for accurate parameter estimates is that the model frequency response shows a
obtained. If the
high sensitivity
sensitivity
with
respect
to the
parameters [11]. The relative parameter

to
magnitude obtained numerically [11]
of the
of
ZF(jco)
each
parameter p{
is
easily
S1(0)
.to(^|ZF(i.)|-Kg55|).
parameters
(3.13,
In addition, the correlation between the
must be low in the inves
tigated frequency
range.
3.3.2
Penetration
Depth
and
tpb
Width
Consider
porous Pt electrode of thickness L
(cf. Fig. 3.1a). So far

be
we
have
only
stated that the finite difference
approach will
But
we
employed
we
for the treat
ment of the diffusion
equation [12-14].
have neither fixed the distance

nor
up to which
we
intend to discretizise the surface
have
fixed the width

We have also
of the surface
not
compartments (especially the tpb compartment).

we
yet decided how many compartments
should
use
for this purpose.
question is generally treated with the concept of the Nernst diffu sion layer thickness or penetration depth, 8 [14-16], whereas the remaining questions must be treated with intuition and physical insight. It was stated above that there are two concentration boundary values, not 0 and xQ at z <*>. In a strictly determined by surface diffusion: xx(t) at z
The first
=
mathematical sense, concentration

an
perturbations
at the
interface, i.e. due
to
applied overpotential, have an effect up to an infinite distance from the interface. In practice, however, there is a limit beyond which changes can be JUx and x is the neglected. This value is generally set to 68 where 8 experimental time interval [14,16]. This approach works fine for time-domain simulations but may it also help for simulations in the fre quency-domain, i.e. for electrochemical impedance simulations?
=
82
3.3
77C 900
800
700
600
500
l(f
T=973K
\ \
\
10 20
30
10i
ReCZp/Q-crrT)
S-H
102
com
/(rad-s-1)
exp[21.11
117.6103 K/ffiT)]
10J
pn
=
U2
10D Pa
j i i
i_
0.8
0.9
1.1
1.2
1.3
103K/7;
Fig.
and
3.2
Temperature dependence
of C0max. The definition of comax
can as a
be
seen
in the
inset of the
figure.
The maximum of
-Im[ZF(jco)]
was
determined
function of T
p02.
The
quantitative
relation between comax and T is

were
parameters given
in the
ence
in Table 3.1
used. The inset shows

=
complex plane
obtained at T
973 K and pQ
figure. The typical impedance 105 Pa. A perfect pQ/2 depend

given
within the Faradaic
a
is found for comax at constant
temperatures from
773 K
(500"C)
to 1073 K
(800C)
(not shown).
83
and
Validation
Analytical
sional
solutions for the Faradaic
impedance
are
available if one-dimen
is
surface
diffusion
(semi-infinite medium; without adsorption)
Warburg impedance is obtained at high frequencies and a perfect semi-circle is found at low frequencies in the complex plane (see inset of Fig. 3.2). The frequency of the maximum value of the imaginary 8 J(Omax/(2D) component, comax, is related to 8 by the expression 2/ Jk [15]. We have obtained simulations for ZF(jco) with the parameters given in
present [15].
A classical
=
Table 3.1 from T for

a
773 K
w
=
(500C)
10
nm.
to 1173 K
fixed value of
105 Pa to 1 (900C) and p0i The temperature dependence of comax

=
Pa is
shown in
Fig.
3.2. A pQ
dependence
was
of comax is found
the temperature range, which

Thus
found
by
others
we
by simulation over experimentally [15, 17].

limit the space discreti
having
found
as
an
expression
for comax and 8,
zation to 68
described above.
we are
Once 8 is determined,
left with the
question
about the number of
com
partments and the

ments
size of the
tpb compartment.
The number of space ele
required for a successful simulation can be reduced drastically by using a space grid with small space elements in the region near the elec trode/electrolyte interface. Joslin and Pletcher [14] and Feldberg [18] have
discussed
some
suitable transformation functions for the space variable with
regards to computing time. The function of Feldberg is an exponentially expanding sequence of box widths. We use increasing compartment sizes which expand according to a geometric series with a constant factor q. With 1.5 < q < 2 this transformation is close to the proposed transformations from Feldberg and loslin and Pletcher, but without making the implementation more difficult. Thus, as soon as we fix the value for the tpb compartment, the number of compartments can be determined from the length 68 and the con
dition for q.
There has been much debate about the extension of the
tpb
of
Sr-doped
LaMn03
trode
cathodes
on
YSZ
(see e.g. [19,20]). There

electrodes is low
is
agreement that the elec
conductivity of these length of the tpb at zero or

of mixed
approximately proportional to the overpotentials. For higher cathodic overpo

to increase due to the
occurrence a
tentials, the extension of the tpb is believed
conductivity of the
cathode at the interface
[21]. Similarly,
propor
tionality
between the electrode
conductivity
can
ae and the
on
length
of the
tpb
has
been determined for porous Pt electrodes mixed conduction in noble metals

the extension of the
YSZ
[22,23].
It is clear that
be ruled out. However, the ideas about electiodes
tpb
of
electronically conducting
metals)
are
(LaMn03
at
equilibrium potential
and noble
sparse.
Wang
and Nowick
[24]
84
3.3
proposed a model where oxygen is supplied by surface diffusion towards the tpb and subsequently diffuses laterally in the two-phase region between the electrode and electrolyte. But, from the rather low solubility and diffusion coefficient of oxygen in bulk Pt [25], we expect this contribution to be negligi ble at bonded (i.e. sintered) interfaces between Pt particles and YSZ. In addi tion, this model is rejected by others [15,26]. Thus, we are left with the picture that adsorbed oxygen is reduced and incorporated near the tpb.
modelling point of view it can be assumed that the election transfer reaction takes place in the tpb compartment of width w. It is thereby not rele vant whether the real process takes place on the Pt surface, between the Pt
From the
grain
these
and the YSZ surface,
on
the YSZ surface,
or
whether
combination of
possibilities
area
takes
place.
The model accounts for the reaction
irrespec
to the
tive of its location. However, the Faradaic current active
IF
is
proportional
lt b w and to the electrochemical rate constants. We feel intuitively that doubling w should doubling the current, and therefore halve the polarization resistance Rp. But what happens, if we keep the product w klc constant and change, for example, the value for w in a certain range? If the Faradaic impedance ZF(jco) was independent of the choice of w (at least for a certain range and when the constraint is applied), we would be released from the task to assign a value to w. In this case we would state that there exists a strong correlation between w and klc. Let us first consider ZF(jco, p) of model Ml [1]
Aa
=
ZF()(o,p)
Rt
1+
*f + *b
jco + 4/cadNoPo
(1
x)
4fcdesN0
(3.14)
where
R-1
It is
w
M0F-zvltpb-[(l-P)f-kh-(l-x)
W-krx]
(3.15)
immediately seen that Rt is insensitive to changes of w, if the product klc is kept constant (note that kb is expressed in terms of k( and remem
fcf). However, the fraction within Eq. (3.14) is strongly sensitive to changes of w if w klc It is not a priori clear how the const behaviour of model M2 will be. Certainly, Rt will exhibit the same properties as in Ml. The sensitivity of Ze(jco) with respect to w should be investigated numerically.
=
.
ber the definition of
85
and
Validation
In absence of detailed information

assume w
we
set
10
nm
for the moment. We
to be
independent
area
of
temperature and oxygen partial pressure.

the active
seems area
With
/^b
in the order of 1
pm/pm2,
will be in the order of 1%

a
of the
apparent electrode
examined
which
to be in
reasonable range. The
problem will be
numerically below.
3.3.3
The Double
Layer Capacitance
capacitive behaviour,
little
While it is clear that electiodes in SOFC do exhibit

attention has been
paid to the nature and the magnitude of the double layer at the electrode/solid electrolyte interface. In addition, there has been some confusion in the literature about the terms 'double layer capacitance' and 'pseudo-capacitance'. We believe that equivalent-circuit models have contrib uted to this confusion. We will give a brief description of the physical phe nomena which lead to the occurrence of "capacitive" behaviour and we will estimate its order of magnitude for a real porous Pt cathode. First, we expect a double layer capacitance at the metal /solid electrolyte interphase. For the moment, we consider the interface as blocking for elec tions and oxygen ions. It is generally agreed that the measured capacitance Cdi of metal/solid electiolyte interphases is a series combination of a diffuse layer capacitance Cd and an inner layer capacitance Q, since there is a mini
mal distance between the oxygen ions and the Pt ions
(assuming
The
boundary
between the metal and the

is
electrolyte) [27-30].
[28]
sharp inner layer

a
capacitance
generally
estimated from
Af, Aov e0e/r
(3-16)
where A, is the apparent electrode area, with electrode material, e0 is the
Acov
is the
electrolyte
e
coverage
permittivity
r
of vacuum,
is
an
effective die
lectric constant
(of order (1
1),
and
is the distance between the metal electrode
and the centres of the oxygen ions therefore be between

to
(a few tenth of
It is
nanometer). Q should
10) uF/cm2.
slowly varying function,

perature
ent
on
of interfacial
expected to be independent, or a potential. Since the concentration of
oxygen vacancies in YSZ is fixed

is to increase the ionic
by the content of yttrium, the effect of tem mobility. However, e and r could be depend
the
potential and/or
the
temperature.
86
3.3
completely blocking electrodes without specific adsorption (of the diffuse double layer oxygen ions at the metal-solid electrolyte interface), is described by (z+ z_) [31]
For the
case
of
c<-A-4-<*{-m)
where
=
=
(3-17)
0) measured relative to 4> at <J>0 is the potential at the interface (x x oo, LD is the Debye length (i.e. the extension of the perturbation in con centration into the electrolyte due to the electric field), and the other symbols have their usual meaning. The Debye length is given by
^d
( ee0RT
=
V/2
(3.18)
2z F cxJ
where cx
is the concentration of mobile ions. However, the
theory
of diffuse
layers assumes mobile point charges and relatively low concentra tions of ionic species. Robertson and Michaels [32] have discussed the possi bility of a diffuse double layer in YSZ in terms of Eqs. (3.17) and (3.18). They
double estimated values for
828 K
LD
between 2.85
nm
at 968 K
(695C)
and 15.4
were
nm
at
(555C). The authors

with this
stated that their

In
experimental
results
in disa
greement
in YSZ is
theory.
addition, since the concentration of oxygen ions
high, it is unlikely that any diffuse layer effects will contribute to Cdl. Using a typical oxygen vacancy concentration of 4.6103 mol/m3 we obtain a Debye length of -0.015 nm at T 1000 K. Thus it is assumed that Cdl is essentially determined by the inner layer capacitance. This implies that the value of Cdi should be basically independent of temperature, oxygen partial pressure, and applied overpotential. Cdl should, however, be dependent on the coverage of the electrolyte surface with the noble metal. In addition, there may be some specific adsorption of oxygen ions at the metal/solid electrolyte
=
interface be present.
There
are
few reports
on
the
investigation
of double
layer capacitances
of
porous metal electrodes
on
YSZ solid
electrolytes.
can
Robertson and Michaels
[32] have given
summary of the values which

are
be found for Pt electrodes
in the literature. The values
in the range of 30
to 1073 K
uF/cm2
to 350
uF/cm2
at
temperatures between
obtained
673 K
(400C)
(800C). These values

EIS data.
were
by fitting equivalent
circuits to
experimental
Obviously,
87
and
Validation
these values
are
too
high to
account for pure inner
layer capacitances.
In
con
reported rather low values between 0.3 pF/cm2 and 1.3 pF/cm2 from potential step chronoamperometry [32]. They fitted experimental current-decay curves to the equivalent circuit
trast, Robertson and Michaels itself have
shown in
Fig.
3.3a. The authors have claimed that the initial current after
=
potential step should decay exponentially with a time constant of x CdlRe is much larger than the when the polarization resistance of the electrode, Rp, resistance Re. From an evaluation of the eigenval uncompensated electiolyte ues of the equivalent circuit shown in Fig. 3.3a and Fig. 3.3d we see that the proposed relation between x and Cdl is approximately met if Rt > 2Re (cf. 3A.2). The condition Rp Re is a necessary one. Unfortunately, the first con dition is rarely fulfilled experimentally even at relatively low temperatures [33]. We believe that the estimated Cdi values from Robertson and Michaels
are a
factor of 2 to 10 too low electrode
(see 3-A.2).
Higher
termed
capacitances (between -0.1 mF/cm2 to lm F/cm2, usually "pseudo-capacitances" [19]) are usually obtained by fitting experi
mental data to Tab. 1 in
equivalent
circuits of the
type shown
in
Fig.
3.3 b
(see also
to the
[32],
a
and
[19, 34]). These high values have been attributed
layer between the metal surface and an adsorbed layer of oxygen atoms or ions. Assuming a complete coverage of the metal surface with atomic Oad species of radius -0.06 nm, we obtain (Eq. (3.16)) a capaci tance of -18 pF/cm2. Smaller coverages imply smaller values. Note that for this capacitance contribution the Pt surface area is of relevance. Typical val
presence of
ues
double
for porous Pt electrodes

et al.
are
in the range of few

an
cm2 (thickness
<
50
pm).
Vayenas
have
proposed
that
"effective electrochemical double

of oxygen ions from the
is established due to
backspillover
in the
spread over pensating (screening) charge

subject
to
a
These ions
the metal surface and
Oad are accompanied by their com metal, thus forming surface dipoles [36].
Pt
layer" tpb [35].
With XPS the authors found two
types of chemisorbed oxygen on
surfaces,
prolonged anodic current treatment. If these surface ions contrib ute to the double layer capacitance, experimentally determined values for Cdi should be dependent on the surface area of the porous electrode (i.e. its thick ness and microstructure), on the applied overpotential, and on the tempera ture, because the equilibrium concentration of adsorbed atomic oxygen on Pt strongly decreases with increasing temperature. However, values below 100 uF/cm2 are expected for typical porous Pt electrodes. There is considerable experimental and theoretical evidence that capacitance values above 100 pF/cm2 are almost exclusively caused by Faradaic proc-
88
3.3
-dl
a)
R.
C,
C2
b)
Ra
Rt
Rn
c)
ZF(jco)
'dl
d)
/? R, /?
equivalent circuits for fitting experimental EIS data.(a) Simplest electrolyte resistance Re, the electrode resistance R and the double layer capacitance, (b) Circuit often found in the literature to fit experimental impedance data where two semi-circle or one broad semi-circle is observed. Numerical fit leads to capacitances in the order of (0.1 to 1) mF. (c) "Equivalent circuit" proposed to determine Cdl, Re, and Rt. No assumptions are necessary for the concentration imped ance Ze(jco). (d) Simplified version of circuit shown in (c). The circuit may account for depressed semi-circles or broad semi-circles in the complex plane.
Fig.
3.3
Electrical
circuit to account for the
89
and
Validation
esses
[37, 38]. The
occurrence
of this behaviour
can
be
easily
understood in
electiolyte systems, as we have shown in part I [1]. These Faradaic processes take place on the metal surface and near the tpb, i.e. they occur in parallel to the double layer charging. This justifies the proposed general equivalent circuit shown in Fig. 3.3c. A blocking interface would simply consist of the electrolyte resist ance in series with the double layer capacitance. The splitting of ZF(jco) into a series combination of the charge-transfer resistance Rt and the concentra tion impedance Ze(jco) has been justified in part I. In model Ml we deter
mined
a
terms of the
dynamic properties
of these cathode/solid
capacitance
C
(4
kadNQp0i
(1
0)
4fcdesN0e)
(3.19)
obviously depends on the rates of adsorption and desorption, as well as on the steady-state concentration of adsorbed atomic oxygen, 8. We imme diately see that C increases with decreasing oxygen partial pressure which is in contradiction to the idea of "pseudo-capacitances" (decreasing p0 lead to lower surface coverages). Note that the occurrence of this capacitive behav iour is entirely caused by the dynamics of the oxygen reduction at the inter face. However, if experimental data are fitted with an equivalent circuit of the type shown in Fig. 3.3b it is expected that high values for Cdl will be esti mated. But, as we stated in part I, parameter estimation requires that the pro posed model may reasonably well describe the behaviour of the real system. Fitting inappropriate model structures to experimental data will give errone ous parameters or even parameters without any physical relevance, even if the "fit quality" is excellent! The use of equivalent circuits of the type shown in Fig. 3.3b is discouraged. We have put some emphasis on this point for two important reasons.
(i)
which
dynamic properties of the electiode/electrolyte interface are reflected by the Faradaic impedance ZF(jco). The experimentally determined imped ance Z(jco) is always obscured by the double layer capaci
aware
We must be
of the fact the
tance,
as
we
have shown above. For
discussion of the
properties
of the interface it is therefore
required
to obtain
Z(jco). Fitting experimental data to an equiva lent circuit may give completely wrong estimates for Cdl and
Zf(jco)
from
90
3.3
Rt, because we first have to choose an equivalent circuit. Unfortunately, we do not know whether the structure of the chosen circuit is appropriate or not. In addition, simple equiv alent circuits can never fully account for the complex reaction
mechanism which is
a
further
source
of
error.
We have
a
already
mentioned that Berthier et al.
[39] have proposed
method which allows for the determination of
Cdl
without
assuming
(ii)
an
equivalent circuit.
is to
The second
important point Cdl

is
recognize
that
an
accurate
accu
estimation of
rate
is
mandatory prerequisite
to obtain
values for the
estimate of
estimation
Rt
on
charge-transfer resistance Rt. An accurate required if one aims to carry out a parameter
experimental
are
the
data. For Ml and M2
we
have
shown that these models

if
not
globally
identifiable with EIS
Rt
is not known
[1]. This
statement
follows: if
Rt can not be determined losing one (important) equation in the parameters. This fact generally drastically decreases the global identifiability of a system. We will illustrate these points in the following sec
tion.
generalized as independently, we are

can
be
3.3.4
Digital
Simulation and Numerical
Aspects
ver
The simulations
were
obtained
by nmning
version 4.2 c of Matlab and
sion 1.3 c of Simulink
on a
Sun SPARCstation 20
running
can
the Solaris 2.4 oper
ating system.
ble
The Matlab
Optimization
and Control
System
be
Toolboxes with
were
used in addition. However, most of the simulations
run
reasona
mid-range personal computer using the student editions of Matlab and Simulink. It is beyond the scope of this paper to discuss in depth the details of Matlab and Simulink. However, with a basic familiarity of the programs and together with the information given in the appendices 3-A.3 and 3-A.4 it should be possible to re-implement the models and to run simu lations. We believe that this is a good starting point to write own programs. The following information is addressed to the reader familiar with the pro
on a
speed
gramming environment.
91
and
Validation
stability problems during simulation of the time dependent behaviour when using an inappropriate integration (e.g. Runge-Kutta or Euler method) algorithm due to the stiffness of the mass balance equation. By using the "gear" method with appropriate step sizes we were able to circum vent these problems. Steady-state values for the state variables were reliably determined with the Simulink function "trim" for any physically reasonable values of the overpotential 11. Appropriate starting values for x and y were
We encountered
given
while
u was
fixed. The state-space vector determined with "trim"
was
used for the extraction of linearized state-space models with the Simulink function "linmod" at the bation level of
corresponding operating point.

The
The default
pertur
for the
10"5
was
used. Different levels could be set to
probe
was
validity
of the linear
regime.
conditioning
of the system
achieved
through the scaling of the state variables with the maximum number of adsorption sites, N0. The values for the input and output quantities were in the range of unity for the chosen geometry, thus no further scaling of these
values
was
necessary. The condition number of matrix A obtained with the

was
Matlab function "cond"
generally
below
104, indicating
that the
prob
lem
was
well conditioned
obtained with the Matlab

mates for the inverse
([40], p. 1-66). Frequency response data were functions "bode" or "nyquist". Numerical esti
resistance R~
were
polarization
conveniently obtained
with the Control Toolbox function
"dcgain".
3.4
3.4.1
Simulation Results
Charge-Transfer Controlled
current
Kinetics
results obtained
K
Exchange
Pt,
density i0.
Experimental
on
the system
02(g)
to
zero
high temperatures (above -1123 moderate cathodic overpotentials indicate

I YSZ at
(850C)), high pQi, and [9,10,41,42]. We

occurs
can near
that the oxygen reduction
under these conditions is
charge
transfer controlled
expect such
the
behaviour if the concentration of adsorbed atomic oxygen of the current
tpb
is
independent
to
through
the interface. This
if the
rate of surface
diffusion and/or the rate of dissociative

near
adsorption
assume
is fast
compared
the electron transfer rate
the
tpb.
We
for the broad
moment that the electrode kinetics is
charge-transfer
controlled
over a
range of temperatures.
92
3.4
Simulation Results
If, and only if, the electrode reaction is dominated by the

process at the
charge-transfer
=
tpb,
then the
following holds (with

RT
=
2 and
[1]) (3-2)
'o
Sf
2F
,._nx
Rt(n=0)
Rt(r| 0) is the charge transfer resistance at equilibrium potential. If Eq. (3.20) applies, the electiode properties can either be described by Rt or iQ. A quantitative expression relating the exchange current density i0 with the T as well as at arbitrary temperatures is oxygen partial pressure at T
where
=
given in part
I of this paper
[1].
At T
T the
expressions
reads
as
f0(r,pO2)
Fig.
2N0Fklc[Vo]
f^} l+K(T)Jp02
of
Po2l~W1
(3-21)
partial pressure experimentally by a temperature. 1/4 number of authors [9, 43, 44]. They found approximately a p0 dependence of i0 at low oxygen partial pressures and a p0 dependence at high oxygen 1/2. partial pressures. This follows immediately from Eq. (3.21) with P
3.4 shows the calculated
on
dependence
iQ
on
oxygen
and
A similar behaviour
was
obtained
one-quarter dependence of i0 on p0 was first analytically obtained by 1/2 and they consid Wang and Nowick [9]. However, they assumed P
The
=
ered the
Langmuir equation 9/(1-8)

->
K(T)Jp^
under the
limiting condi
on
tions of 9
0 and 9 1
on
(see [9] for details). From the available data
oxygen
are
adsorption
Pt it is
questionable
whether these
limiting
conditions
experimental situations considered [33]. However, the one-quarter dependence is also obtained without the simplifications of the Langmuir equation, as we have shown in part I. Note that the p0 depend ence is also a function of the charge-transfer coefficient P. This property has
reached under the
not
yet been stated
in the literature. A measurement of
i0(po )
may reveal the
value of
p accurately and uniquely.
The oxygen
partial
pressure where the maximum of

It is
decreases with
decreasing temperature (Fig. 3.5).

1-2P
+
i0 occurs, given by [1]
p0 *,
P2
^K(T)
1-P PK(T)
(3.22)
93
and
Validation
It is
seen
=
that the
temperature dependence of pQ
as
is
determined
the
by
K(T)
ture
Jkad(T)/kdes(T)
long
as
remains constant
*
over
tempera
range considered. It is also
seen
that the value of p0
is rather sensitive
irmTTf
10
-1
1200
slope (1
p)/2
1100
-2
--
10
1000
CM
'-
6
o
10"3
-_
900
..^-^
10
rA
820
-.
slope ~p/2
10
-5
750
i.hi
"'
'"'
jJ
'
10
101
102
103
104
105
PoJ**
Fig.
3.4
Relation between the
exchange
given
current
density i0
and the oxygen
partial
pres
con
sure.The
stants
temperatures (K)
in Table 3.1
are
within the
were
figure.
The
parameters
and rate
given
(appendix 3-A.l)
used for the simulation. Note that
0.62.
94
3.4
Simulation Results
r=900K
_-/
p
7
0.65
./*
//I
(l
>>
0.5
0.5/#
/ /
/
0.2
/
p
=
"0:=
-P)2 p2*2
0.35
0.1
'
'
10L
101
102
103
104
10J
PO** )2y
Fig.
gen
3.5
Dependence of i0
=
on
the
charge
same
transfer coefficient
as
p.The
3.4. p0
*
simulation
was
obtained for T
900 K with the
parameters
in
Fig.
denotes the oxy
partial
pressure where the maximum value of z0
occurs.
to the value of
p0*
p0
*
P (cf. Fig. 3.5). Eq. (3.22) simplifies K(T)~2 with p 1/2 [44].
=
to the well known result of
In the
literature, the experimentally obtained temperature dependence of

=
was
AHad
on
employed for the ad Edes [44, 45].

-
determination of the heat of oxygen

Note that
ad
and
Edes
are
adsorption strongly dependent

From the
the surface coverage of Pt with atomic oxygen of
(see e.g. [46]).
Langmuir equation it is easily seen that the surface coverage

mum
where the maxi
i0
occurs
is
given by
9*
._ =
*<T>-^ l+W)JPo2
the
(3.23)
which
gives by
use
of
Eq. (3.22)
simple
1-p.
result of
9*
(3.24)
95
and
Validation
Only
in
case
where
1/2
we
have 9*
0.5
[47]. However, if 9>0.2,
AHad
good
becomes almost
independent of surface
coverage
[48]
and
we can con
*
sider the activation energy obtained from

estimate of the oxygen
=
plot of p0 as a adsorption enthalpy AHad at high Pt surface

an
Arrhenius
coverages, i.e. at 9
mined for
9*. We would like to mention that the values deter
AHad by
Okamoto et al.
[44] and Mizusaki
et al.
[45] differ by
an
about 50
kj/mol.
It is
important
with
to note that
Eq. (3.22)
was
derived from
expression relating iQ
al. determined
experimental quantities (Eq. (3.21)).

=
Mizusaki et
,
AHad
from the electiode conductivities ae
R~
whereas
analysis on measured exchange current densities. We will show below that i0* is generally not located at the same pQ as ae*, therefore an Arrhenius plot of pQ (ae*) will not yield AHad. investigated. Fig. 3.6 shows iso baric Arrhenius plots of iQ. With decreasing temperature, the isobars show breaks to steeper slopes, which occur at a higher temperature the higher the p0 Note that only i0(po *) shows a straight line and that the corresponding activation enthalpy for charge transfer is given by
is
.
Okamoto et al. based their
Finally,
the
temperature dependence of i0
AHct*
where
(1-P)a + P-Ea
energies
The
(3.25)
Ea
and
Ea
are
the activation
for the forward and backward

result
in
electrochemical
reaction,
respectively.
Eq. (3.25)
is
easily
obtained from the
p0 with the
general expression i0(T, p0 ) given in part I by replacing expression given in Eq. (3.22). For arbitrary pQ we find a limit
with
ing apparent activation enthalpy at low pQ larly at high pQ wi\hK(T)Jp0 1. In the
K(T)Jp~Q
1, and simi-
first
case we
obtain
AH^t
whereas in the second
case
AHct*-<l^.AHad
(3.26)
AH!!1?!1 rhij
[<t,ct
=
-
AH..*
""ct
T2
'
AH^.
""ad
(3.27)
limiting pQ regimes, as well as the limiting behaviour of i0(po ) is clearly seen in Fig. 3.6. With P 1/2 we obtain the same results as developed by Wang et al. and by Velle et al. [9,10]. A behav=
The transition between the
96
3.4
Simulation Results
iour of
was
const) with temperature similar to the one shown in Fig. 3.6 i0(po found experimentally [9, 49]. With the parameters given in Table 3.1 we
=
obtain
AHJJ^th
AH^
AHct*
=
131
kl/mol,
et al.
AH^,Z
"
=
kJ/mo1'
96
and
183
kl/mol. Wang
[9] found
AHj,
et
kl/mol from the [10] determined
temperature dependence of
=
i0(po
), and Velle
al.
kl/mol from the temperature dependence of Rt(Pcy "H (equivalent circuit fitting of EIS data was used). Both authors used a rela 294 kl/mol. How tively high value for the adsorption enthalpy, AHad
199
=
ever,
relatively large discrepancy

170
exists between the
reported
values for
AHC* (Ref. [9]:

large
kl/mol; Ref. [10]: 126 kj/mol) which
is attributed to the
value used for
AHad. Using
a more
probable
value for the
adsorption
diminishes
enthalpy AHad and AHct* is obtained

In summary,
in the range of -180
kj/mol [48],
this
discrepancy
in the order of 140
kj/mol.
experimentally. The charge-transfer coef ficient P can be obtained from i0(po ) data at high temperatures (cf. Fig. 3.4). Unfortunately, Eq. (3.25) is now not sufficient to estimate uniquely the activa tion energies of the charge-transfer reaction, Ea and Ea It is expected, how AHct*
can
be obtained
ever, that both values
are
not too far
apart.
Estimates of
AHad
are
available
it is
through Eqs. (3.26) and (3.27). For reasons which will become clear below suggested that Rt data are employed rather than i0 estimates.
Electrode
polarization
and
experimental
determination of i 0
So
far
a
we
have assumed that the reaction is
range of temperatures. In this case,
charge-transfer controlled over the exchange current density i0
broad
and the
charge-transfer coefficient P determine the overall electrode characteristics. In solid state electrochemistry it has been common practice to obtain both values from a Tafel-plot analysis of Ip(T|) data. However, the parameters obtained from this analysis are only meaningful, if one charge-transfer (or one chemical) step is actually rate determining the overall electrode reaction
[1,50,51].
But how
can we
test whether this
requirement is fulfilled under
the
experimental
problem will be examined below and we will propose a method in the following subsection which may uniquely clarify whether an electiode reaction is controlled by a charge-trans
fer step
or
conditions considered? The
not. We
=
use
fications:
klc
2-105 m3/(mol-s)
the parameters of Table 3.1 with two and
important
modi
Ed
110
kj/mol.
97
and
Validation
77C
900
t
800
i
700
i
600
i
500
r
io-1
10"2
I IO"3
10"5
0.8
0.9
1.1
1.2
1.3
1.4
103K/r
Fig.
cal
3.6
Isobaric Arrhenius for
expressions
apparent
activation
plot of i0 at different oxygen partial pressures.Analyti the charge transfer activation enthalpy at pQ *, AHct*, and the enthalpies at low and high pQ AH^t and AH^t are given in
, ,
the text. The
parameters of Table3.1
were
used. Note that pQ
*(1100 K)
10
Pa.
Compare
with the simulations of
Fig.
3.4.
98
3.4
Simulation Results
First, remember the
general
definition of the
charge
transfer resistance
^-?)*.
where x{ denotes the
(328)
steady-state surface concentrations at the correspond ing operating point (defined by T|, T, and pQ ). It is seen that Rt can be obtained at arbitrary operating points, whereas i0 (Eq. (3.20)) gives only a description of an equilibrium situation (i.e. where r| 0 and therefore 0). By considering Eq. (3.28) it seems that Rt could be obtained experi 7F
= =
mentally from a small-signal dc analysis
around E
or
around
overpotential, as it was done in the literature [44]. This is not case, as Eq. (3.28) requires that the surface concentrations xi remain constant. which is only Such an analysis will reveal the polarization resistance R equal to Rt if the reaction is charge transfer controlled. Similarly, we can strictly speak of a pure Tafel behaviour only if the concentration of surface species (in our case only Oad) remains constant over the overpotential range where the analysis is conducted. However, surface concentrations can not be measured directly and therefore it is difficult to draw conclusions about the reaction mechanism from fF(T|) curves alone. In addition, it has been shown that an apparent Tafel behaviour may be caused by a competition between surface mass transport and charge transfer, if some requirements are satisfied
[38].
steady-state generally the
fF(n) curves of M2 at 1123 K (850C). It is seen that the IF(r|) behaviour at high pQ follows an ideal Tafel behaviour up to relatively low cathodic overpotentials of approximately -0.15 V. Strong devi ations from the purely charge-transfer controlled behaviour occur at larger overpotentials. The deviation from Tafel behaviour is shifted to lower
Fig.
cathodic
curves
3.7 shows the simulated
overpotentials
an
with
decreasing
pQ
It is further
seen
that the
follow
apparent Tafel behaviour at low cathodic

process and
a
ip(T|) overpotential
a
(with apparently lower P than used for the simulation), indicating

tion between the
competi
charge-transfer
further reaction.
easily found in the deviation of the surface concentration x from its equilibrium x0 value near the tpb. Fig. 3.8 shows the high p0 curve from Fig. 3.7 in a linear plot. Although the deviation from the
reason
The
for the deviation is
Tafel behaviour is obvious, it would be difficult to
recognize
seen
this without the

con
given
curve.
The inset of
Fig.
3.8 shows the behaviour of three surface
centrations at different distances from the
tpb.
It is
that the concentration
99
and
Validation
of
Oad
near
the
tpb strongly
a
decreases with
increasing
Note that
to
cathodic
overpoten
a
tial. This is the the

occurrence
reason
for the deviation from the ideal Tafel behaviour and for
of
concentration
polarization.
very
we
used
this
very
high
value
for
the
surface
diffusion
coefficient
obtain
behaviour
layer of -10 pm. Real values for D are expected to be one to two orders of magnitude below this value at T 1123 K [52]. In contrast to the simulations shown in Fig. 3.7, the real porous electrode/electrolyte system does not exhibit a limiting If(t\)
(D
=
3.5510"9 m2/s).
=
This also
causes a
large
diffusion
10
>
\
\
\
\.
\
'
7= 1123 K
\
\
*\
\
^
\
V
y^
N\-\
\
v
io-1
.
X
\
*-*
^
i\
\
\.
'a
*\
\
\
*
,s
îo-2 5-
\
\
A
i
\
A
\
\
\
1(T3
-
Po2=15pa
2
a
1
:
104Pa
103Pa
i
>
'
in-4
<
-0.5
-0.4
-0.3
-0.2
-0.1
n/Vvs.eq(r=1123K)
Fig.
3.7
Steady-state 7f(n)
behaviour of Model M2 at T
1123 K.The
filled
circles
represent the simulated JF(T)) behaviour. The lines give the IF(r\) behaviour under the
assumption
The
T
=
that the surface concentration remains constant is defined relative to the
(i.e. pure
Tafel
behaviour).
overpotential
1123 K.
as
Parameters:
110
kj/mol;
Equilibrium potential develops at 2 105 m3/(smol); remaining Jtlc

=
which
parameters
given
in Table 3.1
100
3.4
Simulation Results
behaviour under the considered conditions. This is due to the fact that model M2 does not account for the
stiong coverage dependence of the adsorption
desorption rate. The sticking coefficient of Oz(g) on Pt may vary many orders of magnitude with surface coverage [46]. Accordingly, the adsorption rate should strongly increase with cathodic overpotential [33].
and
Let us,
as
it is often done in
curves
seen
practice, perform
Tafel
analysis
an
on
the simu of the
lated
IF(n)
from
=-0.15 V to -0.35 V
Fig.
3.9 shows
some
results. It is
that the simulated
IF(r\)
1
curves
follow
apparent Tafel
7"= 1123 K p
j>^*
"
=io5pa

,y^
/ /
-0.2
/
/
#
#
/ /
04
<
-0.4
/
/
/
/
1
0.3
/
s
/
/
1
1
-0.6
/
/
^02
50nm
-
J
0.1
3.75 nm 5
nm
-0.8
/
-1
III
1
-0.4
-0.2 0
-0.4 ri/Vvs.E
eq
-0.2
(r=1123K)
Fig.
3.8
Deviation of
JF(n)
=
from theoretical Tafel behaviour.Linear

10
plot
of the data
shown in
Fig.
3.7 at pQ
Pa. The filled circles show the simulated behaviour of
M2 and the solid line denotes the ideal Tafel behaviour. The inset shows the
ing
surface concentrations
n
.
as a
function of the distance from the
tpb
and the
correspond applied
overpotential
Note that the surface concentration
gradient extends
over
~10 pm.
101
and
Validation
line
over
the range of
overpotentials
=
considered. However, the estimated
value for the

below the
charge-transfer actual value of P

ones
coefficient
0.62.
decrease with p0
and
are
all
Fig.
3.10 compares the theoretical results
analysis. It is seen, although the values are rather close to each other, that the pQ dependence of i0 estimated from the Tafel analysis is completely different to the expected (theoretical) p0 dependence. It can be further seen that a relative large number of meas urements (or simulations) are necessary to reveal the p0 dependence. It
10l
for
i0
with the
estimated from the Tafel
VI
X
,-1
10
7
'VV (0-49,6.5)
x
^s*\
X
;
^K ^^.
.
*S ">
*^~-^-
V
-
(0.19, 10.5)xs^^^~^^
x
N^-Q^^
'Y
*>.
^V Nw
"^s.
^v\
*V\ ^L
\
*
"""""*>^
10
C4
,-2
^^-~~-^ %^
\.
s-
s
<
^^
\
v
\
*^
\ \
>
-.
'.
~*
(0.08,2.5)
^T~X

*v
'
\
I
\
\ ^
1
L
_
10"
T 1 k
1
*-
*.
*
i
1
'
* *
.
i
:
t
i
10
,-4
pn
2
-
!
c
< >
W Pa
3.16103Pa
* i
i
.
102Pa
10
,-5
-0.5
-0.4
-0.3
-0.2
-0.1
i\/V
\s.
E(T= 1123 K)
Fig.
3.9
Simulated
Ip(T\)
behaviour and Tafel
analysis.The
The value for
Tafel
analysis
was
are was
obtained from the simulated
/F(t|)
data from T| =-0.15V to -0.35 V. The results
given
as
(P, f0/mA-cm"~2) pairs

same
within the
figure.
in the simulation
0.62. The
parameters
as
for the simulations in
Fig.
3.7
were
used.
102
3.4
Simulation Results
should be mentioned that the estimated values of the number of simulated data
iQ
are
rather sensitive to
points used
for the Tafel
analysis.
an
We end this subsection with the
following
does not
conclusions: first,
apparent
Tafel behaviour of the
JF(T|)
curve
assure
that the reaction kinetics is
charge-transfer controlled. Second, Tafel parameters (P and iQ) obtained from values and an a Tafel analysis of IF(t|) data may be far apart from the real interpretation of these parameters will be questionable. Third, measurements of the jf(t|) behaviour impose a large perturbation to the electrode/electro lyte system which may cause irreversible changes to the microstructure and/or the interfacial structure. Finally, Jf(t|) measurements reveal the least possible amount of information about an electrode/electrolyte system, which
nevertheless, might be needed in combination with further electrochemical
10
's
<
s
1
slope(l-$)/2
0.5
from Tafel
analysis
L, theoretical value
0.2
101
itf
10"
PoJ**
Fig.
3.10
Comparison i0
of theoretical and estimated j0 values at T
1123 K.The open
circles represent the estimated

Note that the
can not
be
i0 values from the Tafel analysis as described in Fig. 3.9. compared with the data in Fig. 3.4 because the electrochemi
factor of 10. The
same
cal rate constants differ
by
parameters
as
Fig.
3.7
were
used.
103
and
Validation
methods, such
as
electrochemical
impedance spectroscopy (cf. part I
of this
publication [1]).
Electrode
impedancesdetermination of Rt
and
Cdl.
As
mentioned
above, electrochemical impedance

Faradaic
measurements do not
impedance ZF(jco), but Z(jco) which is capacitance Cdl in parallel and the electiolyte resistance in series. However, EIS might be a way of assessing if there is only one, or if there are more rate limiting steps [51, 53]. Mogensen et al. have claimed that the presence of one semicircle (which is not too depressed), indicates that the rate of an electiode reaction is dominated by one single reaction step. Let us elaborate this state ment by means of the reaction kinetics of model M2 at high temperatures and high oxygen partial pressures. In Fig. 3.8 the simulated JF(n) behaviour of M2 at T 1123K and 10 Pa was shown. The corresponding simulated EIS spectia obtained p0 at different operating points of the IF(n) curve are shown in Fig. 3.11. The Z(jco) spectra at low to moderate cathodic overpotentials exhibit a (almost perfect) semicircle in the complex plane (Fig. 3.11 a). With increasing cathodic n the semicircle becomes depressed and finally, at t\ < -0.3 V, a second semi circle appears (Fig. 3.11b). Note that ZF(ju)) can hardly be observed in the Z(jco) plot (cf. inset of Fig. 3.11a). One should be aware of the fact that EIS measurements only reveal the Z(jto) curves and that the information con tained within ZF(ju)) is not accessible immediately. For the simulation of the spectra in Fig. 3.11 we have assumed that a double layer capacitance is in par allel to the Faradaic impedance. We have taken a value of Cdl 20 pF/cm2. Obviously, if these spectra were measured and if we were interested in the reaction kinetics, we could analyse the spectia with a simple equivalent cir
= = =
directly reveal the concealed by a double layer
cuit and
interpret
the values obtained for the resistances and the

work well in this
cases.
capaci
fail in
tances. This
more
might complicated
simple
case, but it will
certainly
as
We therefore propose to continue
described
below.
Fig. 3.12 shows two series of spectia, each points of M2 but with different values for
The
series taken at different
the double
operating layer capacitance Cdl.
spectra show the Faradaic impedances ZF(jo)) (thick lines) of a purely charge-transfer controlled reaction kinetics (figures on the left), a kinetics
where
charge-transfer
and
a
is in
competition
with surface diffusion
centre),
kinetics where surface diffusion is rate

seen
(figures in limiting (figures on

come
the the
right).
It is
readily
that it is almost
impossible
to
to these conclu-
104
3.4
Simulation Results
r=1123K,/70 =103Pa
n=0V
S
C!
s
l-H
a)
0
3.1
3.2
3.3
3.4
10
12
Re(Z/Qcm2)
1.5
ZF(jw)
Z(ja))
7
0
32k 100k <
ri
-0.30 V
-0.50 V
b)
0
0.5
1.5
2.5
Re(Z/Qcmz)
complex plane.The spectra were sim overpotentials given within the figure. The results can be directly compared with the JF(r|) simulations given in Fig. 3.8. The num bers within the figure denote the frequency in Hz. The same parameters as for the simu lation of the JF(r|) curve in Fig. 3.7 were used. A double layer capacitance of Cdl 20 pF/cm2 was assumed. Note that the Faradaic impedances ZF(jo)) at low cathodic overpotentials are almost invisible because Rt ^p (see inset f upper figure).
Fig.
3.11
Simulated
=
Z(j0))
of M2 shown in the
=
ulated at T
1123 K and pQ
10
Pa at the
105
and
Validation
&
"2
S
S
01 u
of
0 01
Ji
o.
C
CO
M
(0 t0
o
01
to co
&
Uh
-a
o>
.a
to
01
1-1
01
o>
J*
5
05
V V
01
9
M)
01
o
u
JS S 'I
.m
01
cy
>
ja
-
3
o
to
S
CO CO
2
01
5
O
3 -3 5
1 J!
CO
<^
>
CL.H
co
X
-M
QJ 01
-a
^
ft;
V
N
o>
*
"-1
j_
3
N
x CO
<0
g
CU
01
~
of
01
c
I-l
6
W)
S
'
,>
.2
N
CO Oi
c
'
&, T3 SX c
co
'C
jCl,
O)
~
C
O
esp
*-
~&*
^rL
^
0 1V
05
tl
/'*8 O
0
-"*<
ance cor
CO
X,
o
of
0 0
ooe
=*O
<1
(
\
/
n
Su
fti
"j
c
co
c
>
o.,
U
> O
fsi
-"a
co co
01
<"">
CO
^">
01
tj
C
-
a
O
(J
M
o>
>
in
Oi
II
II
O, CL, 3
ik/
d
J
O
10k/
z-
^
^\_m
^-_. -
3
o
o
o
a,
X, *
<u
.z-
c
M
-g
^ 8.
"
39
3
o.S
1
to
.
2J
o
^
01
N
o>
13
^ .2
^1
CO
CO
(T1 +3
106
3.4
Simulation Results
,_
300
. #
100
Ik
4
CN
.*

30
Cdl
10
20jiF
^ #
d
S3
0
.
(iF
.
20k
X5HF 4
*
\
x
lUF J?
.o\xx
V
1
-4
0
i i
i
2
1 1
4
1
6
1
8
1
10
12
16
20
Re(Z/a-cm2)
impedance data.The parameters as given in Table3.1 were used at T 1000K with Cdl 28 pF/cm2 and Re 1.3 Qcm2. Weighted (1/|Z|) random noise of a maximum amplitude of 1% was added to the data. The inset shows the high frequency part of the spectra for decreasing values of Cdl.
Fig.
3.13
Complex plane plot
of simulated
impedance Z(jco) spectra (thin lines). We further see that the actual value of Cdl strongly influences the appearance of Z(ja)) and that the appearance of a single semicircle in the complex plane is by far not a suffi
sions from the
governed by a single step (see [51]). We feel that it is necessary to determine the Faradaic impedance ZF(jco) rather than just the impedance Z(jco), i.e. we need to know Cdl. We demon strate a promising procedure in the following.
Fig.
3.13 shows
a
cient condition that the reaction kinetics is
simulated
impedance
of M2 in the
complex plane.
an
ran
dom noise is added to the spectra. The
impedance
from the
given
3.13
data without
problem fitting the
is to extract the Faradaic
data to
clearly shows the influence of a itance on the ZF(jco). Rt is expected to be in the order of 7 Qcm2 and Re is -1.3 Qcm2. We apply the method proposed by Berthier et al. [39] on the impedance data. Fig. 3.14 shows the final result. The Faradaic impedance is obtained by subtracting Cdl and Re from the impedance data. Once Cdl is
cuit. The inset of
Fig.
equivalent cir double layer capac
107
and
Validation
12
'cdl
II
zg<d)
II
-I *. f-
1
1
i
, ,
ZF0co)
L-r-\RT\- Z9(jco)
1
^Zptjo))
B
C!
o o o o
S3
ii
o o o
o o
oo
\
Rp
1
10
15
20
Re(Z/Qcm2)
Fig.
3.14
Determination of
ZF(j(0)
[39].
from simulated
noisy Z(jO))
data.The
method
from Berthier et al. is used

With
=
The
electrolyte
=
resistance is subtracted from the data.
1.3 Q-cm2 a value of Cdl 28 pF/cm2 is estimated. The inset shows the Re circuit" which describes Z(ja>). Note that Ze(joa) can not be represented by "equivalent
an
electric circuit.
estimated, R
and
in
Rt
can
be
accurately
an
estimated from the function S'
(equation (26)
ance
[39]). S' for the data
set considered is shown in
However, the method requires
accurate estimate of the
Fig. 3.15a. electrolyte resist
Re, as was also mentioned by Berthier et al. [39]. In practice Re is often not accurately known and it is estimated by extrapolating the high frequency impedance data towards the real axis. This may cause large errors in Cdl and, therefore, in Rt as shown in Fig. 3.15b. If Re is only approximately known one can run the algorithm for a series of electrolyte resistances around the expected
mental
value
(Fig. 3.15b).
always
we
We have done
we
so
for
large
Fig.
number of
experi
of the
[54]
and simulated data and
have found that the shown in
shape
Cdl(Ke)
function
looks like the
one
3.15b. Furthermore,
Re is always located near to the maximum of the curve towards higher electrolyte resist ances. This procedure helps to obtain a starting guess for Re. Further refine ment is achieved through an iterative search of the "optimal" (CdI, Re) pair
from simulations
have found that the "true" value for
108
3.4
Simulation Results
by optical inspection of the resulting spectra. In the following we will always give both the Faradaic impedance ZF(jo>) and the impedance Z(ju)).
give only meaningful parameters if the reaction kinetics is dominated by a single reaction step. Interpreting P and, especially, i0 is doubtful. EIS spectra alone do not generally help to clarify the
In conclusion,
a
Tafel
analysis
may
layer capacitance Cdl must be determined and extracted from the EIS raw data. Re and, more importantly, Rt are obtained with reasonable accuracy, where Rt is related through (RT)/(2F) R^1 with the exchange current density iQ (at arbitrary oper i0 question
of
single-step
control. The double
ating points).
A discussion of
iQ
data obtained in this way
seems
reasonable.
as
Much information is contained within the Faradaic illustrated in the
impedance,
further
following
section.
3.4.2
Competition
Between Surface Diffusion and

At
Adsorption
to -773 K
Electrode conductivities.
temperatures below -1073
(800C)
(500C) and
electrode
at
oxygen
on
partial
pressures above ~100 Pa, surface diffusion of
atomic oxygen
the Pt surface is believed to be rate
kinetics
[10,15,45,47,55,56].
Various
determining the overall analytical expressions
IF(T|) characteristics, and the elec trochemical impedance have been presented in the literature. However, it has been always assumed that no adsorption takes place in parallel to the surface 1/2 diffusion process. Under this assumption, a pQ dependence has been jR~ at low pQ In the following derived for the electrode conductivity ce describing
the electrode
conductivity,
the
we
will obtain simulations for
compare the results with

The relation between
Rt and R as a function of pQ the preceding experimental results.

and R~
as a
and T and
R^
function of pQ
is shown in
Fig.
3.16
for temperatures from 773 K
(500C)
to 1073 K
(800C). By use of Eq. (3.20) the
exchange
current densities
spond
to those
given
in
i0 can be obtained from Rt. The iQ values corre Fig. 3.4. The simulations give a picture which is in
reasonable
qualitative
Mizusaki et al.
quantitative agreement with the measurements of (see Fig. 7 in [45]). The maxima of the log(fv~ ) versus
and shift to lower pQ
of R~ with
log(p0 )
there
curves
decreasing temperature. However,
are some
differences that attain further attention.
First, the pQ
dependence
.
region
than in the
considerably stronger in the low pQ high pQ region. Fig. 3.17 shows the pQ dependencies of
is
a
Rp
and
R^
Note that not
clear pQ
is found for the
conductivities, but
109
and
Validation
10J
101
E
o
10
,-i
10
,-3
a)
fl/(Qcm2)
0.8
1.2
1.4
1.6
1.8
/ce/(Q-cm2)
Fig.
3.15
Determination of
two maxima for
showing [39] (Eq. (26)). (b) Dependence lyte resistance Re.
Rp and Rt after subtraction of Cdi-(a) Rt and Rp. The definition of the function
of
Cost function
S'
S'
can
be found in electro
Cdl
on
the initial value of the
uncompensated
110
3.4
Simulation Results
dependence varies continuously over It is clearly seen that a pQ dependence of R~

that the
more
than
one
decade of
is found at low oxygen
pQ^. partial
pressures. The
gen
in
reason
for this
can
be found in the fact that dissociative oxy
adsorption
occur
parallel,
of oxygen molecules and surface diffusion of atomic oxygen the pQ even near the tpb. Analytical solutions describing
10-5
L_
,_
10
101
102
103
104
105
Pon*
Fig.
3.16
Electrode conductivities
as
function of
temperature and oxygen partial
pressure.The temperatures (K) where the simulations were obtained are given within the figure. The data for Rt and R were obtained from the linearized state-space model M2 ((A, B, C, D) quadruple) at the corresponding operating point. The parameters
given in Table 3.1 were used.
Ill
and
Validation
0.8
0.6
CN
,^
00 o
u*^
0.4
33
0.2
Ui
60 o
-0.2
10l
101
10^
io-
Vf
io-
Po/**
dependence of electrode conductivities of model M2.The derivatives of log(R^~ ) and log(R~ ) with respect to log(p0 ) were obtained numerically from the data given in Fig. 3.16. The temperatures (K) are given within the figure for the R~ data. The temperatures for the R^ data can be understood likewise.
Fig.
3.17
Oxygen partial
pressure
dependence of ZF(jco), and larly at high oxygen partial

of
R~
therefore also of R
can
be found in
[57]. Simi
,-i
pressures
seen
is
obtained,
R
as can
be
in
one-quarter pQ dependence Fig. 3.17. It is further found (but not

minus
independent of the charge transfer coefficient P, where in contrast, R^ (pQ ) strongly depends on P (cf. Fig. 3.5). Taking a closer look at the experimental cre(p0 ) data from Mizusaki et al. reveals that the p0 dependence tends to be stronger than 1/2, especially at high temper atures (cf. Fig. 7 in [45]). Similar observations can be made on the early results from Fabry and Kleitz [58]. We again see that a relatively large number of measurements is necessary to reveal the pQ dependence of the
shown) that
(pQ)
is almost
electrode conductivities, otherwise the information
might get
lost in the
experimental errors.
A Pq
dependence
(10
to
of R~
has been
reported
for oxygen
below
100)
Pa
by
number of authors
[59-61]. This
partial pressures is generally attrib-
112
3.4
Simulation Results
uted to gas model M2
phase
diffusion of oxygen in the porous electrode network. Our
can
not account for
this.
It has been claimed
by
Mizusaki et al. that the activation energy for

an
Oad
dif
fusion
on
Pt
can
be obtained from
Arrhenius
plot
of Rl
.
(pQ +),
if surface
diffusion of
Oad
R~
argued that dependence

R"
determining (pQ +) is where

is
the electrode kinetics

6
=
The authors have
1/2
and therefore the
temperature
we
of the concentration term should be excluded. However,
have shown above that
R^ (pQ
higher
*) results
than
at 9*
P and
we
see
that
(p0 t)
is located at
pQ
shown in
Fig.
P
3.16 it is
seen
that the
R^ (p0*). From the simulations log(pQ ) difference between the two

Because R~
is
maxima is almost
independent of temperature.
*
virtually inde Fig. 3.5),

find
we
pendent
of
and Pq
for
R^
at
is
given by Eq. (3.22) (see
also
find that this distance decreases with

simulation that
decreasing
values for
P (we
by
as
pQ
pQ
1/4 for M2 and the other
parameters
given in Table
3.1.
Fig.
3.18 shows the
723 K
seen
(450C)
to
temperature dependence of l/Rp at different pQ from 1073 K (800C). Note that pQ1 > 105 Pa for T > 1000 K. It is
of the
that the
slope
of
log
R~
(pQ +)
versus
1/T
plot
is
approximately
We find
an
independent
temperature
and the value of
P (not shown).
apparent activation energy of -152 kj/mol at high temperatures and a value of -167 kj/mol at lower temperatures. Mizusaki et al. determined a value of
-171
kj/mol
155
experimentally
it is
seen
(see
Fig.
10
in
[45]).
We
assumed
Ed
kj/mol and
that the activation
enthalpy
of R~
(pQ t)
does not
becomes
correspond to the activation energy even more pronounced if a larger value

apparent activation
-873 K
as
of surface diffusion. This for

in the simulation
is used. It shows that the
AHad enthalpy of
R~
(pQ t)
comes
close to
AH^
at
temperatures below Pa)

is obtained
energy of R~ (10
surface coverage
tures. At low
(600C). The apparent activation -200 kj/mol at lower temperatures (high

to -140
regime)
and
and it T
changes
kj/mol
p0
high
can
(low
surface coverage
higher tempera regime) we find a very

at
low apparent activation energy of -45 These simulation results

ture
kj/mol.
dependence
of the
easily explained by considering the tempera concentration impedance Ze(jco) as introduced in
be
*)
pQl
is the oxygen
partial
pressure where the maximum of ae is obtained;

*
we use
this notation in order to avoid confusions with pQ obtained. Note that Mizusaki et al.
use
where the maximum of
R^"1
is
the notation
ae*
for
expressing
pQ *.
113
and
Validation
parti.
From the
two-compartment ZF(jco) transfer function of
M2
we
find
the concentration resistance
[1]
kf
+
Rc
Zeo
0)
Rt 1
f
d
+
kb
u.
(3.29)
4/cadN0Po,
(!"*)
4fcdesN0
'
Remember
the
definitions
of
Td
and
S2/(2D),
=
vadexp[(-Ead)/(RT)], fcdes in terms of k( (see part I) it is seen that the temperature by expressing kb dependence of the product Rt (kt + kb) cancels and we are left with a simple expression for the temperature dependence of Rc. We consider two limiting
=
Kd
D0exp[(-Ed)/(RT)], Vdesexp[(-Edes)/(RT)] Again'

=
cases:
(i)
low T and
high pQ (high
remaining
=
coverage: (1
x)
>
0): surface dif
fusion vanishes (1. term of the denominator in
Eq. (3.29)).
We
expand
result:
the
fraction of
Eq. (3.29)
with
l/kdes
and
obtain with K(T)
Jkad/kdes
and (1 -x) 0 the
following
AHj
and with
=
Edes
given
in
(3.30)
Table 3.1
the
AHj
(ii)
parameters
200
kj/mol.
high
T and low pQ
x >
(low coverage:
0
we
0): proceeding
as
above and with
obtain:
des-d
=
(3-3D
and, accordingly, Ai-L

The simulation results
45
kj/mol. agreement with Eqs. (3.30) and (3.31).
are
in excellent
Obviously, the apparent activation energy may vary in between these two limiting values, as seen in Fig. 3.18 for the simulations of R~ (10 Pa). t Let us finally consider the temperature dependence of (cf. Fig. 3.19). An p0 average apparent activation enthalpy of -150 kj/mol is obtained over the temperature range considered. The value is slightly higher at lower tempera-
114
3.4
Simulation Results
800
700
600
500
77 C
0.9
1.1
1.2
1.3
1.4
103
Fig.
3.18
K/T
Isobaric Arrhenius
were
plots
of electrode
conductivity
R ".The
were
parameters
obtained from
given
in Table 3.1
used for the simulation. The values for R~
the linearized SSM at the
enthalpies AH^
are
corresponding operating point. within the figure. given
The apparent activation
tures
(158kJ/mol)
and
decreases
with
Pt is
(-140 kj/mol). The surface coverage of

constant in the
increasing temperatures relatively high and remains not

et al.
temperature range considered. Mizusaki

activation
[45] deter
mined
an
value of
between
enthalpy of ~220kJ/mol for the maximum the electrode conductivity. Accordingly, a large discrepancy exists our simulations and these experimental results. However, the
apparent
result
was
reported
obtained from
number of different measurements
115
and
Validation
which itself exhibited
rather
large
mean
variation
(see Fig.
to
9 in
[45]).
It is
questionable whether this large value can be attributed by the authors.

We would like to
AHad,
as was
done
point out two important
differences between
our
model M2
investigated by Mizusaki et al. [45, 47]. First, Mizusaki et al. assumed that the charge-transfer reaction was infinitely fast. However, we show below that this influence is significant in the temperature range considand the model
106
105
CN
104
103
102
j
i i L
0.9
1.0
1.1
1.2
1.3
1.4
103K/r
Fig.
R~
3.19
Simulated
temperature dependence of the oxygen partial pressure where the
maximum of the electrode

,
conductivity occurs.The data were obtained from by determining the maximum value for R~ The inset shows (pQ the corresponding equilibrium surface concentrations of adsorbed atomic oxygen.
T) simulations
.
116
3.4
Simulation Results
ered and at
high
-
oxygen
partial
following
formulation
al. made the pressures. Second, Mizusaki et coefficient: diffusion surface for the
D09(l 9). By use of this formulation we obtain simulation results which are in qualitative agreement with the results obtained before with the difference that the pQ dependence of R~ vanishes at low temperatures (T < as experimentally observed by Mizusaki et al. 773 K (500C)) and high pQ
D0(9)
=
,
[45]. However, there

concentration
can
be
no
data found in the literature
concerning
of
the
Pt.
dependence of the surface diffusion coefficient Accordingly, the proposed formulation seems rather arbitrary.
Electrode
Oad
on
polarization. Fig. 3.20 shows simulation results for the IF(T|) behaviour at 973 K (700C) at low cathodic and anodic polarizations. The
results
can
be
directly compared
(see Fig.
our
with the simulations and the

8 in
experimental
There is
results of Mizusaki et al.
[47]
and
Fig.
11 in
[45]).
reported results. We find cathodic currents in the simulations at relatively high pQ of 10 Pa to 10 Pa. The reason for this can be found in the strong pQ dependence of the
agreement
between
simulations and
good limiting
Oad in the model M2. To improve the model, the rate constants for the adsorption and desorption should be taken as a function of the surface coverage. It is known from adsorption studies that the initial sticking coefficient of 02(g) on Pt surfaces may vary many orders of magnitude, depending on the Pt surface coverage (see e.g. [46,48]). The inset of Fig. 3.20 shows the JF(T|) relation at small overpotentials and compares with the behaviour we would obtain if the reaction was charge
equilibrium
concentration of
transfer controlled. A
these low low
large
difference between these the
curves
is
seen even
at
overpotentials. Evaluating
slope
.
of small
overpotentials will therefore reveal the electrode not the inverse charge-transfer resistance R~ Only if the reaction kinetics is charge transfer controlled, i.e. Rt R small signal dc analyses reveal Rt. The difference between the two curves is attributed to a concentration polariza tion which can be clearly seen in the Faradaic impedance which is shown
=
signal dc curves at conductivity R~ and
below.
More information about the rate
limiting process is obtained from the pQ dependence of the limiting-current I,. For the system Pt, 02(g) I YSZ at high cathodic overpotentials, pQ and pQ dependencies of I{ have bee found [9,
is
59,61]. The stronger dependence
generally attributed to gas mass transport limitation whereas the weaker dependence is attributed to a surface diffusion limitation. However, clear relationships become apparent only at oxygen par-
117
and
Validation
h(Po ) behaviour of M2 from 873 K (600C) to 1073 K (800C). A clear p3^ dependence is obtained at lower oxygen partial pressures. At higher pQ the slope of log[Ii(po )] versus log(pQ ) decreases towards -3/5. This behaviour is
tial pressures below -10 Pa.
Fig.
3.21 shows the simulated
l_i
it
-0.1
-0.05
0.05
0.1
r|/V
Fig.
3.20
Simulated
JpOl) relationships
is
under different oxygen within the

.
partial
pressure condi
Pa
tions at 973 K
(700C).The pQ
at
given
Pa
figure.
The solid line shows the the

=
oretical Tafel behaviour at pQ
=10
The inset shows the results for pQ of 10 mV,

as
10
(real and Tafel behaviour) and

in EIS. From
a
=
dc
analysis
of the
R_
=
obtained:
Rt
10.5
Q-cm2,
usually employed small-signal data in the inset the following results are 29.9 Q-cm2. Compare these results with the impedance
overpotentials
small
spectra
in
Fig.
3.22 at the
same
conditions.
118
3.4
Simulation Results
explained
charge transfer resistance Rt decreases to very low values and the entire electrode polariza tion is caused by the surface diffusion of Oad and the adsorption of 02(g)Because the later two processes occur in parallel, a pQ dependence of
as
follows: at
high
cathodic
overpotentials,
the
Il(p0 )
is found. This is consistent with the simulation results for the R

as
(p0J
behaviour
shown above
is dominated
ence
by
the
Rt, (Fig. 3.16). Rp concentration polarization and
If
then the electrode reaction therefore

a
pQ
depend
/j. However, such a p0 has not yet been observed experimentally, probably because most of the studies were performed with
is also found for
porous electrodes. We would

electrodes where the Pt
expect
the described behaviour at Pt

in the order of
pattern
strip width is
(10.. .100)
pm, i.e. consid
erably larger than the Nernst diffusion layer width 8.

One
might expect that further information is obtained from the temperature dependence of the limiting current. The temperature dependence of I\(Pq ) is directly obtained from the data shown in Fig. 3.21. For the limiting behav
iour
at
=
low
64
Pq
we
find
a
an
average
apparent kj/mol
at
activation
energy
of
AH,.
of
kj/mol,
where
value of -76
is found at low
tempera
tures and the value decreases to -54

our
knowledge,
no
high temperatures. To the best corresponding experimental data are reported in the
kj/mol
must be from
literature
wise gas
(note that the results
non-porous electrodes, other
limiting process). By consideration of Eq. (3.29), and with kb > 0 it is seen that a rather complicated temperature dependence of I\(Pq ) results, where the activation energies of surface diffu sion, adsorption, and desorption have an influence, although an analytical
diffusion could be the
can not
expression
Electrode
be derived for
limiting case.
experimentally found that the impedance Z(ju)) in the complex plane exhibits as a single (depressed or Warburg-like) semi-circle at intermediate temperatures and at high pQ [15, 42,45,55,56, 61,62]. With decreasing pQ a second semi-circle generally appears [15,41]. There can no study be found where EIS spectra were recorded under a cathodic or anodic polarization of the cell. The interpreta tion of the spectia has been generally difficult and is further complicated by the presence of the double layer capacitance Cdl. As we have shown in the previous section, it is necessary to consider the Faradaic impedance ZF(jco) which can be obtained from the measured impedance Z(jco) by subtracting the double layer capacitance and the electrolyte resistance. In the following we will give both the Faradaic impedance and the impedance, assuming that
Impedances.
It has been often
119
and
Validation
10'
10L
'a
< E
io_1
10"
0.6 0.4
r=973K
0.2
10
,-3
po=l05Pa
tl
=
/ 0 *
-0.6 V
200
400
x(nm)
10',0
10'
\&
io-
10"
10'
Po,***
Fig.
limiting-current behaviour of M2.The temperatures (K) are given within the figure. The same parameters as in Fig. 3.20 were used. The iF(T|) behaviour was simulated to -0.6 V and the corresponding current was taken as Zj. the inset shows the concentration gradient (surface coverage 9) of Oad near the tpb
3.21
=
Simulated cathodic
at T
973 K,
-0.6 V, and
pQi
10
Pa.
constant double
ture
layer capacitance Cdl dependent electrolyte resistance Re

a
of 20
pF/cm2,
as
well
as a
tempera
in series is
present.
we
To obtain
simulate
complete picture of the electrode behaviour at 973 K (700C) the frequency response at different overpotentials and compare ZF(r|)
behaviour.
the
Fig. 3.22 shows simulated EIS spectra for two different pQ at low cathodic overpotentials in the complex plane. It is readily seen that an interpretation of the impedance alone is difficult. In con
tiast, the information is contained within the Faradaic
results with the
impedance.
From the
120
3.4
Simulation Results
25
8/
^-
vN,806m
ZQ(o)
ZpOco)
20
n*
n=-o.5v3m^
Ik 2k
C!
15
3k
10
a)
Re(Z/2-cm2)
120
9m
Z(jW)
/28m/^
^^
Tl
=
Zp(jco)
A
-g80
a
/
0.5M
-0.5 V
_()
IM
8
*
Tl=-35mV
7 40
_^~
"--.
N^2
\
b)
0 0 50
V
1
-10 mV
\ 806m \
100
150
Re(Z/Q-cm2)
Fig.
The
3.22
same
Simulated
impedances
as
=
at T
973 K
(700C)
at
parameters
for the simulation of the
employed. Spectra at (a) pQ tials as given in the figure.
105
overpotentials n. JF(r|) curves in Fig. 3.20 were
different
Pa and
(b) pQ
103
Pa for different
overpoten
121
and
Validation
knowledge of Rt can immediately
with respect to R
and the
shape
of the
impedance
,
arc,
we
infer the reaction mechanism. At

we
Rc
Rt)
and
find
Rt~ Rc (where that a competition exists between the charge trans high
pQ
fer process and the chemical processes. From the conclude that the surface diffusion process the
and
shape
of the
causes
ZF(jco)
understood
JF(r|) data at high pQ (Fig. 3.22 why the /F(r|) behaviour resembles a
Rc. From a and Fig. 3.20)
ZF(ju)) arc we comparison of

it
can
be well
over
Tafel behaviour. The
all kinetics is still influenced
by
the
relatively large charge
transfer resistance
Rt.
If the p0
is
lowered, the reaction kinetics is almost completely domi
by the surface diffusion process (Rt Rp). In both cases, the concen tration polarization increases with increasing cathodic overpotential, which can be readily explained with the decrease of Rt with cathodic overpotential (as long as Oad near the tpb is not too far from the equilibrium concentra
nated
tion).
Note that the values for
Rt
and R
obtained at
high
pQ
and
zero over-
potential (Fig. 3.22 a) are in full agreement with small-signal dc analysis in Fig. 3.20.
It
was
the values obtained from the
parallel process of 02(g) adsorption and Oad sur face diffusion was responsible for the limiting-current behaviour. This can be seen from the ZF(jco) at high cathodic overpotentials (see inset in Fig. 3.22). However, more information is obtained from a Bode plot of the ZF(jco) data and the slope of the log|ZF| versus log(u)) curve (Fig. 3.23). We have dis cussed some properties of frequency response data in Bode plot representa tion in more detail in part I of this publication [1]. With increasing cathodic overpotential the influence of the adsorption process can be seen in the high frequency part of the spectra: the w dependence of |ZF| changes from -1/2 to -1. This behaviour becomes more pronounced with decreasing temperatures. However, we believe that this behaviour is particular to the modelling of the
said above that the
adsorption process and that real electrodes should not show a first-order dependence of |ZF| at such high frequencies. Remember that the adsorption of 02(g) was assumed to occur directly from the gas phase on the Pt surface. Relatively high rate constants for the adsorption and desorption were chosen.
This the
causes
short relaxation times for this process which

It is well known that the
can
be observed in
spectra.
act
chemisorption
of oxygen
proceeds
via
one or more sors

as a
physisorbed
reservoir. A
precursor states
more
[63, 64]. Accordingly, these precur
refined model should include this
dynamic
behaviour
[33].
122
3.4
Simulation Results
a)
co/(2tc-s_1)
b)
co/(2rc-s
l)
and different cathodic overpo
Fig.
3.23
Simulated
=
impedances
Pa.
at T
973 K
(700C)
impedance ZF(jw) and the impedance Z(jto). (b) Phase angle of the corresponding data. Note the change of slope in the log[|ZF|] versus log(o)) plot from -1/2 towards -1 at high frequencies with increasing cathodic overpotential.
tentials.p02
10
(a) Magnitude of
the Faradaic
123
and
Validation
3.4.3
Sensitivity Analysis
and Practical
Identifiability
Sensitivity of ZF with respect to the unknown parameters. The sensitiv ity of the Faradaic impedance, S, with respect to the unknown parameters,
high in order to obtain accurate quantitative parameter esti mates from experimental data. For model M2 we assumed that only the charge-transfer coefficient, P, and the forward electrochemical rate constant, k^q, are unknown. The remaining parameters were assumed to be known with high accuracy. Fig. 3.24 shows the sensitivity of |ZF| with respect to P and k^q. S(P) is relatively low compared to S(k\q). We may infer that the higher the frequency the better. However, at high frequencies the influence of the electrical double layer becomes dominant and ZF(jco) must be first obtained from Z(jco) raw data. This procedure generally introduces rela tively large errors in the high frequency part of the ZF(jco) data. Therefore, P can not be estimated accurately from EIS measurements. However, as shown above, P can be obtained from the dependence of the charge-transfer resistp, should be
30
26
^
(S
a
-
??,
to
0.4
C!
**^
u.
-
18
14
oV(27t-s_1)
Fig.
3.24
were
Sensitivity
of
IZpl
=
with respect to the unknown
parameters.The
simula
tions
obtained for T
is
973 K in oxygen
(cf.
simulations in used
to
Fig. 3.22a).
the
The
magni
tude
of
sensitivities
ZF(jco) S(P)
also shown.
Eq. (3.13)
was
calculate
individual
and
S(kl).
124
3.4
Simulation Results
ance,
Rt, on the oxygen partial pressure, pQ (cf. Fig. 3.4). k\q is accurately obtained from EIS measurements.
assumed
so
Once
is known,
This method works well for the considered system if, and
only if,
the remain
in real
ing parameters are well known (as we have

porous
far). However,
electrode/electrolyte systems the length of the tpb, /^b, can be only estimated to 10% or even less. Similarly, we have no estimate for the width of the active area, w (see above). Unfortunately, the sensitivity of |ZF| is large with respect to w and /^b (cf. Fig. 3.25), which can be easily understood: the larger the length of the tpb and/or the larger the width of the active area, the higher the higher the rate of the electrochemical reaction is and therefore the lower Rt and R becomes. Accurate estimates of l^b and w are therefore a mandatory prerequisite to obtain accurate estimates of keq from EIS measure ments. This means that pattern electiodes of noble metal electrodes on (pref
erably single crystal)
electrodes if fix
one
solid
electrolytes
must be
employed
a
instead of porous
seeks for the electrochemical rate constants. This allows to

to
a
/^b experimentally
certain value within
small range,
as
long
as
the
30
26
6
03
22
a
N
18
14
10l
101
w1
10J
10<
103
co/(2jc-s_1)
Fig.
w
=
3.25
Sensitivity
of
IZFI
with
respect
as
to the
length
of the
tpb
and the width of the 3.24

were
active area.The 10
nm.
same
parameters
Fig.
used with
125
and
Validation
microstructure remains stable at
high temperatures.
We are, therefore, left

area w.
with the
question
of how to obtain the width of the active
discussing Eqs. (3.14) and (3.15) we found that Rt is insensitive to changes in w if the product w klc is kept constant (remember the definition of klc). We now choose a reference value for w as wN 10 nm and express the forward chemical rate constant by A:lc wN/w. The simulations of |ZF| for different values of w are somewhat surprising (cf. Fig. 3.26). We find that |ZF| is rather insensitive to w, if w is in the order of (1...10) nm. As already const. Surprisingly, R is only stated, Rt does not depend on w if w klc slightly depending on zu (cf. Fig. 3.26a). However, we find that the frequency dependence of |ZF| depends on the width of the active area w. At low values of w, ZF follows an almost perfect -45 line with respect to the real axis in the complex plane, indicating surface diffusion limitation. This behaviour dimin ishes at high frequencies with increasing size of w where a co- dependence of |ZF| is found (see also Fig. 3.23a for w =10 nm). Obviously, this effect is caused by the space discretization and is not a structural property of the
=
While
model. However, due to the low

w
sensitivity
nm
of
|ZF|
with
respect
to
(if
klc
const)
we a
can
obtain rather accurate estimates of
klc
from EIS
measurements if
area w.
value of
(1...10)
is assumed for the width of the active

we
This is close agreement with what
would
expect intuitively for

we
w.
Practical cal
identifiability.
we
In
part I of this publication
proved
the theoreti
identifiability
of the model parameters of model Ml and M2 with EIS.
However,
have shown above that the feature of
sensitivity
must
be also
are
considered.
Unfortunately, theoretical identifiability and high sensitivities

requirements
for
an
only
necessary
accurate
a
parameter
estimation. If
a corre can
lation between parameters exists, become
numerical parameter estimation
impossible as we show now. 105 Pa, and with the remain Let us produce ZF(jto) data at T 973 K, pQ ing parameters given in the appendix (Table 3.1). It is now the objective to estimate the unknown parameters from the generated data and the model M2, while different values for p [P, klc] should be used as starting guesses
= =
problem is well known from numerical optimization methods. We consider the weighted sum of squared terms (see appendix 3-A.4 for more mathematical and computer implemen
generation
were
than for the
of
ZF(jco)
used. This
tation
details)
126
3.4
Simulation Results
7 = 973 K
pO2=105Pa
^5ft^
4
^"N
lur
"X
\
'
\\
-
0
'
/
w
=
If
2
'
'
2 S
nm nm
nm
-
-A
1
/ / / / / // 1 / /
/
10
///
-8
1//
1
20
nm
0
12
i
a)
10
15
14
i
16
20
25
30
35
Re(Z/Qcmz)
-"-"T
^\IZFI
0.12
\ \ \
/
/ / /
-
30
26 E
20
nm
0.08
CO
^/ xv
\ \
'
22
-
CI
N
10 nm^^/
\ \
0.04
H
\ \
18
nm
__^~^*^
w
n nn
nm
's^
102
103
10< 103
14
10l
10'
0)/(27l-S_1)
Fig. 3.26 Sensitivity of IZFI with respect to w with under the (a) Zp shown in the complex plane for different values of w
text in at
condition from 2
w-klc
to 20
const.
the
figure).
The inset shows the

w.
different levels of
(- -) corresponds
high frequency part to IZpl at w 10 nm.

of
=
nm nm (see (b) Sensitivity of IZpl ZP
127
and
Validation
Fig.
3.27
Correlation between
and
fclc.The parameters given
in
Table 3.1
were
used to
calculate/(p) (Eq. (3.32)).
The bold line denotes the minima of the function f(p).
fW
*
ih X<Zf(P> 0
*
rF|
zf(/>>
0)2
(3.32)
,-
ZF(i) denotes the generated data. Fig. 3.27 shows the function f(p) for this particular problem. There are a few things worth to note. First, the sensitivity of f(p) with respect to klc is considerably larger as to a (as already mentioned above). Second, there exists a strong correlation between a and klc which is reflected in the fact that the cost function f(p) exhibits a shallow minimum. Although the absolute minimum can be found numeri cally at P PN and A:lc fclcN for these noise free data, this is generally not the case for experimental (and therefore noisy) data. It becomes clear that the numerical estimates of a from EIS data may be completely wrong. Accord ingly, a must be obtained from different measurements than EIS measure ments, even if S(P) was high (but which is not the case as shown in Fig. 3.24). Once P is determined, fclc can be obtained accurately. We have shown that the electrode reaction of the Pt, 02(g) I YSZ system is dominated by surface diffusion of atomic oxygen species over a large range
where
= =
128
3.5
Summary
and
Conclusions
aV(2K-s-')
Fig.
sion
3.28
Sensitivity of IZpl with respect of Oad.See explanations in the text.
to the activation
energy of the surface diffu
of
operating
conditions.
Accordingly,
we
can
expect that the sensitivity of
|ZF|
with respect to the surface diffusion coefficient of

can
Oad, D,
is
high and,
can
therefore, its value

more,
be estimated
easily
from EIS measurements. Further
the
dependence
a
of D
on
the surface coverage of Pt with
Oad
be
obtained from shows the

It is
seen
series of measurements and of

is
parameter
estimations.
Fig.
3.28
sensitivity S(Ediii)
|ZF|
with respect to the activation energy of D,

at low
Ediff.
that
extremely high, in particular
frequencies.
3.5
Summary
and Conclusions
It has been the purpose of this paper to demonstrate the tation of

a
computer implemen
describing the oxygen reduction at interfaces between Pt and YSZ. The simulated steady-state and small-signal behaviour have been compared with reported data. A procedure for the identification of the rate constants of the considered model has been attempted.
kinetic model
129
and
Validation
Although
the considered Pt,
Oz(g)
I YSZ
seems
to be
quite
well understood
electrode/solid electiolyte system, the actual

of the reaction mechanism is the theoretical
by far not a
procedure for the identification straightforward and easy task. From

unique
identifi
to be
analysis we
determined the conditions for the
ability of the unknown parameters which proved ness for the practical identifiability.
We suggest the
ters
only of limited useful

the model parame
following procedure for the estimation of of model M2 describing the Pt, 02(g) I YSZ system:
(i)
Determine the
versus
charge
transfer coefficient The
P from log(R^ )
values should
measurements
log(pQ ) plots
at -1000 K.
be obtained from electrochemical
Rt(pQ ) impedance
by subtracting
(ii)
the double
layer capacitance.
of the
charge transfer reac tion, AHci*, from an ln[f0(po *)] versus 1/T plot. Note that i0(po *) is accurately obtained from Rt data which can be enthalpy
obtained
as
-
Determine the activation
described
in
(i).
The
relation
i0
(RT)/(2F)
Rj"
can
be used to obtain
z'0.
(iii)
adsorption enthalpy AHad for high surface coverages from a ln(pG *) versus 1/T plot either at high Pq and low T (high surface coverage), or at low pG and high T (low surface coverage). Note that a large amount
of data is available in the literature for
Determine the oxygen
Ead
and
Edes,
as
well
asfcadand/cdes.
(iv)
From electrode with well known
geometry (e.g. strip elec
length of tpb, no porosity, and known Pt surface area), obtain impedance spectra. Use the parameter
estimates obtained in
trodes with well known
(i)
to
(iii) and
estimate
klc
with the
numerical method described.
(v)
Estimate
D(Oad)
and
Ed
from EIS measurements of elec
tiodes described in
(iv).
data and model
It is clear that
validation of
should be carried out
experimental continuously.
parameters
130
References
Model M2 accounts for the
adsorption
and
desorption
of oxygen
a
on
the Pt
surface, the surface diffusion of atomic oxygen, and for

fer reaction
near
two-electron trans
the
tpb. However,
much information is available about the be included in of

a
interaction between
refined model.
02(g) and Pt surfaces which could First, the adsorption/desorption dynamics

more
02(g)
on
the Pt
surface should be modelled in several orders of
detail,
as
the kinetic constants may vary
magnitude over
the pQ
range considered. To
diffusion
fully describe
diffusion and
the behaviour of porous electrodes, gas Knudsen
mass
(binary
can
diffusion) should be taken
into account. This
be
easily
accom
plished
with the numerical method
presented
in this paper.
centration
dependence
of the surface diffusion coefficient
Finally, the con of Oad could be
accounted for in the model.
Acknowledgments.
The financial
portation,
thank sions. In
gratefully acknowledged.
The authors wish to
present colleagues
in the Chair of Nonmetallic Materials for many useful discus

to A.
particular we are indebted Matlab/Simulink code examples.
Bieberle and R. Stadler for
carefully testing the
References
[1]
tem. Part I:
J. Gauckler. Theoretical analysis of the Pt, 02(g) I YSZ sys general framework, modelling, and structural investigation. /. Electro
chem. Soc, submitted.
[2]
[3]
The MathWorks, Inc. Matlab 4.2c.

The Mathworks, Inc. Simulink User's Guide. 24 Prime Park
Way, Natick,
Mass.
01760,1993.
[4]
The Mathworks, Inc. Matlab User's Guide. 24 Prime Park

1992.
Way, Natick, Mass. 01760,

Mc
[5]
G. N.
Graw-Hill Book
Vanderplaats. Numerical Optimization Techniques for Engineering Design. Company, New York, 1980.
L. Michelsen. Solution
[6]
J. Villadsen and M.
ofDifferential Equation Models by Polynom ial Approximation. Prentice-Hall, Englewood Cliffs, NJ, 1978. of Partial Differential Equations.
Clarendon Press,
[7]
G. D. Smith. Numerical Solution
Oxford, 1985.
[8]
G. Ehrlich and K. Stolt. Surface diffusion. Ann. Rev.
Phys. Chem., 31:603-637,1980.
131
and
Validation
[9]
Wang and A. S. Nowick. Cathodic and anodic polarization phenomena at platinum electrdoes with doped Ce02 as electrolyte: I. steady-state overpotential.
D. Y.
/. Electrochem. Soc, 126:1155-1165,1979. [10]

O.
J. Velle, T. Norby, and
P. Kofstad. The electrode
system 02/Pt/ /Zr02:8Y203
in
vestigated by impedance
[11]
M. Knudsen. A
tem
spectroscopy. Solid State Ionics, 47:161-167,1991.

In
sensitivity approach for estimation of physical parameters. Identification, pages 533-538, Copenhagen, Denmark, 1994. IFAC.
Sys
[12]
S. W.
Feldberg. Digital simulation: a general method for solving electrochemical diffusion-kinetic problems. Electroanalytical Chemistry, 3:199-296,1969.
S. W.
na:
[13]
Feldberg. Digital simulation of electrochemical surface boundary phenome Multiple electron transfer and adsorption. Comput. Chem. Instrum, 2:185-215,
1972.
[14]
T.
Joslin and D. Pletcher. The digital simulation of electrode processes, procedures for conserving computer time. Electroanal. Chem. Interfac. Electrochem., 49:171-186,
1974.
[15]
M.
J. Verkerk,
M. W.
J. Hammink, and A. J. Burggraaf. Oxygen transfer

with
on
substi
tuted
ance
Ce02 electrolytes platinum Zr02, Bi203, study. /. Electrochem. Soc, 130:78-84,1983.

digital
simulation
and
electrodes. II. A-C
imped
[16]
D. Britz,
J. Heinze, J. Mortensen, and M. Storzbach. Implicit calculation of bound
ary values in
ment.
applied
to several
types of electrochemical experi
/. Electroanal. Chem., 240:27-43,1988.
[17]
J. Fouletier, H. Seinera, and M. Kleitz. Measurement and regulation of oxygen con

tent in selected
gases
using
solid
electrolyte
cells. II. Differential gauge.
/. Appl.
Electrochem., 5:177,1975.
[18]
Feldberg. Optimization of explicit finite-difference simulation of electro phenomena utilizing an exponentially expanding space grid. Refinement of the joslin-pletcher algorithm. /. Electroanal. Chem., 222:101,1981.
S. W.
chemical
[19]
M.
Kleitz, T. Kloidt, and L. Dessemond. Conventional oxygen electrode reaction:
moxed ConductorsProc.
de, Denmark, 1993.
High Temperature Electrochemical Behaviour of Fast Ion and Miof the 14th Rise Int. Symp. on Mat. Sci., pages 89-116, Roskil Rise National Laboratory.
[20]
Siebert, A. Hammouche, and M. Kleitz. Impedance spectroscopy analysis of La1_xSr;i:Mn03-yttria-stabilized zirconia electrode kinetics. Electrochim. Acta,
E.
40:1741-1753,1995.
[21]
H. Lauret and A. Hammou. Localization of oxygen cathodic reduction zone at lan thanum manganite/zirconia interface. /. Europ. Ceram. Soc, 16:447-451,1996.
[22]
J. Mizusaki, K. Amano, S. Yamauchi, and

sonse
K. Fueki. Electrode reaction and repsensors.
characteristics of zirconia oxygen gas
/. Chem. Soc Jpn, 6:1160-1166,
1985.
132
References
[23]
T.
Kenjio,
Y.
Yamakoshi, and K. Wada. An estimation of the electrode-electrolyte
contact area
by linear sweep voltammetry in Pt/Zr02 oxygen electrodes. /.

A. S. Nowick. Diffusion-controlled
Electro
chem. Soc, 140:2151-2157,1993.
[24]
D. Y.
Wang and
polarization of Pt, Ag, and

of oxygen in
Au
electrodes with
doped
ceria
electrolytes. /.
Electrochem. Soc, 128:55-63,1981. and
[25]
L. R. Velho and R. W. Bartelett.
Diffusivity
solubility
platinum
and Pt-Ni
alloys.
Met. Trans., 3:65-72,1972.
[26]
N. L. Robertson and
J. N. Michaels. Oxygen exchange
on
platinum
electrodes in
zirconia cells:
Location of electrochemical reaction sites.
J. Electrochem. Soc,
137:129-135,1990.
[27] [28]
J. R. Macdonald. Trans. Faraday Soc., page 943,1969.

R. D.
ing
[29]
solid
Armstrong and R. Mason. The double layer capacity measurements involv electrolytes. Electroanal. Chem. and Interfacial Electrochem., 41:231-241,
Electroanal. Chem. and In
1973. R. D.
Armstrong. The metal-solid electrolyte interphase. terfacial Electrochem., 52:413-419,1974. Armstrong.

The Application volume 7, pages 157-202. The Chemical
[30]
W. I. Archer and R. D.
Electrolytes,
[31]
1987.
ofA.C. Impedance Methods to Solid Society, London, 1977.
[32]
N. L. Robertson and
tem: state and
[33]
tional
J. Gauckler. Reaction kinetics of the Pt, 02(g) I c-Zr02 sys parameter estimation. To appear in Proceedings of the 11th Interna Conference on Solid State Ionics, Hawai, 1997.
L.
[34]
T.
Jacobsen, B. Zachau-Christiansen,
In F. W. N.
Bay,
and S.
Skaarup.
SOFC cathode mech
M. Mogensen, and Poulsen, Bonanos, Zachau-Christiansen, editors, High Temperature Electrochemistry: Ceramic and MetalsProc. of the 17th Rise Int. Symp. on Mat. Sci., pages 29-40, Roskilde, Den mark, 1996. Rise National Laboratory.
anisms.
B.
S. Lindenroth,
[35]
C. A. Cavalca, G.
cation of
actor.
Larsen, C. G. Vayenas, and

oxidation
G. L. Haller. Electrochemical modifi
CH3OH
selectivity and activity on a Pt single-pellet catalytic re
/. Phys. Chem., 97:6115,1993.
[36]
C. G.
Vayenas
and S. G.
Controlled Promotion
Neophytides. Electrochemical Activation of Catalysis: In Situ of Catalyst Surfaces, volume 12, pages 199-253. The Chemical
Society, London,
[37]
1996.
J. Mizusaki, K. Amano, S. Yamauchi, and K. Fueki. Response and electrode reac tion of zirconia oxygen gas sensor. In T. Seiyama, K. Fieki, J. Shiokawa, and
133
and
Validation
S. Suzuki, editors, Chemical Sensors, volume 17 of Analytical
Chemistry Symposia
Se
ries, pages 279-284, Amsterdam, 1983. Elsevier.
[38]
B. A.
van
Hassel, B. A. Boukamp, and A. J. Burggraaf. Electrode polarization at the
Au, 02(g)/yttria stabilized zirconia interface: Part I: Theoretical considerations of

reaction model. Solid State Ionics, 48:139-154,1991.
[39]
F. Berthier,
J.-P. Diard, B. Le Gorrec, and C. Montella. Method for determining the

of
an
faradaic
impedance
electrode reaction:
Application
measurements.
Corros., 51:105-115,1995.
[40]
The Mathworks, Inc. Control
System
Toolbox User's Guide. 24 Prime Park
Way,
Nat
ick, Mass. 01760,1992.
[41]
A.
J.
A.
Winnubst, A. H. A. Scharenborg, and A. J.
Burggraaf.
The electrode resist
ance
of
Zr02-Y203(-Bi203)
solid
electrolytes
with Pt electrodes. Solid State Ionics,
14:319-327,1984.
[42]
J. E. Bauerle. Study of solid electrolyte polarization by a complex admittance meth ode. /. Phys. Chem. Solids, 30:2657-2670,1969.
M. J. Verkerk, M. W. J. Hammink, and A. J.
[43]
tuted
sistance
Zr02, Bi203, Ce02 electrolytes by D-C polarization. /. Electrochem. Soc, 130:70-78,1983.

with
and
Burggraaf. Oxygen transfer on substi platinum electrodes. I. electrode re

Study
of oxygen
[44]
H. Okamotoa, G. Kawamura, and T. Kudo.

num
through
observation of
exchange
current in a solid
adsorption on plati electrolyte concentration

Electrode
reaction
at
cell. Electrochim. Acta, 28:379-382,1983.
[45]
J. Mizusaki,
Pt,
K. Amano,
S. Yamauchi,
and
K. Fueki.
02(g)/stabilized
zirconia interfaces. Part II: electrochemical measurements and
analysis.
[46]
Solid State Ionics, 22:323-330,1987.
H. P. Bonzel and R. Ku. On the kinetics of oxygen
adsorption
on a
Pt(lll) surface.
Surf. Sci., 40:85-101,1973.

[47]
J. Mizusaki, K. Amano, S. Yamauchi, and K. Fueki. Electrode reaction at Pt, 02(g)/stabilized zirconia interfaces. Part I: theoretical consideration of reaction
[48]
J. L. Gland,
face.
Sexton, and G. B. Fisher. Oxygen interactions with the Pt(lll) Surf. Sci., 95:587-602,1980.
B. A.
sur
[49]
N. Nicoloso, W. Kernler, B. Leibold, A. Lobert, and W.
Weppner.
Electrical
re
sponse of oxygen
sensing Ti02
surfaces and fractal Pt/YSZ interfaces. Solid State
Ionics, 28-30:1637-1643,1988.
[50]
J. O. Bockris and London, 1970.

M.
A. K. N.
Reddy. Modern Electrochemistry, volume 2.

S. Primdahl. SOFC anode kinetics. In
and MetalsProc.
Plenum Press,
[51]
ture
Mogensen, S. Sunde, and Electrochemistry: Ceramic
of
the 17th Rise Int.
Sci., pages 77-100, Roskilde, Denmark, 1996. Rise National
High Tempera Symp. on Mat. Laboratory.
134
References
[52]
R. Lewis and R. Gomer. 1968.
Adsorption
of oxygen
on
platinum. Surf. Sci., 12:157-176,
[53]
Mogensen and S. Primdahl and M. Juhl. In U. Summing, S. C. Singhal, H. Tagawa, and W. Lehnert, editors, Proceedings of the Fifth International Symposium on Solid Oxide Fuel Cells (SOFC-V), page 385, Pennington, NJ, 1997. PV 97-40, The Electrochemical Society, Inc.
M.
[54]
J. Gauckler.
La2Zr207 formation
systems.
netics in
Lag 85Sr015MrL,03,02(g)
I YSZ
and oxygen reduction ki Solid State Ionics, submitted.
[55]
Raistrick, and R. A. Huggins. AC admittance measurements on sta bilized zirconia with porous platinum electrodes. Solid State Ionics, 1:251-271,1980.
T. M. Giir, I. D.
[56]
J. Sasaki,
H.
Mizusaki, S. Yamauchi, and K. Fueki. Studies
of stabilized zirconia cell
systems by complex impedance
on electrode processes method. Bull. Chem. Soc.
Jpn., 54:1688-1692,1981.
[57]
G. Reinhardt.
Phasengrenzreaktionen an Perowskitelektroden auf stabilisiertem Zr02: Implikationen fur die Abgassensorik. PhD thesis, Universitat Tubingen, 1994.
[58]
P.
Fabry
and M. Kleitz. Influence of the metal and the
the characteristics of the oxygen electrode reaction J. Electroanal. Chem. Interf. Chem., 57:165-177,1974.
on
electrolyte composition on solid oxide electrolyte.
[59]
T. H. Etsell and S. N.
Flengas. Overpotential behaviour of stabilized zirconia solid

/. Electrochem. Soc, 118:1890-1900,1971.
electrolyte
[60]
T. M.
fuel cells.
Giir, I. D. Raistrick, and R. A. Huggins. Steady-state D-C polarization char acteristics of the 02, Pt/stabilized zirconia interface. /. Electrochem. Soc, 127:26202628,1980.
[61]
D.
at
Braunshtein, D. S. Tannhauser, and I. Riess. Diffusion-limited charge transport platinum electrodes on doped Ce02. /. Electrochem. Soc, 128:82-89,1981.
[62]
H. S. Isaacs and L.
on
J. Olmer. Comparison of materials as oxygen catalytic electrodes zirconia electrolyte. /. Electrochem. Soc, 129:436-443,1982.
on
[63]
J. L. Gland. Molecular and atomic adsorption of oxygen Pt(S)-12(lll)x(lll) surfaces. Surf. Sci., 93:487-514,1980.
A. C.
the
Pt(lll) and
[64]
face. /. Chem.
Luntz, M. D. Williams, and D. S. Bethune. The sticking of 02 Phys., 89:4381^395,1988.
on a
Pt(ll 1)
sur
[65]
Franklin, J. D. Powell, and A. E. Naeini. Feedback Control of Dynamic Systems. Addison-Wesley, Reading, MA, 1994.
C. F. Bernasconi. Relaxation Kinetics. Academic Press, Inc., London, 1976.
R. Gorte and L. D.
G. F.
[66]
[67]
Schmidt, Desorption kinetics with precursor intermediates. Surf. Sci.,
76:559-573,1978.
135
and
Validation
Appendix
3-A.l
Reaction Model Constants and Parameters
Table 3.1
Quantities
Symbols
area
Values
Units
Ref.
Apparent
electrode
10-4
0.7
m2
1
Electrolyte
coverage
^cov 'char
L
[1] [1] [1]
Characteristic
length
pm pm
nm
Electrode thickness
Extension of
20 10
tpb
Azx D0
Surface diffusion constant

Activation energy of surface
4.65 155
10-*
m2/s
kj/mol
[15] [52]
diffusion Number of surface sites for

atomic oxygen
d
N0
v*d
1.6603
lO"5
mol/m2
s"1
[63]
Frequency factor of oxygen adsorption Frequency factor desorption

of oxygen
109 io12
No
[67]
vdes
m2/(mo-s)
[67]
Activation energy of oxygen
adsorption
Activation energy of oxygen
Ead
Edes
33
kj/mol
[48]
200
kj/mol
[48]
desorption
Concentration of oxygen vacancies in YSZ
[V0]
4.65
103 104
mol/m3 mol/m3
kj/mol [9,10]
Concentration of oxygen ions in YSZ

Activation energy of for
[Oc]
4.45
ward electrochemical
tion
reac
E\
125
136
Appendix
Table 3.1
Quantities
Activation energy of back
Symbols
Values
135
Units
Ref.
ward electrochemical
tion
reac
El
*lc
p
T
kj/mol
[9,10]
Forward electrochemical
rate constant
2-106
0.62
m3/(smol)
1
Charge
transfer coefficient
Temperature
650... 1200 1 to
Oxygen partial
pressure
Po2
105
Pa
3-A.2
Determination of
Cdl by
Potential
Step Chronoamperometry
impedance of a Pt, 02(g) I YSZ system can be reasonably well described by the equivalent circuit shown in Fig. 3.3d. The only difference to the equivalent circuit of Fig. 3.3 c is that we assume that the Faradaic impedance ZF(jco) can be approximated by a conventional parallel circuit of a capacitance C and a concentration resistance Rc. From a node analysis (see, for example, any textbook about electrical engineering) of this circuit we obtain the following state-space description for the circuit in Fig. 3.3 d
Let
us assume
that the electrochemical
-1/Cdl(l/Re + 1/Rt)
l/(CRt)
l/(CdlRt)
-1/C(l/Rt + 1/Rc)
[l/(CdIRe) 0] [-1/Re o]
[1/RJ
(3-A2.1)
with
x(t)
Uix(t)
and where T denotes vector
m2(o]
"o
"(f), and y(0
l/Re(u(t)-ul(t)),
are
transposition.
Two relaxation times tx and x2
137
and
Validation
symbolic mathematics program such as Mathematica or Maple). Quite lengthy expressions for x4 are obtained. The faster relaxation time is associated with the double layer capac itance, although in a rather complicated form. Can we simplify the analytical expression for x{? At temperatures around -950 K we find typical values for Rc in the order of 100 Q-cm2 and C is typically in the order of 1 mFcm"2. The values for Rt, Re, and Cdj are at least one order of magnitude lower. This makes a simplification to a certain extent of the expression for t^ possible. In addition, if Rt Re we can finally derive
obtained from the
eigenvalues
of the matrix A
(use
Cj]RRt
x'a^fLet
us now
(3"A2-2)
analyse the relative error we make in the estimation of Cdl when experimental potential step chronoamperometry data are evaluated with the expression t* ReCdl instead of the expression derived above (note that the exact value for x of the equivalent circuit shown in Fig. 3.3a is easily obtained from a node analysis as x (CdlReRt)/(Re + Rt) which corresponds to Eq. (3-A2.2)). The result is shown in Fig. 3-A2.1 for C 1 mF, Rc 100 Q, Cdi 1 pF, and Re 10 Q. It is seen that the expression x* ReCdl is only a good approximation for x if Rt > (5... 10) Re. If Rt < Re, the values for Cdl are estimated too low if the step response data are evaluated with the expression for x* instead of x. In addition, the expression derived above for Xj (Eq. (3A2.2)) is a very good approximation down to very low values of Rt. We conclude that the true values for Cdi of Pt/YSZ interfaces can be obtained from potential step chronoamperometry experiments if the current decay curves are evaluated with Eq. (3-A2.2) if Rt Re, which is generally ful filled at low temperatures. However, numerical estimates of Rt (and Re) are required. But, as we show in the main text, Rt is related with the exchange current density i0 which itself can be obtained from a Tafel analysis. Unfortu nately, a Tafel analysis only gives reasonable values for /0 if the reaction is charge-transfer controlled, which is certainly not the case for the Pt, 02(g) I YSZ system at temperatures below 1000 K. On the other hand, at high temperatures the reaction would be charge-transfer controlled which implies that Rt R (i.e. Rc 0), thus making a simplification of the equation describing the relaxation time impossible. We propose to employ the method of Berthier et al. [39] for estimating Cdl from impedance data, as demon
=
strated in the text.
138
Appendix
0i
-1
logctyjy
potential step responses of equivalent circuits.The ratio x/x* is shown (relative error). Only if Rt > Re, the error is below a factor of 2. The fol lowing parameters were taken (see equivalent circuit of Fig. 3.3d): Re 10 Q, Rt 10 Q, 0.1 ms and X 0.045 ms. The rela Rc 100 Q, Cdl 10 pF, C 1.5 mF. We obtain X*
Fig.
3-A2.1
Comparison
of
tive
error
is
a
a
factor of ~2 for these parameters (see

+10 mV
figure).
The inset shows the current
response to
potential step input.
3-A.3
Implementation
In this
and Simulations of Model Ml
General.
example
the
implementation and
simulations of model Ml
Only a basic familiarity with the pro grams is assumed which can be obtained by working through the introduc tory chapters of the handbooks [3, 4]. A very good introduction to block diagrams can be found in the textbook from Franklin [65]. The reader is encouraged to try the implementation for himself and to experiment with the model. All the examples shown below can be worked through with the stu
dent version of the software
in Simulink and in Matlab is shown.
(Matlab:
are
version 4.2; Simulink: version
1.3). The
3-A.l
concern
parameters used for simulations

and evaluated at T
=
taken from Table 3.1 in

=
appendix
need to
1000 K and pQ about the parameters for the moment.
1 atm. There is
no
139
and
Validation
Fig.
3-A3.1
Simulink block
diagram
for the
adsorption/desorption dynamics.The
can
initial value of the
integrator
block is set to xO. The simulation

an
be followed within
the Simulink window

to
any connection
by connecting line (although it
Auto-Scale
will be most
Graph from the Sinks Block Library interesting to follow x (t)). Set the
parameters
in the Simulation-Parameters... sub-menu and start the simulation. This pos
sibility
is convenient in the
early stage
of model
testing and debugging.
Adsorption dynamics.
First, the
implemented
parameters
in
block
as
adsorption and desorption dynamics is diagram (Fig. 3-A3.1; filename: simadsl.m). The
are
defined
p02
NO kad
=
1;
1.6e-5;
in
units
of
(10^5
Pa)
1.8888e7;
=
kdes
4.3007e6;
The initial value of
is set to xO
0.65. The rk45
(Runge-Kutta
fifth
order) integration methods

tol
=
is used with
le-3;
=
minstep
le-6;
maxstep
le-3;
options
xO
=
[tol,
minstep,
maxstep];
0.65;
=
[t,x]
rk45('simadsl', plot(t,x),
1.5e-2,
xO,
options);
ylabel('x')
subplot(221),
xlabel('t/s'),
140
Appendix
0.68
200
^v
/
'
0.67
Is]
N
o5 100
CO
^^s.
0.66
'
n
0
0.65 0.01
4r\n
200
400
Real(Z,Zf)
x10" 10
110*
o
-
3"
o
o
g-10*
10"
-0.2
-0.1 etaA/
0.1
-0.2
0.2
voltage/V
Fig.
ters
3-A3.2
Simulation results for model Ml at reference conditions.The

were
parame
sub
from Table3.1
evaluated
at
1000
and p02
a
atm.
plot (221)
shows the time response of x(t)
for
small deviation from the
equilibrium
ance
value X0. subplot (222) shows the Faradaic

=
impedance and
V
the
imped
A (larger semicircle) double layer capacitance of Cdl 10e-6 wasassumed. subplot (223 ) showsthe charge transfer resistance Rt and the polarization resistance Rp as a function of the overpotential eta. subplot (224) shows the current-voltage behaviour of Ml.
at eta
and eta
-0.8
(smaller semicircle).
The
subplot(221)
Graph
of
Fig.
3-A3.2 shows the time

can can
dependence
of the surface
on
concentration. The simulation
also be followed within Simulink be found in the Sinks Block
the The
Auto-Scale
block which
can
Library.
integration parameters
submenu.
be set
directly
in the Simulation.Parameters...
The surface concentration attains its
equilibrium value
X0
K*sqrt(p02)/(1+K*sqrt(p02))
141
and
Validation
where
sqrt(kad/kdes)
The relaxation time for small
(cf. part I).

tau
=
perturbations
is
given by [66]
l/(4*kdes*X0+kad).
Note that the result for the relaxation time is based the
on
the
assumption
that
perturbation
is small. If the
starting
value is far from the
equilibrium
value, the simulated values for the relaxation time will deviate from the
small-signal value.
Electrochemical reaction.
We
now
include the electrochemical reaction.

Simulink block
diagram (filename: simmodla.m). See the main text and Table 3.1 for a detailed description of kf, kb and the remaining parameters. Non-linearities are due to the exponential dependence of kf and kb on the overpotential. The Fen block in the Nonlin ear Block Library is best used for this purpose. Note that the eta (t) block corresponds to an inport block and that the IF(t) block corresponds to an outport block from the Connections Block Library. From this block diagram we can easily obtain the Faradaic admittance YF(jco) at equilibrium potential.
Fig.
3-A3.3
shows the
corresponding
We define the
following
A
=
constants
ac
0.62;
2.73e-7;
8.314;
1000;
96487;
f kf
F/(R*T);
=
2.7474e3;
kb
5.7577e3;
Note that the electrochemical rate constants
can
not be chosen
independently
(cf. part I).

is set to
a
It is
good
idea to check the time
different value than the
dependent behaviour now. If xO equilibrium one, the system will relax

a
towards the decrease to
equilibrium
state
within
short time. The current should

If
(or very low values) due to the constraint linearized state-space model (SSM) is obtained as follows:
zero
(Eeq)
0. The
XO
K*sqrt(p02)/(1+K*sqrt(p02))
=
[a,b,c,d]
linmod('simmodla',
XO,
0);
142
Appendix
eta(t)
Fig.
3-A3.3
Simulink block
diagram
of Ml in order to extract linearized state-space
models.The
integrator block
is set either to 0
(zero)
or
to XO.
where the
is
a,
b,
to
c, d
quadruple denotes
that XO is
was
the linearized state-space matrices. It

as an
important
recognize
given
argument
to
the function
zero
linmod. If
no
argument
given,
for
a
the function linmod would take

a
for
the surface concentration which would result in
wrong SSM. See also the
on-line
help (help linmod) impedance form,
description
of the purpose of the function
and its arguments. Note that than in
we
have the SSM in admittance form rather

a
because "simmodla" defines
model of the form
YF(s)-r)(s) where s is the Laplace variable, ri(s) is the Laplace transform of the input, IF(s) is the Laplace transform of the output, and YF(s) is the Laplace transform of the Faradaic admittance.
IF(s)
=
We continue with the transfer function to obtain the electrochemical

ance
(we
use
deliberately
as
"electrochemical
ance" because,
it should have become
imped impedance" and not just "imped clear, we could analyse different
143
and
Validation
input/output relationships (e.g. current as output))

[numYf,denYf]
w
= =
the oxygen
partial
pressure
as
input
and the
ss2tf(a,b,c,d);
logspace(-l,5,100);
=
[reZf,imZf]
Zf
=
nyquist(denYf,numYf,w);
reZf
j*imZf;
Note that
where Zf denotes the Faradaic
impedance.
we
changed
the varia
bles for denYf and numYf in the
input of the nyquist function to obtain the result for the impedance (see help nyquist). A simple calculation reveals the electrochemical impedance Z including a double layer capacitance Cdl
an
and
electrolyte resistance Re
=
Cdl
w
=
10e-6;
Re
10;
the
Z
w';%
transpose
+
frequency
=
vector!
j*w*Cdl
l./Zf;
Re
l./Y;
Let
us
plot the results (Fig. 3-A3.2)

plot(real(Zf)
'-');
500 -100
+
subplot(222),
real(Z),
axis
Re,
-imag(Zf),
'',...
-imag(Z),
axis([0
equal;
300]),...
xlabel('Real(Z,Zf)'),
...
ylabel('-imag(Z,Zf)'),
grid;
The low
ance,
frequency intercept of Zf
and
correspond to the polarization resist
Rp
l/(d-c/a*b),
the
high frequency intercept
of zf
corresponds
to the
charge
transfer resist
ance,
Rt
1/d,
and the
ance,
high frequency intercept of z corresponds to the electrolyte resist Re (see part I of this publication for further details). It is seen that the
144
Appendix
reaction kinetics is almost
entirely
controlled
by
the
adsorption
of oxygen.
The
charge transfer resistance is low compared with the polarization resist ance. It is generally a good idea to validate the simulations with analytical results. In part I of this publications we give the linearized SSM in analytical
form
al= bl=
cl=
-4*kad*pO2*N0*(l-X0)
2*ac*f*kf*X0
+
4*kdes*N0*X0
kf-
kb;
2*(l-ac)*f*kb*(l-X0);
-2*N0*F*A*(kb+kf);
dl=
2*N0*F*A*(2*(l-ac)*f*kb*(l-X0)
2*ac*f*kf*X0);
which Let
us
are
equal to the a, b,
c, d
matrices obtained with the function linmod.

a
know obtain simulations at
cathodic
overpotential
of
eta
-0.08.
With
eta
-0.08;
=
[X,U,Y]
trim('simmodla',
=
XO,
eta,
[
X,
],
U)
;
],
[1],
]);
[a2,b2,c2,d2]
linmod('simmodla',
and with the
same
calculations
an
as
in the
equilibrium
case are
we
obtain the
impedances
procedure
zf and z at
overpotential
of -80 mV which
hold
also shown in
subplot(222) of
as
Fig.
3-A3.2
(use subplot (222),

are a
on, and the same
things which are noteworthy about these three lines of Matlab code. If an overpotential is imposed at the input, the system state will change to a new steady state. The value for the state variable x will be lower than the equilibrium value X0 (cathodic overpo tential). The corresponding current is given by Y. The output of trim is used as the input of the function 1 inmod which give the linearized SSM at the new operating point. Note that Rp decreases with increasing eta. However, increasing eta to much higher values will increase Rp drastically because the steady-state values for X decrease. We find that the reaction is limited by the rate of adsorption. If we wanted to obtain simulations at overpotentials with the analytical
in the first
case). There
few
model,
ble
x
we
had to substitute the state variable X0 with the actual state varia
on
analytical expressions of the state-space matrices. This requires either an analytical solution of the mass balance equa tion, or that we solve this equation numerically. This can be done with the
eta)
constr
(depending
in the
Simulink function
(or, if available, with the function
f solve
from
145
and
Validation
the
Optimization Toolbox).
We
see
that it is much
more
convenient to find the
steady-state point with the function trim. The function constr may solve a number of different problems and it will be needed for parameter estimation (fitting). The function trim makes use of constr. It is worth to know the abilities and limitations of trim and constr in some depth.
Let
us
consider the behaviour of

run
Rt
and Rp
over a
range of
overpotentials
from 0.2 V to 0.1 V. We
the
following commands:
etaList
for
m
=
[-0.2:0.04:0.1];
1:length(etaList),
etaList(m);
eta
[X(m),U(m),Y(m)]=trim('simmodla',x0,eta,[],[],...
[1],[]); [a2(m),b2(m),c2(m),d2(m)]
X(m), Rt(m) U(m));
=
=
1inmod('simmodla',
...
l/d2(m); l/(d2(m)-c2(m)/a2(m)*b2(m));
Rp(m)
end
Occasionally,
the
following warning message may appear

of
Maximum number
iterations
exceeded
increase OPTIONS(14)
In this
case
trim has not found

more
solution after
default number of iterations

and the function
(options (14)). For
details about the

or
options vector
trim, refer to the manuals
the on-line
that any
help (help
foptions; help
should be taken
The results
trim). We would like
to
point out
warning message
seriously and the reason for it should are finally plotted in a semilogy plot
subplot(223),
be found
(and eliminated).
semilogy(etaList,
grid
Rp,
'o',
...
etaList,Rt,'*'),
xlabeK'eta/V),
ylabel('(Rp,Rt)/Ohm')
exponential dependence of Rt on eta is readily seen. Finally, we look at the steady-state current-voltage curve of model Ml. All blocks in the model simmodla are selected and grouped. A Repeating
where the
146
Appendix
m
eta(t )
Sut>systern
IF">
eta
Fig.
3-A3.4
Simulink block
diagram
of Ml for simulation of
current-voltage
behav
iour.The
port is
Subsystem contains the block diagram given in Fig. needed to plot the data in an I (U) diagram.
3-A3.3. The second out-
Sequence
block from the Sources Block
Library
is used
as
input
and
second
outport is used for the feed-through of the input (cf. Fig. 3-A3.4; filename: simmodlb.m). The vector [ 0 dt 2*dt 3*dt 4*dt] is used as time value
and
[0
-du
du
0] is used
as
output value
is almost
in the
Repeating Sequence
con
block. We
scan
with 6 mV/s
(which
zero
for the system under
sideration).
dt
100;
du
=
0.3;
TF
4*dt;
TF,
[T1,X1,Y1] [le-3,
If
=
gear('simmodlb',
TF/20]);
=
X0,
...
TF/1000,
V
Yl(:,l);
Yl(:,2);
subplot(224),
plot(V,If),
grid
The results
can
be found in subplot (224) of
ing
The
cathodic and anodic behaviour is found
Fig. 3-A3.4. Note that a limit at relatively low overpotentials.
step response
we
to
an
in 3-A.2. Because Cdl
potential step at the input can be simulated as shown and Re play a significant role in the time-dependent
I-V
curve
behaviour
must
include them in the model.
We learn from the EIS
spectra and the
that further processes, not

must
just
the dissociative oxygen
adsorption
near
the
tpb,
play
significant
role in the towards
supply of atomic oxygen. Surface diffusion of atomic oxygen the tpb must be taken into account when investigating the kinetics of
gas electrodes.
high temperature oxygen
147
and
Validation
3-A.4
Implementation and Simulations

In this
of Model M2
appendix we present the implementation of model M2 in Matlab and Simulink. Special emphasis is given on the implementation of the mass transport phenomena in Simulink. Note that the full version of Simulink is required to perform the simulations (the student version is limited to 40
General. blocks per
model). The parameters used for the simulations
are
taken from
=
Table 3.1 of
appendix
3-A.l and evaluated at T

on a
973 K and
p0z
103
Pa.
Matlab version 5.1 and Simulink version 2.1
SPARCstation 5
operating
under Solaris 2.5.1
were
used for the simulations.
Programme
ters
initialization.
We first define the model constants and parame
(see also appendix 3-A.l).

=
Aelectrode
Acov
le-4;
% %
apparent
electrode
area
=0.7;
=
electrolyte
coverage
Lchar
2e-6;
characteristic
*
length
%
tpb
R
F
=
4*Aelectrode/Lchar
%
% % % % % %
sqrt(1-Acov);
constant constant
constant
Eq.
(2-A2.2)
8.314; 96487;
=
gas
Faraday Avogadro
Na T
=
6.023e23; 973;
=
temperature
in units
of
in
units
of
p02
Voo
le-2; 4.65e3;
4.45e4;
(10^5
Pa)
oxygen oxygen
vaccancy
concentration
Oox
ion
concentration
The
penetration depth
=
8 is obtained
as
described in subsection 3.3.2:
DO
4.65e-4;
=
surface
diffusion constant
energy
Ediff
D
=
155e3;
activation
surface
D0*exp(-Ediff/(R*T));%
=
diffusion
coefficient
wmax
exp(21.11-14150/T);
wmax*(p02)A(1/2);% cf.
=
Wmax
Fig.
3.2
delta
6*2/sqrt(pi)*1/(sqrt(Wmax/(2*D)));
Having determined the penetration depth we can divide 8 in compartments of increasing size according to a geometric series (note that we fix the width of the tpb compartment to 10 nm):
148
Appendix
dzl
10e-9; 2;
% % % % %
width
of
tpb compartment
guess
qO
n
=
starting
number
of
10;
=
compartments;
dzl
A
=
10e-9;
width active
of
tpb compartment
around
dzl*tpb;
area
tpb
fzero('compart',
qO,...
%
[],[],dzl,delta,n);
dz for
find
series
of
factor
=[];
k=l:n,
=
width
compartments
dz(k)
end
dzl*q"(k-l);
where
'compart'
f
is
small M-file called compart.m:
function f
=
compart(x,dxl,delta,n)
-
dzl/delta
(1-x)/(l-xAn);
The
midpoints
of the compartments
are
obtained from:
for
pp=l:length(dz),
=
Zaxis(pp)
end
sum(dz(1:pp-l))
dz(pp)/2;
and the time constants for surface diffusion
(Eq. (3.9))
are
obtained
as
Tdiff
dz.A2./(2*D);
We continue with the constants for the
adsorption and desorption:

of
NO
Iel9/Na;
=
%
%
number
adsorption sites
of
nadO ndesO
Ead
=
le9;
=
freq.
factor
factor
adsorption desorption
for for
2el2/N0;
% % % %
freq.
of
33e3;
=
activation activation
activation
energy
adsorption desorption
Edes
DH
=
200e3;
energy
l/2*(Edes-Ead);
enthalpy
We
now
determine the electrochemical
quantities:
149
and
Validation
Elf
%
125e3;
activation
energy
of
forward
reaction
=
Elb
De
ac
=
135e3;
Elf
-
backward
reaction
Elb;
%
0.62;
=
charge
transfer
coefficient
kad kdes
K
=
nad0*exp(-Ead/(R*T));
=
ndes0*exp(-Edes/(R*T));
;
sqrt(kad/kdes)
=
ff
TO
F/(R*T);
1000;
=
reference forward
temperature
rate
in
klfChem
klfTO K0
=
=
2e6;
chemical
%
constant
klfChem*exp(-Elf/(R*T0));
cf.
Eq.
(2.60)
sqrt(nadO*exp(-Ead/(R*T0))/...
(ndes0*exp(-Edes/(R*T0))) )
klbTO
=
klfT0*Voo/0ox*K0;
=
cf.
Eq.
(2.62)
klbChem
klbTO*exp(Elb/(R*T0));
Note that the backward chemical rate constant k-
(klbchem)
must be
expressed in terms of the forward chemical rate constant klc (klf Chem). This must be accomplished via Eq. (2.62). The equlibrium potential is obtained as follows (cf. Eq. (2.59)):
EeqT
=
1/(2*ff)*log(klfChem/klbChem*...
exp(-(Elf-Elb)/(R*T))*Voo/Oox*K);
EeqP
=
l/(4*ff)*log(p02);
EeqT
+
Eeq
EeqP;
and
finally (cf. Eq. (2.74)):

=
klfEq
klbEq
klfChem*exp(-Elf/(R*T))*exp(-2*ac*ff*Eeq); klbChem*exp(-Elb/(R*T))*exp(2*(1-ac)*ff*Eeq);
We
finally
add
some
electrolyte
one
resistance
(thickness: 0.5
mm; area: 1
cm2)
to
and further
assume
that
half of the
electrolyte
thickness is
contributing
the
electrolyte
sigma
Re
= =
resistance
(three-terminal measurement):
1.63e2*exp((-0.78*1.602e-19*Na)/(R*T))*le2;
*
0.5
l/sigma*0.5e-3/le-4;
150
Appendix
At
zero
current the surface
coverage is
given by (cf. Eq. (2.58)):
xO
x
=
K*sqrt(p02)/(1+K*sqrt(p02));
ones(n,1)*x0;
%
surface
concentration vector
The last command generates
vector of
length equal
to the
number of
com
partments. Under zero current conditions there will be no concentration gra dient, therefore, all components of the vector x will be equal.
It is
generally useful
parameters
are
to
keep
all these parameters and constants within
dif
ferent parameter M-file, except the temperature and oxygen
partial
pressure.
The
loaded into the
workspace
from within the main program
where
appropriate.
diagram.
In
Simulink block
Eqs. (3.10)
to
(3.12) the
mass
balances
were
given
block
for the various
diagram
of Ml
compartments. We start our considerations with the (cf. Fig. 3-A3.3). The block diagram of the tpb compart
ment of M2 is obtained
in
Eq. (3.10)).
are
The
by adding the blocks for surface diffusion (last term resulting diagram is shown in Fig. 3-A4.1. Note how we
con
added the terms for surface diffusion and that the electrochemical rate
stants
defined
were
slightly
different than in
Fig.
3-A3.3. In Ml the results for
kf and kb
obtained from:
kf
klfEq*Voo;
kb
klbEq*0ox;
Using
as
1000
Kandp02
we
obtain the
same
results for kf and kb
appendix 3-A.3. Note also that the initial value of the integrator block must be set correctly, this is best accomplished by introducing a vector x of appropriate length (equal to number of compartments) and setting the initial
in
conditions of each individual
compartment
to
(i). The
same
time constants of the surface diffusion process
(compare
the
applies to the multiplication
block with 1 / Tdi f f
(1)).
Similarly we obtain the block diagrams for the other compartments. The complete block diagram for M2 is obtained by packing every compartment into a subsystem and by connecting these subsystems appropriately. Fig. 3A4.2 shows an example with four compartments and the notation introduced in Eqs. (3.10) to (3.12). The entire block diagram can be easily extended to
more
than four
compartments by copying and pasting

it with the
an
intermediate sub
system and connecting
remaining part.
Note that the initial condi-
151
and
Validation
Oad(1)
Oad(2)ad(2)
l*^*"^
eta(t)
Fig.
3-A4.1
Simulink block from Ml with
diagram
for the
tpb compartment
is the
of M2.We
used
the
block
diagram
process
IF
(marked
(Fig. 3-A3.3 ) and added dropped shadows), eta(t)

is fed into this
the blocks for the surface diffusion
system input quantity and

atoms in Oad (1) is fed into com-
(t) is the
system output quantity. The concentration of adsorbed oxygen

two
compartment patment
two.
(Oad (2))
compartment and
Oad(3)
Oad(2)
%
oo
Oad(4)
Oad(1)
>
i=3
Oad(3)
>
i=2
Oad(2)
eta(t)
>
tpb
IF(t)
Fig.
tem
3-A4.2
Simulink block
to the block
corresponds
diagram of M2 with four compartments.The tpb subsys diagram shown in Fig. 3-A4.2.
152
Appendix
tions of the
integrator
for every
blocks and the 1/Tdiff (i)
blocks must be set
appropriately
subsystem. For clarity the block diagram of subsys tem 2 is given in Fig. 3-A4.3. Obviously, only the blocks representing the sur face diffusion process and the adsorption/desorption process are present.
The initial condition for the
stant for the surface
integrator
block is set to
(2) and the time

we
con
diffusion is set to Tdif f (2)
(note how
defined the
vector of Tdif f).
Simulations. Simulink block under the

can
run
simulations of M2
we save
create
diagram
mode 12
with ten
.
(n
10) compartments. We
this file 3.22b
name
m.
We show in detail how the results from
Fig.
be obtained.
We
begin
T
with the Faradaic

=
impedance
0.01
at zero
overpotential (note
that
we
defined
973andp02
above):
0);
[a,b,c,d]=linmod('model2',
[numYf,denYf]
w
=
x,
ss2tf(a,b,c,d);
w
=
logspace(-l,5,100);
=
w'
[reZf,imZf]
Zf
Y
= =
nyquist(denYf,numYf,w);
Cdl
Z
=
=
reZf
j*imZf;
+
20e-6;
Re
+
j*w*Cdl
l./Zf;
l./Y;
Oad(2) Oad(1)
Oad(3)
Fig.
3-A4.3
Simulink block
main text for further
diagram explanations.
for
compartment
two of M2
(subsystem).See
153
and
Validation
subplot(221),
real(Z),
axis
plot(real(Zf)
'g-');
Re,
-imag(Zf),
'b-',...
-imag(Z),
equal;
xlabel('Real(Z,Zf)'),
ylabel('-imag(Z,Zf)')
3.22b for
=
which should value

Rp
=
give
the
curve
shown in
resistance
Fig.
0. Note that the
for
the
polarization
973andp02
=
(Rp
l/dcgain(a,b,c,d)
of
in
82.52 should also be in

=
agreement with the simulation results given

0.01.
a
Fig.
It is
eta
3.16forT
more
interesting
to the
to consider
situation where
we can
cathodic
overpotential
is
imposed
system.
Note that
not
simply repeat the calcula

x,
tions from above with [a,b, c,d] =linmod( 'model2 ',

x
eta), because
does not contain the actual
the
steady-state steady-state equilibrium point:

=
values. We first have to determine
eta
-0.035;
=
as
in
Fig.
3.22
options(2)
le-6;
options(4)=le-8; options(10)
while
=
le3;
xtemp
>=
x;
options(10)
100,
options(14)=100;
[X,U,Y,DX,options]=trim('model2',...
xtemp,eta, [],[], [1],[],[],[],options); xtemp
end
=
X*(l+eta*randn(l));
Type
help
f options to
get
more
information about the options. We
use
the while within

tor
a
loop
because the function trim does not
always
find
solution
vec
reasonable number of iterations. The result of trim is the state
X, the
input u
and
the output
Y.
Check these results
by typing:
x
=
0.1151 0.1202 0.2165

0.2141
0.1278 0.1388
154
3.5
Summary
and
Conclusions
0.1536
0.1718 0.1907 0.2059
U
=
-0.035
Y
=
-3.2038e-04
input overpotential of -35 mV and that Y cor responds to an output current of -0.32 mA/cm2. The sort order of the X vector
Note that
u
corresponds
to the
seems
somewhat
strange,
but the necessary information

as
can
be obtained
from the variable info which is obtained
follows:
>>
[str,xo,info]
info
'
model2;
>>
model2/Subsysteml/Oad'
'mode12/Subsys tem2/Oad' 'model2/SubsystemlO/Oad' 'mode12/Subsystem9/Oad'
'model2/Subsystem3/Oad'
'model2/Subsystem4/Oad'
'model2/Subsystem5/Oad' 'model2/Subsystem6/Oad' 'mode12/Subsys tem7/Oad' 'mode12/Subsys tem8/Oad'
This order is
obviously
in
agreement with the order of
X.
The concentration
profile
of adsorbed oxygen is
easily
obtained with:
plot(Zaxis,
sort(X));
We
can now
obtain the linearized SSM
as
follows:
[al,bl,cl,dl]=linmod('model2',
X,
eta);
155
and
Validation
Note that not the initial values within the
integrator
x
blocks
are
used
by
the
function linmod, but that the state vector

are
is evaluated. The initial values
contained within the vector
to
plot
the results.
procedure as above can be used Compare again with the curves shown in Fig. 3.22.
xo.
The
same
Similarly, current-voltage simulations can be obtained as described in appen dix 3-A.3. Limiting currents are determined with trim using high cathodic overpotentials (cf. Fig. 3.21).
156
Part
III
The Interface between
La0.85Sr0.15Mnt/3+5
and
Yttria-Stabilized Zirconia
158
Chapter
Lanthanum Zirconate
Formation
and
Oxygen
Reduction Kinetics
Abstract
growth of lanthanum zirconate (LZO) between (001) single crystals of 9.5 mol% Y203-stabiUzed Zr02 (YSZ) and 0.95... 1.10) perovskites were porous La085Sro.i5Mny03g (y investigated. The perovskites were screen-printed on the solid electrolyte and sintered in air at 1373 K for short periods. High
=
Nucleation and
resolution
transmission
electron
microscopy, electrochemical
force
impedance spectroscopy, and atomic employed for interface characterization.

tration in the
microscopy
were
The manganese
concen
perovskite
affect the onset of nucleation and the
growth
LZO
rate
of lanthanum zirconate. Excess lanthanum oxide
within the
perovskite reacts immediately with YSZ to form dense layers. Layer growth kinetics is controlled by bulk diffusion perovskite
leeds to the reductive forma
of cations. Stoichiometric
cathode/electrolyte interface after a few minutes of sintering. The A-site deficient perovskite is char acterized by the reductive dissolution of Mn into YSZ in the early
tion of cubic LZO islands at the
*)
Submitted to Solid State Ionics.
La2Zr207
Formation
and
02
Reduction Kinetics
sintering stage
and
by
pronounced
surface diffusion of cations.
perovskite is reached, reductive nucleation of LZO originates. Island growth is control led by surface diffusion of cations and the supply of lanthanum.
After the critical Mn concentration in the
The electrochemical
properties
of the cathode/YSZ interfaces

LZO at the
are
strongly influenced by the formation of boundary. Charge transfer, dissociation

nated from electrochemical
triple phase
are
of adsorbed molecular discrimi
oxygen ions, and surface diffusion of atomic oxygen
impedance data.
strontium
Keywords.
(SOFC).
Lanthanum zirconate
(La2Zr207); lanthanum
manganite;
oxygen
reduction; electrochemical kinetics; electrochemical impedance; solid oxide fuel cell
4.1
4.1.1
Introduction
General
ion
conducting Yttria-Stabilized Zirconia (YSZ) and perovskite-type Sr-doped LaMn035 (LSM) have been widely used as electrolyte and cathode materials in Solid Oxide Fuel Cells (SOFC). The target operating tempera tures of SOFC have been markedly reduced from -1273 K (1000C) to Oxygen
-1173 K
(900C)
or even
less
over
the past ten years. A further reduction of
the
operating temperatures
seems
a
required
cause an
to circumvent the
or
use
of expen
sive interconnect
materials, such
lanthanum chromite
nickel base
alloys.
But lower
operating temperatures
increase of the electrode and elec
tiolyte resistances, thus, the overall power output of the cell decreases. These circumstances have heightened the need for a better understanding of the factors influencing the electrochemical properties of SOFC electrodes. Of par ticular interest is the interface between the cathode and the electrolyte, i.e. the triple phase boundary (tpb) region, where the reduction and incorporation of adsorbed oxygen species is supposed to take place [1]. Nowadays, it is gener ally accepted that the electrochemical properties of LSM cathodes depend to a larger extent on the nanostructure and the phase composition of the inter face, than on the microstructure of cathode layer. The formation of badly con ducting foreign phases during heat treatment and/or operation is believed to be the main factor for a degradation of the electrochemical properties of per-
160
4.1
Introduction
ovskite cathodes. Lanthanum zirconate zirconate
(La2Zr207,
abbr.
LZO) and strontium

with
(SrZr03,
abbr.
SZO)
are
well known to form under certain condi
tions. The successful
employment
activity for
extent
of Co and Fe
containing perovskites
at
high
electrochemical
SOFC
on
operation
intermediate tempera
or
depend to a large mation of foreign phases.
tures will
the
ability
to
control
inhibit the for
4.1.2
Lau and
Microstructure and
-Chemistry
Singhal [2] first reported pyrochlore-type La2Zr207 formation between diffusion couples of dense Lag 9Sr01MnO3 and (ZrO2)0.8(YOi .5)0.2 single crystals. La2Zr207 and perovskite-type SrZr03 have been found to form at interfaces between YSZ and (La,Sr,Ca)Mn03 at high temperatures in
air
or
[3-4]. The
amount of LZO has been found to decrease with
increasing
Sr
longer reaction periods or higher sintering temperatures, respectively. Formation of SrZr03 has been found to occur between heavily doped La1_xSrt.Mn03 (x>0.3) and YSZ [8,4,9,10]. A-site deficiency in (La,Sr)1_yMn03 has been shown to decrease or even prevent zirconate formation during high temperature treatment. Yamamoto et al. [11] found no reaction product by X-ray diffraction analysis for the mixture of La08MnO3 and (ZrO2)0.84(YO15)016 after sintering at
to increase with
Ca substitution for La
[5,6,7], and
1473 K
1573 K
ment.
(1200C) for
192 h;
however, when the temperature

zirconate
was
was
raised to
(1300C), lanthanum
detected after 50 h of heat treat

reactive than the sto
(La,Sr)0 9Mn03 was

[5].
was
found to be
In
considerably less
an
ichiometric material
addition,
induction
period
for zirconate
formation
observed when A-site deficient LSM
was
used [5,12]. The fol
lowing explanation [12] was given: Mn diffuses in larger quantities than La, therefore lanthanum manganite depletes in Mn which further leads to La203 precipitation, which itself immediately reacts with YSZ to form LZO. These experimental findings are in good agreement with the chemical equlibria
calculations
of
mixtures
of
(La1_x_ySrxCay)Mn03
and
(ZrO2)087(YO15)0.i3 by Yokokawa et al. [13,14]. The reaction of LaMn03 with Zr02 has been characterized as a combination of the LZO formation and a
reduction of the Mn ion [15]. The
valence state of
thermodynamic origin
of the
driving
force
of this reaction has been attributed to the destabilization of the unusual
Mn3+
in the
perovskite
case
in presence of zirconia.
Thermody
lanthanum
namic studies showed for the
of
LaMn03 that the relatively stable tetravrise

to
alent
manganese
ions
in
the
perovskite give
the
161
La2Zr207
Formation
and
02
Reduction Kinetics
nonstoichiometry.
between
oxidized in the
nese
It
was
pointed
out
[15-16]
that when
La2Zr207
is formed
LayMn035 and YSZ, a small number of the manganese ions may be

perovskite
structure. In to
contrary, the dissolution of manga

from the size of manganese ions:
is reductive. This
seems
originate
the ionic radius of the tetiavalent state is small, and this makes it easy to accommodate the La
nonstoichiometry
in the
relatively large
size of the divalent ions
perovskite phase, whereas the ensures the large solubility into YSZ
(see [16] and references therein).
Manganese, a major constituent of doped LaMn03, is known to be a mobile species at high temperatures and can easily dissolve from lanthanum manganites into YSZ, thereby changing the properties of the cathode and electio lyte surface [2,3,8,12,17,18]. Diffusion coefficients of Mn in (ZrO2)0^(YOj 5)0 2 single crystals were reported to be (10-13 to 10"12) cm2/s at
1673 K
(1400C) and
two
orders of
magnitude higher
[2].
This
large
difference has been attributed to fast
polycrystalline YSZ diffusion paths through

in
were
grain boundaries [3, 6,19].

lated from chemical shown that manganese
as can
Total solubilities of manganese oxides
calcu
equilibria
calculations
by
Yokokawa et al.
be dissolved up to 11.4%
(2.1%
as
[20]. It was Mn3+ and 9.3%
(Zr02)o.85(YOL5)o.i5 at 1573 K (1300C) in air. At 1273 K (1000C), calculated solubility is lowered to 5.1% (1.4% and 3.7% for Mn3+ and Mn2+, respectively). This contradicts the observations of Roosmalen and Cordfunke
in
Mn2+)
La^Sr^MnOs (x 0, 0.15, 0.3, 0.5) into YSZ from diffusion couple experiments. They observed a mass tiansport of lanthanum and strontium from the perovskite into YSZ. How ever, the previously mentioned studies were performed under different experimental conditions and employed different sample preparation and characterization methods, which may be the basis to discrepancies and disa greement concerning the reaction mechanism of YSZ with LaMn03 based cathode materials. This conjecture is supported by Yokokawa et al. [21] who pointed out that oxygen plays an important role in the reductive dissolution of manganese from the perovskite phase in YSZ:
no
=
[4] who found
diffusion of manganese from
MnOn(p)
MnO,(YSZ) + (n'
n)/2
02(g).
(4.1)
Oxygen removal may be hindered in dense diffusion couples, therefore retarding manganese dissolution. In contrast to Mn, diffusion and solubility of La from the perovskite phase in YSZ has generally found to be much
162
4.1
Introduction
smaller, whereas Sr diffusion and solubility in YSZ have been found

almost
to be
completely absent [2,8,11,12,18].

was
Also
migration
of Zr and Y into the
perovskite
observed
[6,8].
4.1.3
Influence
on
on
Electrochemical
Properties
type
The literature
the relation between electrode characteristics and the

is far less extensive in
and amount of
foreign phases
=
comparison
(1000C)
to thermo
dynamic studies. La!_xSrxM03 (M
Yamamoto et al.
[9] first showed the influence of annealing

at 1273 K
on
Cr, Mn, Fe)/YSZ interfaces
the
cur-
rent-overpotential behaviour at 1073 K (800C). The overpotential of these cathodes was not significantly affected with the annealing process. However, at annealing temperatures of 1373 K (1100C) the overpotential increased rap idly with annealing time. This was attributed to the formation of large
amounts of
SrZr03
which
was
detected with
X-ray
diffraction. On the other
r/-sputtered LaCo03 cathodes increased rapidly with annealing time, which the authors explained by the chemical reaction of YSZ and LaCo03 to form lanthanum zirconate. Similar results were found by Ivers-Tiffee et al. [22]. Kaneko et al. [12] followed the change of the electro chemical impedance during sintering at 1673 K (1400C) in air and investi gated the interfaces after sintering with EDX. Both the high frequency resistance and the low frequency resistance increased markedly with time
hand, the overpotential for
and
a
the presence of LZO
was
observed after
sintering.
The authors
explained this increase in electiode resistance with the formation of a LZO layer at the interface, but they did not attribute any relaxation frequency to a particular electiode process. They noted that the cathodes were almost dense after the experiment and the low frequency losses were in the range of (0.01 to 1) Hz. From this it seems unlikely that the increase in cathode resist ance was caused entirely by the LZO layer, rather gas phase diffusion through the almost dense cathode must have been mainly responsible for the low frequency losses. Electrochemical impedance spectroscopy (EIS) was also employed by Elangovan et al. [23] to study the La0 89Sr0 jMnO^ air I YSZ sys significant changes in the high frequency part of the spectrum during operation at 1273 K (1000C). Although they failed to prove the existence of foreign phases at the interface by means of SEM in this work, they concluded from diffusion couple studies [3] that lanthanum zirconate must have formed at the interface. Similar experiments were carried out by Kenjo et al. [24] who conducted polarization measurements at 1173 K (900C)
tem. The authors found
163
La2Zr207
Formation
and
02
Reduction Kinetics
on
YSZ-LaMn03
in air.
cathodes mixtures sintered at 1273 K
(1000C)
to 1573 K
(1300C)
They
detected traces of lanthanum zirconate at the cath
ode/electrolyte interface by means of XRD after removing the cathode. Although, a general correlation between the amount of LZO and polarization resistance Rp was found, no detailed explanations were given for the increase in Rp. It was argued that a layer of badly conducting LZO simply increases
the ohmic resistance of the cathode. We note that those studies
out at
ances were
carried
high operating temperatures of -1273 K (1000C) where cathode resist are generally low (< 1 Q-cm2) and where it is experimentally difficult to impedance
measurements up to
obtain accurate electrochemical
quencies. Using
more
lower
temperatures for cathode

on
high fre characterization would yield

[25,26].
of the oxygen reduction
information about the oxygen reduction reaction mechanism
We will
give
brief review
the present
knowledge
reaction mechanism in the discussion section.
Recently, transmission electron microscopy (TEM) studies were performed by Tricker and Stobbs [17] on porous La0.8sSr015Mn03/YSZ reaction couples which were sintered at 1573 K (1300C) and operated at 1273 K (1000C) in air. The authors were able to detect grains of lanthanum zirconate in an early stage of growth. Growth of LZO was predominantly epitaxial and directed away from the parent YSZ into the abutting LSM. Similarly, Clausen et al. [18,27] performed TEM studies on diffusion couples as well as on pressed
and sintered mixtures with different ratios of manganese
YSZ.
excess
LSM and
They
concluded from their measurements that nucleation of LZO
occurred at the interface between LSM and YSZ

rial from both the cathode and the
grains
with
supply
of mate
electrolyte. According to these authors, the diffusion of manganese into YSZ causes manganese depletion of the LSM and in the case of stoichiometric LSM chemically active La203 is formed at
the interface, whereas this process is
in the LSM.
impeded
or
delayed by
an excess
of Mn
They
further showed, that the extra manganese does not have to
be contained within the

increase the manganese
ions.
manganite
structure, but that it is sufficient to of
activity by
means
doping
the cathode with Mn
Although these TEM measurements gave a
rather detailed
picture of the
microstructure and
microchemistry
the
of the YSZ/YSZ/LZO interface, the of how the electrochemical proper
authors gave
interfaces.
no answer on are
question
ties of cathodes
influenced
Ostergard et al. 1273 K (1000C) on slurry coated and screen printed cathodes. Unfortunately they carried out TEM not on
by the presence of LZO at cathode/electrolyte [28] performed electrochemical measurements at

LSM-YSZ
these
composite samples but on
164
4.1
Introduction
dense
pellets
of mixtures between
LSMy and YSZ. Nevertheless, the polariza

i.e.
tion resistance
ues
Rp for the oxygen reduction at 1273 K showed decreasing val

by increasing composite cathode, and Rp decreased with parallel, samples with manganese excess
no
upon
increasing the length of the triple phase boundary,

excess.
the volume amount of YSZ in the
increasing manganese
In
and low amounts of YSZ
developed
lanthanum zirconate, whereas stoi
large amounts of YSZ showed the K. The performance presence of lanthanum zirconate after sintering at 1573 increase of the cathodes has been explained with the increase of the length of the tpb and an improved electrode adhesion. Mn dissolution was considered as the controlling factor for LZO formation; however, the authors did not quantify the different factors which influence Rp.
chiometric cathodes and cathodes with
4.1.4
Open Questions
the fact that
a
and Aims of the
Study
Despite
have
most
faces
large number of experimental and theoretical studies been performed, important questions are not yet answered. First and important, it is unclear how the oxygen reduction at LSM/YSZ inter is influenced by the presence of LZO and the microchemistry of the
seems
play an important role in the kinetics of the LZO formation. But, does A-site deficiency in LSMy lead to an incubation time in LZO formation and to a decrease in LZO growth, or were these con clusions drawn due to the detection limits of the experimental apparatus employed? And finally, can we circumvent the formation of detrimental for eign phases by lowering both the fabrication temperature and operating tem
interface. Second, Mn
to
perature, and/or by choosing appropriate cathode stoichiometiies?

The purpose of
our
work
was
to
investigate
the influence of the manganese
stoichiometry
in
La0.8sSr015Mny03 (LSMy)
upon the nucleation and the
growth of lanthanum zirconate at 1373 K (1100C) in air at electrode/electro lyte interfaces, and to simultaneously determine the electrochemical proper ties of these interfaces. The study was performed with porous screen-printed cathodes on (001) YSZ single crystals. After sintering, the cathode layers were
first removed before any further microstructural formed. Atomic force and
investigation
was
per
microscopy (AFM) X-ray photoelectron spectros copy (XPS) were used for analysing the YSZ surfaces. High resolution (HR) TEM was employed for structural analysis and phase analysis of the YSZ sur
faces after heat-treatment. Electrochemical
was
employed
to monitor the
impedance spectroscopy (EIS) frequency response of cathodes during the
165
La2Zr207
Formation
and
02
Reduction Kinetics
heat-treatment process. Distinct differences in nucleation and

were
growth
of LZO
depending on the stoichiometiy of LSMy. Surface diffusion of cations was predominant in case of near-stoichiometric and A-site deficient LSMy. LZO islands formed predominantly at the tpb which caused an increase of the cathode resistance. The charge-transfer reaction was found to be not rate determining at temperatures below 1173 K (900C). The electiode
found
resistance
was
attributed to the dissociation of adsorbed oxygen and the
sur
face diffusion of atomic oxygen.
4.2
4.2.1
Experimental
Procedures
Sample Preparation
couples
were
prepared from dense YSZ substrates and porous per ovskite layers. Single crystals of 9.5-mol% Y203-stabilized Zr02 (25x25x0.5 mm, (001) orientation, polished on both sides) (Zirmat Corp.,
Reaction
N. Billerica, MA,
USA)
were
obtained. The
impurity
content of the
raw
mate
single crystal fabrication is low, and the impurity concentration of the single crystals is expected to be even 1 to 2 orders of magnitude lower than of the raw materials due to the single crystal fabrication process (skull melting). The primary crystallite size of the perovskite powders (ball milled after calcining at 1223 K (950C) for 2 h) (SSC Inc., Woodinville, WA, USA) was -250 nm. The powders were strongly agglomerated. The powder com positions were verified with inductively coupled plasma (ICP) atomic absorption spectroscopy (AAS). Two powders with nominal stoichiometiies of La0.85Sr0.i5Mn{).95O3 (LSMo.95) and La085Sr015Mno.9803 (LSMa98) were
rials for used in this
Pastes of
study.
were
prepared by mixing appropriate amounts of pow der (71.9 wt%) with a solvent (24.5 wt%) (diethylene glycol monobuthyl ether acetate, Fluka AG, Buchs, CH), a binder (0.9 wt%) (Ethyl cellulose, Ethoxyl content 48%, Aldrich, Inc., Milwaukee, WIS, USA), and a dispersant perovskites
(2.7 wt%) (Furan-2-carboxylic acid, Fluka AG, Buchs, CH)
Screen
in
an
agate
mortar.
printing pastes with higher manganese contents (0.98<y<1.10) were prepared by adding Mn(N03)2-4-H20 (Fluka AG, Buchs, CH) (dissolved in ethanol) in appropriate amounts to the LSM0 98 powder before preparing the
paste. This procedure
ensures
that the additional manganese is and within the
homogene
Table 1
ously distributed on the powder surface
organic paste.
166
4.2
Experimental Procedures
Table 4.1
the cation
Characteristics of the
ratio
to
used in this
cation
(column 3) refers
paste.
the
nominal
study. Note composition of

consist
that
the the
screen-printing
LSMy
(y
1-02)
screen-printing
pastes
of
Lao 85Sr0 jsMrio 9803 powder
with additions of manganese nitrate.
Sample
LSMa95
Description
SSC, Inc., calcined 1223 K for 2 h,
ball milled
Mn/(La
0.95
nSr)
LSM0.98
SSC, Inc., calcined 1223 K for 2 h,

ball milled
0.98
LSM102
LSMg 98
with additions of
1.02
Mn(N03)2-4H20
LSMy (y
>
1.02)
LSMq 98 with additions of Mn(N03)24H20
>1.02
summarizes the
were
used in this
study.
Note that
doped
powders posed to be on the particle surface, as well as within the organic paste. Per ovskite layers were screen printed (325 mesh) on YSZ substrates. The samples were sintered at 1373 K (1100C) in flowing air for periods from 15 min to 12 h using a chamber furnace (Nabertherm HT10/18, Naber
not calcined
before use, i.e. the additional manganese is sup
by means of a thermocouple which was located close to the samples. The samples were held at 1073 K (800C) before and after sintering in an supplementary furnace. The heating
was
GmbH, FRG). The temperature
controlled
rate
was
K/min from
room
temperature
a
to 873 K
(600C) with
dwell time
heating rate of 3K/min to 1073 K. The samples were taken from the supplementary furnace, put into the sinter ing furnace for the desired period, and subsequently put back into the fur nace held at 1073 K. The cooling rate from 1073 K to room temperature was 3 K/min. Home-made high purity alumina crucibles (CERALOX HPA0.5 Mg, Condea, Tucson, AR, USA) were employed as sintering supports. The pore size distributions and porosities of cathodes were obtained from mer cury-intrusion measurements (model 2000, Carlo Erba, Italy) on -0.12 g of sintered screen-printing paste. The cathode layer thickness was -20 pm after sintering. In order to examine the YSZ surface and the reaction products on the YSZ surface after sintering, the sintered porous perovskite layers were dissolved with concentrated hydrochloric acid in an ultrasonic bath at room
of 4 h at this
temperature followed by
167
La2Zr207
Formation
and
02
Reduction Kinetics
temperature. Finally, the samples

and lanthanum zirconate dissolves
are
were
cleaned with water and ethanol. YSZ
stable
against hydrochloric
acid whereas
LSMy
rapidly.
4.2.2
Investigation
of Surfaces and Interfaces
Topographic observations of YSZ single crystal surfaces were conducted with AFM (TMX 2010, TopoMetrix, Santa Clara, CA, USA). All the AFM experi
ments
were
conducted in air
using
constant force mode. A
square
pyrami
dal
Si3N4 tip
with radius of curvature of -100 nm,

nm
produced
lateral and
respectively. The base of the pyramid consisted of a square with sides -5 pm long. The aspect ration was about 1:1. A tripod scanner (70 pm scan range) was used for scanning large ranges. Higher resolution was obtained with a tubular scanner (7 pm scan range).
vertical resolutions of 2
and 0.5 nm,
analysed quantitatively, with each image consisting of 1024 lines with 1024 points. The quality of the silicon nitride tip was regularly checked with a sample of known surface structure. Numerical analysis of surface data was carried out with the AFM software package (version 3.08) on a windows compatible (486) personal computer. Raw data were first corrected for sample tilt before conducting numerical analysis. Quantitative estimates of the volume amount of surface phase, its average height, the YSZ surface coverage, and the length of the tpb between the YSZ
Five
images
from each
sample
were
surface and any surface

HRTEM
foreign phases
were
obtained.
analyses were conducted on YSZ surfaces. Electron transparent sam ples were prepared by dividing, polishing, and argon-ion-thinning. Follow ing standard procedure of mechanical pre-thinning of cross-sectional specimens, two slices from the sample were epoxy bonded in a metallic tube face to face. This composite was sliced, mechanically thinned, and polished
to
a
thickness of
(20.. .30)
pm. Plan-view
samples
were
cut into disks of 3
mm
dimpled from the substrate side to a final thickness of 20 pm. In both instances, final thinning to electron transparency was done by argon-ion beam thinning. Micrographs were obtained with a HRTEM (model CM30, Philips) operating at 300 kV.
diameter
using
an
ultrasonic disc cutter and then
Energy-dispersive X-ray analysis (EDX) (VOYAGER III, Noran Instruments, Middleton, WI, USA) was used for elemental analyses of foreign phases on
the YSZ surface.
168
4.2
Experimental Procedures
XPS
sputter depth profiles
were
recorded in
=
Perkin-Elmer PHI 5400 ESCA
1253.6 eV). Using an electron take-off system using Mg Ka excitation (hv angle of 43, the analysed surface area was 1.5 mm2. Sputter depth profiling
was
performed using
argon ions at 3.3 keV. The
sputter
rate
was
calibrated
with reference films to
3.7nmmin-1
for
Si02.
The
sputter
rate ratio between
Zr02 and Si02 is 0.46 therefore giving a sputter rate of 1.7 nmmin-1 for Zr02. The depth profiles were acquired as a set of discrete sputter cycles inter
rupted by
XPS measurements of the Zr 3d, Y 3d, La 3d, Sr 3d and O Is
core-level lines. The atomic concentrations
reported
here
were
calculated
using PHI sensitivity
factors.
4.2.3
Electrochemical
Investigation
working electrodes (lxl cm, -20 pm thickness) and reference elec trodes were applied to YSZ single crystals by screen printing. Platinum gauzes (52 mesh, Fisher Scientific, Pittsburgh, PA, USA) were pressed by hand into the freshly printed perovskite layers. The gauze was fixed at the edges with a ceramic two-component binder (type 1500, Firag, Ebmatingen,
Perovskite
CH), and further coated with diluted
screen
printing paste
in order to have
good
wires
electrical contact between the cathode
layer
and the gauze. Platinum
(0.35
mm
diameter)
were
used to contact the gauzes. The counter elec
prepared from Pt paste (C 3605 P, Heraeus GmbH, Hanau, FRG) where we first dc-sputtered -50 nm of Pt on the YSZ surface (model SCD 040, Bal-tec, Balzers, FL). The in-plane conductivity of unsintered and sintered cathode layers, as well as the conductivity of dense cathode material, was measured with four-probe measurements. The layers were screen printed on
trodes
were
polished alumina potential probes.
rods
(3x3x40 mm).
were
Pt wires
were
used
as
current leads and
Electrochemical measurements
conducted in air
to 1373 K
temperature range of
723 K
(450C)
atmosphere over the (1100C) during heating and
cooling cycles. Steady-state current-potential curves and electrochemical impedance spectra were obtained (Model IM6, Zahner GmbH, FRG) in a three-electrode, four-lead configuration. The measurements were carried out < 105 Pa). in air or 02/N2 mixtures (5 Pa < Impedance measurements pQ were carried out at equilibrium potential Eeq (if not otherwise stated) in potentiostatic mode over a frequency range of 10 mHz to 100 kHz or less. The excitation voltage was 20 mV at T < 873 K (600C) and 10 mV at temperatures above. Short electrical wires were used to minimize inductive errors at high
169
La2Zr207
Formation
and
02
Reduction Kinetics
high temperatures due to low electrode impedances. The fre uncompensated electrolyte resistance Re was determined from the high data in a complex plane plot. The polari quency intercept of the impedance in the zation resistance Rp was obtained from the low frequency intercept of the complex plane plot. The dc resistance was obtained from the slope
frequencies
and
steady-state I(r\)
curve
at rj
0. A further
analysis
of
impedance
data will
be described in the discussion section.
4.3
4.3.1
A
Results
Cathode Microstructure and Electrical
electron
YSZ
Conductivity
a
scanning
micrograph
of
fractured
cross
section of
porous cath
ode
the
single crystal is shown in Fig. 4.1. The micrographs show typical morphology of the La0 85Sr015Mny03 layers obtained in this study.
layer
on a were
The cathodes
even was
without cracks and adhered well to the YSZ substrate,
after
only
15 min of
sintering.
The average
grain
on
size of the cathodes
in the range of 0.3 pm to 0.8 pm,
depending
the
sintering period.
Fig.
4.1
SEM of sintered
LSMT
02
cathode
on
YSZ
single crystal.-The sample
was
sin
tered at 1373 K
(1100C)
in air for 2 h.
(a)
Overview of the microstructure.
(b)
Necks
02
around the LSM
grains
and at the contacts between the YSZ surface and the
LSMj
grains
formed
during sintering.
170
4.3
Results
Neck formation between the cathode between the cathode
grains,
as
well
as
at the
interface
grains
and the YSZ
(Fig. 4.1b). SEM-EDX gave no spective of the composition of the cathode) at the interface or for interdiffusion of cations. The porosity of Lao^SiaisMn^^ cathodes changed from
T/C
1000 800
electrolyte surface, can be observed indication of formation of foreign phases (irre
600
r-.
500
i
400
105
D D
D
D D
:
.
_ _
_
10<
c*
o
mo*omD
4>
O
o
cooling
o
10J
7
.
~.
heating
dense
LSMQ 98
LSM0 9g
o o
porous, sintered
o
porous, unsintered porous, unsintered

i
LSMQ 9g
LSMQ 9g
i
(+4% Mn)
i
10^
0.8
1.2
1.4
103K/T
Fig.
4.2
4-probe electrical conductivity

were
of
LSMy
cathode
layers
in air.The
in air, held for 2
screen-
printed samples
heated with 3 K/min to 1223 K
(950C)
h, and
subsequently cooled to room temperature with 3 K/min. For comparison, the electrical 4-probe conductivities of dense bars (sintered at 1623 K (1350C)) and porous LSMo98 layers (sintered at 1373 K (1100oC) for 2 h) are given.
171
La2Zr207
Formation
and
02
Reduction Kinetics
-55% in the green state to -42% after 12 h of
sintering
=
at 1373 K
=
(1100C),
where the
observed
content
mean
pore diameter increased from d
0.32 pm to d
0.5 pm. We
by
SEM that cathodes densified faster the
higher
their manganese
was.
Nevertheless, the porosity did
not decrease to values less than
40% at
excess.
sintering temperatures
of 1373 K for cathodes with 10% manganese

our
The cathode materials in
study
with y
0.95 to 1.10
were
single
phase perovskites
ther
of rhombohedral structure. We could not detect any fur
phase in sintered cathodes by X-ray diffraction; however, cathodes with higher amounts of manganese (y 1.16) showed the presence of Mn304
=
grains
in the TEM.
conductivity of the cathode layers followed the general dependence for small polaron conductivity. Fig. 4.2 shows the variation of log(o T) vs. 1/T of freshly screen-printed porous layers of LSM098 and LSMX 02 on polished alumina substrates and compares the results of porous and dense LSMq 9g- Note that the cathode layers were not heated to 1373 K but only to 1223 K (950C). Nevertheless, the cathode layers cracked during cooling below 723 K (450C) due to the thermal expansion mismatch between alumina and slightly sintered porous LSMy. Note that the electrical conduc tivity of unsintered cathode layers is relatively high after the heat treatment at 1223 K in comparison with sintered cathodes. The addition of Mn ions to the screen printing paste has a beneficial influence on the electrical conduc tivity of unsintered cathodes at lower temperatures during heating. There is no significant difference in the conductivity of undoped and doped (+4% Mn) LSM0 98 after heat treatment at 1223 K.
The electrical
4.3.2
Interface
Development During Sintering

(y
=
Manganese
Deficient Perovskite
0.95).
Fig.
4.3
depicts
XPS
a
sputter
porous
depth profile from a YSZ surface which was sintered La0 85Sr015Mno 9503 (LSM0.95) cathode layer at 1373 K in air
with
for 2 h. The YSZ
single crystal was completely transparent after removal of the cathode. The surface layer (after 30 sec of Ar+ sputtering) of this sample is seen to contain primarily Zr, La, and O. The concentration of Sr decreases from ~1% at the
surface to less than 0.5% after 30
nm
of
sputtering.
In
comparison,
Y is
present
method
at the surface and its concentration increases to the nominal value of

nm
YSZ after ~30
of
sputtering.
Mn is below the detection limit of the XPS
(~0.1%).
The
composition
of the surface
layer
is
seen
to remain
172
4.3
Results
^sputter'1
0 20 40 60
10
20
/min sputtei
30
40
Fig. 4.3
XPS sputter
depth profile of a La-ridi surface layer on YSZ single crystal.

a
The first few nanometers of the surface show

tration of Sr is below 1%.
La/Zr ratio of -1.35. The atomic

~40
nm
concen corre
Beyond
s
sputter depth of
of
the
composition
sponds
to
the nominal
composition
(Y015)019-(Zr02)o.8i-
The
sample
was
first
sam
sputtered with Ar+ during 30 ple surface not shown) [32].
for removal of carbon
(composition
of 'as received'
approximately
constant
over
the first 20
nm
and the La/Zr atomic ratio is
During depth sputtering, electrostatic charg ing of the sample surface occurred after -15 nm of sputtering. The La/Zr ratio before Ar+ sputtering of the sample was -0.65, i.e. the Zr4+ concentra tion within the first (0.5... 1) nm was distinctly higher than the La3+ concen
nm.
-1.35 within the topmost 15
tration. However, the carbon concentration before
sputtering (as received
sample)
result. TEM
was
-50% and, therefore,
care
must be taken in
interpreting
this
images
4.4
of
cross-section of the YSZ surface studied with XPS

are
as
described above,
shown in
Fig.
4.4
Even under
low of
magnification
a
(Fig.
a)
it is clear that the YSZ surface contains
grains
new
phase
which
cover
the YSZ surface
entirely. Fig.
4.4b shows the Selected Area Elec-
173
La2Zr207
Formation
and
02
Reduction Kinetics
a)
o
o
9
ft
o
cf
t>
(5
Cf
%
.
O
5
9
O
O
O
<3
.
<*
o
i
*D
#
O
o
CP
*D
.
)
o
(i
o
.
O
<3
%
.
'
o
Q
o
P
o
Q
o
b)
Fig.
tal
4.4
TEM
images
and
of lanthanum zirconate islands grown
surface.(a) Bright
field
image
of LZO
grains
of uniform
(001) YSZ single crys thickness and size, (b) Sim

on a
ulated
(right side)
experimental (left) [Oil]
SAED of
epitaxial
LZO
on
(001)
YSZ
sur
face. The filled circles in the simulated pattern represent the YSZ reflexes where the open circles represent the LZO reflexes. Given (hkl) refer to LZO. The structural data from Deiseroth
[29]
were
used for simulation
(oxygen parameter:
0.295).
174
4.3
Results
Fig.
4.4
(continued) (c) High resolution image of lanthanum

a
zirconate
grain
in
[Oil]
direction. The inset shows
magnified
selection of the
is
top
of the island. An
into the inset for
experimen comparison
tally
obtained HR
image
of YSZ in
[Oil] direction
pasted
(darker square).
tron Diffraction
(SAED) pattern
of the surface
a zone
ulations for YSZ and diffraction spots

tion
are
La2Zr207
caused
as
with
region and compares with sim axis of [Oil]. The wide and intense
parameter which
is -2.08
by
the YSZ substrate whereas the weak diffrac

a
spots index perfectly

0.5142
nm
fee with
unit cell
times the lattice
parameter of the YSZ substrate (9.5 mol% Y203-stabilized;

consistent with the reaction
a0
[30]).
are
These
findings
nm
product
a
on
the surface
being
of of
lanthanum
zirconate,
La2Zr207,
is odd and
which
has
lattice
parameter
an
a0
1.0786
are
[29, 31]. The diffraction spots n{hkl} (n being

n
integer)
present
LZO
weak when
are
strong when [011]

beam
is
even
[31]. Although
are
the
in
{200} reflections
the SAED
not allowed with

was
direction, they
pattern. This
also observed
by
Clausen et al.
[18]
and is
175
La2Zr207
Formation
and
02
Reduction Kinetics
explained by
the
double diffraction,
(111)
(111)
(200). The diffraction pat

4.4 a grew
tern also reveals that the LZO
grains
shown in
Fig.
epitaxially
on
(001) YSZ surface
{001}LZO||{001}YSZ
<100>LZO||<100>YSZ
which is in
(4.2)
the
agreement with previous
LZO reflections
splitting of the reveals that the epitaxy is not perfect, but that a slight misoriresults
[17]. Finally,
entation exists between the YSZ substrate and the LZO
grains.
It
was
not pos
sible to determine the cation concentration of the LZO

TEM-EDX due to the size of the and Mn in the YSZ
grains reliably
grains
a were
with
grains; however,
the concentrations of La
adjacent
our
to the lanthanum zirconate
below
the detection limit of

the surface
TEM-EDX. In addition, Mn could not be detected in

a
layer. Fig.
4.4c shows
HRTEM in
[Oil]
direction of
single
LZO
Fig.
4.5
AFM of
lanthanum zirconate
a
layer covering
YSZ
single crystal
surface.
(a) 2-dimensional
LZO grains
view of
(800x800)
urn area
Note the
preferential
orientation of the
[32].
176
4.3
Results
Fig.
4.5
(continued) (b)
Lower
right part
of
(a) shown
in
surface
plot
to
depict
the vari
ations in
layer height.
same
Note that
Fig.
4.3 and
Fig.
4.4 show the XPS
profile
and HRTEM
images
of the
sample surface, respectively.
grain.
Note that the surface of the
grain
shows
high-resolution (HR) pattern

grain
was
which is
apparently equal layers

of this
to the
pattern of the YSZ substrate (cf. inset of

LZO
Fig. 4.4c).
We found that every
investigated
covered with
few atomic
resolution contrast to the
phase. Note that the transition from the LZO high high resolution image of the surface phase is seen to
can
be continuous. No dislocations
be
seen.
Fig.
4.5 shows the
topography of the
same
YSZ
sample
of the
surface. It is
seen
from
the AFM
image
in
Fig.
4.5 a that the lanthanum zirconate

to the <100>
axes
grains
are
preferen
which is
size
tially
in
orientated with
respect
(001)
YSZ surface. The
average
height
of the surface
layer
shown in
Fig.
4.5b is
(18
3)
nm,
agreement with the XPS results reported
in
Fig.
4.3. The average
grain
of the LZO
grains
is about
(120
40)
nm.
Nucleation of LZO
grains
occurred
around the contact between the LSM after
grains facing
the YSZ surface. Even
sintering periods of less than 15 min, the YSZ surface was almost com pletely covered with islands of LZO of considerable thickness (-5 nm). The growth constant D of the reaction layer was evaluated through the Wagner
equation,
x
=
t, where
t.
is the average thickness
as
function of the
we
sintering
time
=
With
x=(183)nm
at 1373 K.
and
t=2h
estimate
logD/(m2-s_1)
-(19.35 0.15)
177
La2Zr207
Formation
and
02
Reduction Kinetics
Slight Manganese
Deficient Perovskite
(y
0.98).
Fig.
4.6
shows
AFM
images
of the
development
of lanthanum zirconate islands
at 1373 K
(1100C)
in air between cathode
layers
of
during sintering La0 85Sr0 isMn0 9803 and

grains
of the islands is
YSZ. It is discernible that the islands grow in between the cathodes and the YSZ surface towards the cathode. The cube-like and the islands show
a
shape
preferential orientationship with the YSZ substrate. By looking closely at the islands in Fig. 4.6a it can be seen that the large islands are made up of four smaller islands (embryos). During sintering the embryos grew in diameter and height until they faced each other and therefore formed a single island. These islands further grew in height and diameter until most of the YSZ surface was covered by a relatively thick layer
Fig.
4.6
AFM
images
of
(001)
YSZ
single crystal
on
surface covered with
cube-shaped
scale,
islands of lanthanum zirconate.The colourbar

taxial LZO
the
right
denotes the
(a) Epi
nm an
grains (1)
on
top
of the YSZ surface after 30 min of

is
sintering
at 1373 K
(1100C)
in air. The average island size
(0.50.1) pm
and the average

at
z
=
height
parent
is -35
after 30 min. Note that the YSZ level is

obvious orientation denotes the
approximately
phase.
60
nm
and that there is YSZ.
relationship
between the LZO
grains
with the
(2)
tpb
between YSZ, LZO, and the gas
178
4.3
Results
Fig.
4.6
(continued) (b)
is
Same situation
nm
as
in
(a) after
12 h of
is
sintering The original YSZ

nm
surface level
at
135
The average island
height
-125
of
cube-shaped
in the
z
lanthanum zirconate islands
(Fig. 4.6b).
Note also the differ
ences
scale of these two
figures
and compare with
Fig.
4.5. The initial
surface coverage after 15 min

to be -50%
was
estimated
numerically
from AFM
images
(Fig. 4.7b). length
This value increased to -90% after 12 h of
sintering
period.
the
The
of the
ter between the LZO
tpb, l^h, was obtained by estimation of the perime grains and the YSZ surface numerically. The length of
rapidly within the first 30 min of sintering and slowly decreases with increasing sintering time. A clear correlation between /w,b and Acov is seen. Fig. 4.7c shows the average height of the LZO islands, hav,
increases
tpb
which
was
obtained from the estimated volume amounts of LZO
on
the YSZ
surface, standardized with the corresponding surface coverage.
In this way
can
hav corresponds
to
an
apparent LZO layer thickness and the results
be
compared
a
with those of
as
LSM0 95.
case
The
growth
rate of the island
height
follows
different law
in the
where the LZO
layer
is dense.
179
La2Zr207
Formation
and
02
Reduction Kinetics
10
!
-
6
a
a.
T>
X^
a)
10 100
1000
t/min
15 min 30 min lh
ot
B
3.
A 2h
4h
12 h
D.
w> 1
A
A
b)
0.4
0.5
0.6
0.7
A
cov
0.8
0.9
Fig.
of
4.7
LZO island
versus
tpb
shown
50% of the
growth kinetics at 1373 K between LSM098 and YSZ.(a) Length sintering time at 1373 K in air. The region marked contains at least predictions, (b) Length of tpb shown versus YSZ surface coverage with LZO
islands.
180
4.3
Results
200
un-r\
"av
.t
u$l
D())(1373
100
K)
1.8710"22 nVs"1
a
> Rl
50
2.48
c)
20 10
t
sine
10
Vs
(continued) (c) Apparent layer growth numerically estimating AFM images.
Fig.
4.7
kinetics. The data
were
obtained
by
Fig.
4.8
shows
bright
field TEM of
LZO island. A
as
sharp boundary
dislocation net
com
between the YSZ and the lanthanum zirconate,

work around the
well
as a
grain boundary,
can
be
seen.
The LZO island grew
pletely towards the cathode side and not into the YSZ. The boundary is remarkably flat. The lattice constant of LZO was estimated from a [Oil] SAED
pattern
over as
a0
1.077
was
nm.
The cation concentration in the islands
(averaged
islands)
determined with TEM-EDX. We obtained

+
(40.30.1)% for
La, (6.50.2)% for Y, and (53.20.2)% for Zr. The Zr/(La
Y)
ratio is therefore
equal
to 1.14 at
Zr concentration of 19.3%. The Zr/Y ratio in the LZO
islands is 8.1, which is
larger
than in the YSZ

was
(nominal 4.26). The
amount of
Sr and Mn in the LZO islands

Mn detected in the
below the detection limits. The amounts of
topmost YSZ surface near and below the LZO islands was
less than 0.3%. Sr and La could not be detected in the
near
very low,
generally
YSZ. Note that the YSZ surface

nanometers
the LZO level
compared
with the
original
grain is lowered by a (cf. Fig. 4.8). This was
few also
181
La2Zr207
Formation
and
02
Reduction Kinetics
Fig.
4.8
Bright
field TEM of LZO island
on
(001) YSZ surface.The sample

zone
was
sin
tered for 4 h at 1373 K in air. The island has its <011>

beam. A
axis
parallel
to the electron
magnification
of the upper
right edge
of the island is shown in
Fig.
4.9.
observed in the AFM faceted after the
investigations.
In addition, the YSZ surfaces

treatment.
were case
often
with
high-temperature
a
Again,
as
in the
LSM0 95,
were a
we
found from HRTEM

thin
(Fig. 4.9)
10
that all
investigated
LZO islands
covered with
layer (<
nm)
of material of cubic
symmetry with
zones
unit cell
parameter of -0.5 times the lattice parameter of LZO. The layers
are
found to be
10-15 atomic
inhomogeneous in thickness. Relatively layers) are found at the top of the islands
grains
and the LZO islands is
can
thick
(up
to
where the contact

to be.
between the LSM
supposed
to the
Very
is
thin
regions (1-3
Note
atomic
layers)
be observed at the side walls of the islands.
again
that the transition from the LZO

no
phase
surface
layer
con
tinuous and that
dislocations
can
be
seen.
A-Site Deficient Perovskite

a
(y
1.02).
a
Fig.
4.10a shows
an
AFM
image
of
YSZ surface which
was
sintered with
porous
La0 ss^rg lsMnj 02O3

as
cathode
at 1373K
(1100C)
in air for 2 h. The surface
topography
well
the
is dominated
by
evenly
distributed
rings [32].
The thickness
as
height
of the
in
rings
mor-
increase
rapidly
with
increasing sintering
time. No distinct
changes
182
4.3
Results
+S9
i
l ^
vcv
.3
Fig.
4.9
HRTEM of LZO island surface The image shows the upper

in
right
area is
of the
island shown with

a
Fig
of
a
4 8
(rotated clockwise by 90) The
entire LZO island
covered
thin
layer
cubic
phase
with
lattice constant of -0.5 times the lattice constant
of LZO.
183
La2Zr207
Formation
and
02
Reduction Kinetics
phology
can
be noted with AFM up to 4 h of
sintering.
a
From XPS
measure
ments and HRTEM
investigations
we
found that the
rings
which formed at
defect
early sintering
obtained
times consisted of
Mn-doped
and
YSZ with
high
Mn
density.
over
The atomic concentrations of the islands
were
estimated with TEM-EDX. We
(13.8
0.8)% Y, (78.7
near
1.6)% Zr,
at 1373
(7.4
1.0)%
(average
in
islands, sample sintered for 2 h

substrate shows steps
K).
Note that the surface of the YSZ
the islands which is
clearly
in
see
Fig.
4.10b.
Around the island the surface of the YSZ is lowered with

time
increasing sintering
was
typically prolonged sintering (> h), we found again cube-shaped islands on top of the zirconia rings (Fig. 4.11). The change in morphology towards the cube-shaped islands can be well observed from this image. After
z
in
(cf.
scale bar
Fig.
4.10b). The step size

4
the YSZ
~5nm.
After
nucleation, these islands further grew and exhibited
characteristic cube
shape as (y 0.98).
=
observed
The rate of
in
the
case
of
the
manganese deficient
perovskite
one
growth
of these cube
shaped
islands
was
about
to
Fig.
4.10
AFM mages of
was
(001) YSZ surface

added to the
after
sintering with
area.
La0 85Sr015Mn, 02O3

was
cathode.Mn nitrate
starting powder (LSM098)

YSZ surface
to obtain the nominal
composition, (a)
for 2 h.
AFM image of
larger
The cathode
sintered
184
4.3
Results
Fig.
4.10
(continued) (b)
AFM
image
of
single
island after 4 h of
sintering.
Note the
z
slope
down of the YSZ surface towards the island. The
original
YSZ level is at
=0
nm.
two orders of
magnitude
lower than that of the LZO islands in the

information obtained from the AFM
case
of
LSM0 ggwe
From the
morphological
we a
images
supposed
that these cubic islands consist of lanthanum zirconate.
To prove this
hypothesis,
investigated sample
In
some
of these
samples
with the
HRTEM. Plan-view TEM of
sintered for 4 h reveals that every
large
island consists of several smaller islands
with the AFM
investigations. image.
fee with
(Fig. 4.12), which is in agreement addition, the stepped YSZ surface can be
SAED
clearly
seen
in this
The
[001]
pattern of this sample shows

times the lattice param
intense diffraction
peaks
from the YSZ

a
parent material (Fig. 4.12). The weak
reflections index
as
lattice
parameter -1.98
eter of YSZ. XPS measurements of this
sample
revealed about 4 atomic per diminished within 15

was
nm
cent of La within the surface. The La concentration
of
sputtering.
Note that XPS
probes
the entire surface which
in this
case
only partially
field TEM of
Both island
covered with islands.

a
Fig.
4.13a shows
cross-sectional
12 h of
bright
ring-shaped
show
a
island which formed

at the
during
and
a
sintering.
tips
sharp boundary
top
different contrast.
185
La2Zr207
Formation
and
02
Reduction Kinetics
From HRTEM
images (Fig. 4.13b)

SEAD
it is
seen
that the
tip
consist
was
mainly
of lan
thanum zirconate with small inclusions of from the
c-Zr02.
This
also confirmed
[Oil]
patterns
as
of the islands. The lattice constant of the LZO
phase
was
determined
-2.09 times the lattice constant of the YSZ
parent
material. The deviation from
perfect epitaxy samples
was
-1. Note also the difference
in the LZO lattice constant of the
sintered for 4 h and 12 h, respec
tively.
In addition,
we >
investigated
AFM
the behaviour of interfaces between
(001) YSZ
with
and
LSMV (y
and
1.02).
at
investigations
no
of YSZ surfaces after
sintering
LSM}10
12 h
LSMX16
showed almost
1373 K.
indication for LZO formation up to islands could be
of
sintering
Occasionally, cube-shaped
no
detected after 12 h. HRTEM and SAED gave

tion.
indication for LZO forma
Fig.
4.11
02
Density
cathode
z
sliced AFM
image
nm.
of YSZ surface after
long-term sintering.The
of the
a
LSM!
areas
was
smtered for 10 h. Note the These

areas
typical square-like morphology

also exhibit
at the
level above -250
typical
orientation rela
tionship
with the
(001)
YSZ
single crystal
surface.
186
4.3
Results
Fig.
4.12
Plan-view TEM of YSZ surface.The

are
The dark horizontal lines

dark
Bragg
on
contours.
sample was sintered for The c-Zr02 islands show

can
4 h at 1373 K.
as
clusters of
with the
rings.
Note how the
steps
the YSZ surface
be
clearly
seen
(marked
white
arrow).
The inset shows the
corresponding
SAED
pattern.
Fig.
4.13
(next pages) Bright-field

-7% Mn
TEM of
cross
section of
ring-shaped
island. The
sample was sintered for c-Zr02 which contains

left
12 h at 1373 K in air.
(a)
The lower part of the islands consist of
(referred
to the cation
concentration), (b)
HRTEM of
tip
shown in
(a).
187
La2Zr207
Formation
and
02
Reduction Kinetics
188
4 3
Results
189
La2Zr207
Formation
and
02
Reduction Kinetics
4.3.3
Electrochemical
Properties LSMq 98
Cathodes
impedance spectra were recorded during the heat treatment of La0.85Sr0 ^MrtQ 9803 (LSM0 98) cathodes on (001) YSZ single crystal electro lytes. The spectra were taken at the same temperature during heating and
Electrochemical
cooling. In Fig. 4.14 a typical electrochemical impedance of the La0 85Sr015Mno 9803, air I YSZ system before and after sintering at 1373 K (1100C) is shown in the complex plane. The frequency response of unsin
complex plane over the temperature range of 773 K (500C) to 1273 K (1000C). Also the frequency response of sintered cathodes is similar in the complex plane. In contrast, the frequency response of unsintered and sintered cathodes was completely different. Fig. 4.15 compares the frequency responses of unsin tered and sintered LSMq 98 cathodes in air taken at the same temperatures. It is clear that the phase maxima shifts to higher frequencies with increasing temperature. Note the marked broadening of the dispersion due to sintering, which becomes more pronounced at lower the temperatures [25]. The polari zation resistance Rp is increasingly dominated by the low frequency losses
tered cathodes is similar in the
La0.85^r0.15Mn0.98^3 6
air, 7
=
974 K
20
C4
YSZ
"
not
sintered
<&
Ik
S
o
337
o

10
10k
3k
.107
o
o
^34
o
7
0
V
*=
a)
-10
*e+*p
I.I.
20
40
Re(Z/Q-cm2)
Fig.
4.14
Typical complex plane plot

interface
of
the
electrochemical
impedance
of
LSMq 981 YSZ
obtained at 973 K
during heat treatment in air.The shown measurements (700C) in air. (a) Cathode impedance before sintering.
were
190
4.3
Results
80
-1
La0.85^r0.15^n0.98^3+8
air, r=974K
60 e
V N
sintered at 1373K for 2 h
U^
YSZ
o
o
40
o o
11
3
o
34.
o o
20
"
107
10kî<^
R
e
341m
108m
|
+
/?
e
/?
p
-20
b)
Fig.
4.14
50
100
Re(Z/ftcm2)
(continued) (b)
Cathode
impedance after sintering at 1373 K (1100'C) for 2 h. The numbers within the figures denote the frequencies in Hz. The frequency range was limited to (0.1... 105) Hz. No inductive behaviour was observed at high frequencies. Re denotes the uncompensated electrolyte resistance and Rp is the polarization resistance
of the electrode.
with
decreasing temperature. The resistances from small-signal ments at equilibrium potential were in accordance with the R
from EIS measurements,
dc
measure
determined
below
indicating the probed frequency range.

an
that
no
polarization
losses occurred
Fig.
4.16 shows
Arrhenius
plot
from 773 K to 1373 K in air. The

-1000 K
are
conductivity, o~e apparent activation enthalpies, AH^,
of the cathode
below
significantly
are
lower than
AH^
above 1100 K. Note also that

are
AH^
of ae of unsintered and sintered cathodes

tures but that ture
comparable
at
high tempera
in
they dependence of Rp of different samples was similar to the one shown Fig. 4.16, although the absolute values of ce varied within a factor of two.
The influence of the oxygen
rather different at lower temperatures. The tempera
These
ments
sen
partial pressure p0 on oe is shown in Fig. 4.17. data were obtained from impedance measurements and dc measure on one sample during its heat treatment. The temperatures were cho
in order to obtain the pQ
dependencies
partial
where oe exhibited different
activation
energies.
The oxygen
pressure
dependencies
of ce, i.e.
191
La2Zr207
Formation
and
02
Reduction Kinetics
10"
7=779K
50
6
CI
-
10J
102
*
a)
101
10
!-l
10
101
102
103
104
103
u)/(2ix-s-1)
10J
7"=974K
50
10^
101
b)
10l
10
8o
o.o.P..P0.0
-1
10
101
10z
10J
10*
10
m/(2n-s~l)
10J
7= 1173 K
50
B
a
-
io1 10
t
c)
10,-l
oo' i.i..fg.?'.!
10"1
10
101
102
103
104
105
co/(2rc-s_1)
during heat treatment.The spectra were recorded at the same temperature during heating and cooling while keeping the temperature constant during the measurement. Electrochemical impedances shown at
Fig.
4.15
Bode
plots
of
LSMq 98 cathodes
on
YSZ
(a)
779 K
(506C), (b)
IZ I after
974 K
(701 C),
and
(c) T
1173 K
(900C). ()
IZ I before
sintering; (- -) sintering.
sintering; (o) phase angle
before
sintering; (*) phase angle
after
192
4.3
Results
77C
1100
900
decrease of ae
700
500
10'
during sintering
10',0
A//i=182kJ/mol
C4
B
C/3
<u
10,-1
AfT
190 kJ/mol
A//
=
10,-2
90 kJ/mol
10,-3
A//
125kJ/mol
0.8
io3K/r
Fig.
4.16
Arrhenius
room
plot of conductivity
to 1373
ae of
LSMq 9s
cathode.The
sample
was
heated from
temperature
K, held for 2 h, and subsequently cooled.
<5e
<*=
pQ
for the different
temperatures
are
given within
the
figure.
Note the
change of the slopes, m. A selection of the corresponding impedance data of unsintered and sintered cathodes is given in Fig. 4.18. With decreasing pQ the low frequency losses of the cathode increase, independent of the temperature.
193
10
rf^
N
i-t
o
m
=
10"
0.38
0.44
'0-2
0.22
i
>
o
N)
m m
=
0.50
m
10"
0.24
10 ,-3
a c
n
H
S
z
m
=
0.39
10"
O
10"
7=1123 K r=873K
7= 1223 K
m
a)
b)
10"
7= 1123 K
O
*
T=1093K
T= 893 K
to
10 i-5
10^
101
10^
10j
104
103
10U
10'
10^
103
104
103
Po2/Pa
Fig.
4.17
Oxygen partial pressure dependence of electrode conductivity of LSM0 98 cathode.(a) Results obtained during heating of unsintered cathode, (b) Results obtained during cooling from 1373 K. The measurements were obtained with a sample different from the one which results are shown in Fig. 4.15 and Fig. 4.16. The slopes of the curves in the log(K ) versus log(pQ ) m> were obtained
>
from
least-square
fits of the
experimental
data
over
the range indicated with the line.
IO2
unsintered, 7=873 K
10J
E
u
8 io2^
CI
N
-
IO1
101
2.410JPa
8 Pa
10' ,0
---
310Pa
10
102 103
IO4
10u
60
'
"
105Pa
105Pa IO1
io-2 IO2
lO-1
10
101
10 1-1
CO/(27l-S_1)
*
IO3
IO4
IO5
(0/(27I-S_1)
x
8 Pa
\
"
---
310Pa
A
----'-''
S
o
40
105Pa
,-''",'''
00
^^~
\\
\\
00
40
f
9-
20 20
-
\
IO2
10"2
IO-1
10
IO1
IO3 104 b)
(0/(27t-S"1)
a)
(jn/(2n-s~l)
Fig.
4.18
impedance
of
LSM098 cathodes.Unsintered
cathodes
at
(a)
CO
873 K
Oxygen partial pressure dependence (600C) and (b) 1123 K (850C).
4
10
x.
sintered, 7= 1093
K
x. X,
x
.
sintered, 7=893 K
*x
IO2
*^
X,
x*
% 10I3
XX^
x"x.
C!
2
^^x
^X>>*.
-^^^-0.5
^X*
Xfc
IO1
o
o
N
14 Pa
^^*xi>.
"
1
---
10
10'
..]
.
. . .
102Pa 3.5103Pa 105Pa

10
2.8103Pa 105Pa
10u
IO4
10"
10' IO3 10L
IO2
10J
10'
IO2
IO3
IO4
IO3
0)/(27t-s-')-h
CO/(27t-S_1)
O
m
80
-----
14 Pa
---
R
H
"v,.*
60
---
.-.;"-* ""iii^ ,''" /
5
^
180)
60
*
^^
80)
/
/
/ K / /
102Pa 3.5103Pa 105Pa
^
/
e-
40
40
"%>
^~*""x^
^"~~^~'
2.8103Pa 105Pa
N
J
'
'
""O 'n
m
/
^-
/
/ /
/ *
H
/ /
20
-
y y
10J IO4
y
IO3
20
to
""
""
^T
10^
10'
IO2
IO-1
d)
10
10'
IO2
IO3
IO4
IO5
c)
G0/(27I-S-')
(0/(27I-S_1)
Fig.
at
4.18
(continued) After sintering

1373 K within the
(1100C) for
2 h in air at
(c)
1123 K
(850C)
and
(b)
at 893 K
(620"C). The oxygen partial
pressures of the measurements
are
given
figures.
4.4
Discussion
4.4
4.4.1
Earlier
Discussion
General
investigations
of lanthanum zirconate formation between LSM and

a
layer of lanthanum zirconate causes the deterioration of the oxygen reduction properties of the cathode. It was concluded from XRD measurements that A-site deficiency in
YSZ led to the conclusion that low
conducting
dense
LSMy may prevent, or at least retard lanthanum zirconate formation between LSMy and YSZ. It was the main purpose of this study to identify the influence
of lanthanum zirconate at the
triple phase boundary (tpb)
upon the oxygen

answer
reduction kinetics of
LSMy/YSZ interfaces.
We further wanted to
the
questions of
the incubation time and the role of the manganese content in the
out here that
LSMy.
experimental approach differs on a number of points from earlier investigations. First, we studied the behaviour of porous cathodes on single crystal YSZ. Using single crystals has the advan tage, that the influence of impurities usually present in polycrystalline YSZ (e.g. Si02, see e.g. [33]), can be eliminated. Porous cathodes are representative of the actual cathode/electrolyte interface in SOFC. Second, actual sintering temperatures and periods were employed, in order to be able to study the electrochemical properties of the (well performing) interfaces. Last, we employed a number of sensitive surface and interface investigation tech niques in parallel to obtain a conclusive interpretation of the nucleation and growth mechanism of lanthanum zirconate between YSZ and
We would like to
point
our
clearly supported the hypothesis of an incubation time [6] with increasing Mn content. Additionally, we have found that the Mn content in LSMy drastically influences both the nucleation and the growth kinetics of LZO at the cathode/ electrolyte interface. From the electrochemical imped
ance
Our
findings
have
measurements
we
have demonstrated that the presence of LZO at the
tpb drastically
influences the oxygen reduction
properties
of the electrochem
can
ical interface. For the first time it has been shown that the AFM
be
suc
cessfully employed to obtain cathode/electrolyte interface.
information about the nanostructure of the
197
La2Zr207
Formation
and
02
Reduction Kinetics
4.4.2
Lanthanum Zirconate Formation
Bulk diffusion limited
growth.
Sintering
(1100C)
of porous
LSM0 95 cathodes
on
(001) YSZ single crystals

in
at 1373 K
in air results almost
immediately
fine-grained, homogeneous layers of La-rich LZO on the YSZ surface (Fig. 4.4a). The reason for the low activation energy for La2Zr207 nucleation
be found in the close lattice match of the The
can
(001) surfaces of YSZ and
pyrochlore structure may be compared to a fluorite structure with one out of every eight oxygen ions missing. If these vacant sites were also occupied, the formula type would be A2B208 instead of A2B207 [31]. From the [Oil] SAED pattern (Fig. 4.4b) we find that the lattice constants of
La2Zr207.
[001] and [010] direction agree with those of pure La2Zr207 from the literature [31,29, 34]. We find a misalignment of the [100]Lzo ax*s
the LZO
grains
in
referred to the
[100]Ysz ax*s
f ~1-
Although we found from powder XRD measurements that the LSM0.95 was single phase, we suppose that traces of La203 were present in the powder. It
is well known that the detection limit of the XRD method is ~3 vol%. Excess
La203
from the Mn-deficient
LSMy
is
chemically
active and reacts immedi
ately at high temperatures with YSZ to form LZO. Nucleation and growth of LZO is facilitated by the use of porous cathodes which allows surface diffu sion of cations and unhampered oxygen exchange with the surrounding
atmosphere.
Let
us
From this information, certain conclusions
can
be drawn about
the mechanism of LZO nucleation and
first consider the
growth (cf. Fig. 4.19). phase diagram of the Zr02-La203 system [34].
La2Zr207
exists and has
a
At
temperatures below
2100 K,
wide solid solution
La203 concentrations, pyrochlore co-exists with Zr02, where a hexagonal lanthanum oxide ss appears at higher La203 concentra tions. Cubic ss of both the CaF2 and T1203 type exist at temperatures above 2200 K. With increasing temperatures, excess La203 may be transported to
(ss) range.
At lower
the interface either
by
surface diffusion of cations
or
by
densation mechanism. The
hypothesis
was
of the second mechanism is

covered with LZO
vaporization-con supported
grains
at the
by beginning
the fact that the YSZ surface of the
rapidly
and/or the YSZ

and its presence
sintering process. The presence of Mn within the LZO layer surface adjacent to the LZO grains was not demonstrated is not expected, because the La is provided from the excess
once a
layer forms, further layer growth is limited by bulk and/or grain boundary diffusion of Zr4+ and/or La3+ across the LZO layer. From our AFM and HRTEM measurements we found that the
La203. Obviously,
dense
198
4.4
Discussion
LZO
layer
grew almost
exclusively
towards the cathode and
only
to
minor
extent
(ratio -10:1)
into the YSZ. Is this tantamount to the statement that the

rate of
bulk
(or grain boundary) diffusion
Zr4+
is
controlling
the LZO
layer
growth kinetics in the early growth state? Brugnoni et al. [35] investigated the LZO layer growth kinetics at the inter face between porous La0 85Sr015Mn03 and YSZ polycrystals at temperatures between 1573 K (1300C) and 1773 K (1500C). By interpolating their data to constant the for obtain 1373 K we layer growth (1100C)
logD
1373 K
/(m
2
s
-19.9, which is in rather close agreement with the
result
we
obtained. Nevertheless,
they
than
measured the LZO

we
significantly higher temperatures

nesses
did, and
et al.
growth kinetics at they obtained layer thick

[35] concluded from
their
in the range of micrometers.
Brugnoni
a)
I-
(001) YSZ
200
nm
b)
Zr
4+
Fig.
4.19
Schematic view of the LZO
layer
formation at the interface of

near
LSMq 95
and
YSZ.(a)
Nucleation of
epitaxial
LZO islands starts
the
LSMq 95 grains.
Growth of
LZO islands takes
place along quent layer growth is limited by bulk diffusion of Zr4+ depending on the distance to the nearest LSMg 95 grain.
the YSZ surface until
a
dense
layer is obtained, (b)
Subse
and surface diffusion of
La3+,
199
La2Zr207
Formation
and
02
Reduction Kinetics
SEM-EDX measurements of the interfacial
region
that the diffusion of
La3+
determining step, as was concluded by others [4] (though these authors used dense diffusion couples), but which is in contradiction to our experimental findings. Both authors found reaction layers which almost completely grew towards the YSZ. Our XPS measurements of the freshly prepared sample (before Ar+ sputter ing) showed that the topmost surface layer was strongly enriched in Zr4+. In through
the reaction
layer
is the rate
addition, HRTEM images indicated the presence of

cubic
and
a
few atomic
phase
on
top of the LZO grains (cf. Fig.

of the
4.4 c). From the
layers of a phase diagram
high resolution images of this surface region with experimentally obtained high resolution images of YSZ, we conclude that the surface layer consists of cubic-stabilized Zr02 (c-Zr02). It is known that La can be dissolved in YSZ up to a few at% [5], which leads to a slight increase of the lattice constants. However, La is not known to stabilize Zr02 in cubic symmetry [34] but it is likely that La3+ and Mn2+/3+ are present in the top most layer. The cubic stabilization may be due to these doping elements and the influence of the cubic LZO lattice facing the c-Zr02 layer. Let us come back to the question whether the LZO layer growth is deter mined by the Zr4+ diffusion through the layer. It is probable that the Zr4+ transport takes place predominantly through the grain boundaries, which are generally 3-5 times thinner than the LZO grains (cf. Fig. 4.5b). Subsequent distribution of Zr4+ takes place by surface diffusion. The mean distance
comparison
between the LSM
(cf. Fig. 4.1), which is about 10 times the mean LZO grain size. Accordingly, the supply of Zr4+ is supposed to be much faster than the supply of La3+ by surface diffusion. This may
grains
is of the order of 1 pm
explain
Zr4+
the appearance of the
c-Zr02 layer
From the
found
on
the LZO
grains:
excess
reacts with
oxygen to intermediate
is
c-Zr02
and later transforms to LZO

it is not
when sufficient
La3+
present.
present experimental data
predictions about the layer growth mechanism at higher temperatures or in a later growth stage. It may be that the mechanism changes as soon as the excess La203 is consumed and, therefore, La3+ must be supplied by a different mechanism.
possible
to make
Surface diffusion limited
growth.
Sintering
(1100C)
on
of porous
LSM0 98 cathodes
a
on
(001) YSZ single crystals

in
at 1373 K
in air results after
few minutes
epitaxial, cube-shaped
images
we
LZO
grains
the YSZ surface. From the AFM and
the TEM
conclude that the LZO islands grow

and the YSZ surface. The most
between the
LSM0 98 grains
interphase striking feature of

as an
200
4.4
Discussion
the LZO islands is its very
clearly
visible cube
shape
on
the
(001) YSZ single

axes
crystal
grains
ance
surface. It is
are
likely
the
that the orientation of the cube

axes
of the LZO
parallel
to
[100] and [010]
of the YSZ surface. The appear
of the island did not

and the
scan
depend
on
the relative orientation between the
sample
as an
direction of the AFM
probe,
i.e. it
we
can
not be
considered
artifact. We would also like to mention that
obtained similar results

can
with
polished
YSZ
polycrystalline samples
when the LZO
was
and that these observations
also be carried out with the SEM. In contrast, Tricker and Stobbs
observed
[17]
epitaxy only
formed
during operation,
other
incoherently. They concluded that an oxygen ion flux in the vicinity of the interface during operation must be controlling LZO nucleation
wise LZO formed
process. Our observations contradict these conclusions.
sharp boundary between the islands the YSZ parent material we conclude that the growth of the LZO islands is controlled by surface diffusion of Zr4+ along the LZO side walls towards the top of the LZO islands. This explains the growth law obtained for the apparent LZO layer thickness, hav, which is clearly different from the growth law of dense layers. An exponent of 2 is expected in Wagner's law, if volume diffusion is rate limiting. Higher exponents are indicative for surface diffusion [36]. LZO islands growth is, therefore, expected to be much faster as in the case where an initial dense layer forms. But even after 12 h of sintering at 1373 K, the LZO layer is not dense and Zr4+ tiansport can still take place by surface diffusion. As soon as the YSZ surface is entirely covered with LZO, further growth is bulk diffusion limited and the mechanism is similar with the important difference that in this case as in the case with LSMq 95, dense layer growth starts at a layer thickness which is about two orders of magnitude larger (~200 nm) compared with dense LZO layers obtained with LSMo.95shape
Nucleation of the LZO islands does not, the
at
as one
From the
of the LZO islands and the
would expect,
occur
where
LSMq 98 grain and the YSZ surface are in immediate contact but it occurs the tpb (cf. Fig. 4.20). Similarly, Clausen et al. [18] has found from TEM
nucleation takes
our
investigations of YSZ-LSM phase boundaries that LZO place at the interface. This does not agree completely with
findings,
but
they
observed LZO islands in
late state of
can
growth (after sintering

be observed. We
at 1573
K)
typically find embryos around the contact sites. The reason for this phenomena can be explained as follows: because the region near the tpb of unsintered LSM grains on YSZ surfaces is highly curved, the free surface energy can be
not
where the actual location of nucleation

four LZO
201
La2Zr207
Formation
and
02
Reduction Kinetics
a)
I-
(001)
200
nm
YSZ
Fig. 4.20 Schematic view of LZO island formation and growth at the interface between LSMo98 and YSZ.(a) Nucleation near the tpb. (b) Growth is limited by surface diffu sion of Zr4+ along the LZO islands. La3+ is supplied from the LSMq 98 grain.
diminished
by decreasing
this
the curvature of the contact. At
relatively
low sin
tering temperatures
(see
and
a
occurs
predominantly by surface
and references
diffusion of cations
textbook about
are
sintering, e.g. [37]
therein). Because Zr4+
likely to form LZO in presence of oxygen, nucleation of LZO nuclei takes place in this convex interface region (cf. Fig. 4.20). Supporting this hypothesis is the experimental fact that the YSZ surfaces were stepped
after
a
La3+
heat treatment
(even
at
low
temperatures
as
1373
K) and that the YSZ
surface
sloped
down towards the LZO islands. The first fact is due to the
slight misorientation of the (001) single crystals, where the second fact is clearly related to the surface diffusion of cations from the YSZ parent mate rial. Further support is given by the HRTEM observation of the LZO islands. These were covered with a few atomic layers of c-Zr02. Although the sam ples were not quenched to room temperature from 1373 K (but only to 1073 K, cf. the experimental description), it seems that the high temperature
202
4.4
Discussion
preserved. A few atomic layers of c-Zr02 are seen on the side walls of the LZO grains, whereas a relatively thick region of c-Zr02 is seen on top of the island. By closer examination of HRTEM images of the island shown in Fig. 4.8 we find that the thickness of the c-Zr02 layer on the side wall does not depend on the crystallographic orientation of the habitus plane. We further observe that the LZO cube surface, which is supposed to be in contact with the LSMq 98 grains during sintering, is covered with c-Zr02 of
situation
was
-10 atomic From
layers (Fig. 4.9) as well. these experimental findings

rate would decrease with
we
would
expect that the LZO island

because the manganese
the
growth
activity
islands
increasing time,
in the
is
supposed
to increase
markedly
we
vicinity of
growth
near
front
of the LZO islands. The concentration of Mn in the YSZ surface

was
the LZO
distinctly below by
TEM
or
1% and
could not detect any Mn in the LZO

no
islands with TEM-EDX. We could also find
manganese
containing precip
itations, either
(although they ing the removal of the porous cathode). These findings the reductive formation of La2Zr207 [21]
AFM
could have
disappeared dur can be explained with
(Lax _xSr )Mn03

=
zZr02 + [(5
5')/2
3z/4]02(g)
(4.3)
In order to
(La1_x_2Sry)Mn03_8. + (z/2)La2Zr207
originated
from the A-site
where the reaction
nonstoichiometry.
reacts with
lower the A-site occupancy and to oxidize the manganese ions
(Mn3+
Mn4+)
in the
perovskite,
La in the
perovskite
Zr02
to form
La2Zr207. In addition, the reductive dissolution (cf. Eq. (4.1)) seems to play to a certain extent.
manganese
of manganese ions in YSZ

Due to the
relatively large
deficiency in LSMq 98, rather substantial amounts of LZO can be expected. Additionally, supply of manganese deficient LSMq98 is ensured because the LZO islands grow towards the unreacted LSMq 98. Accordingly, a decline of the growth rate is not expected until a dense LZO layer forms and further supply of Zr4+ is controlled by grain boundary or bulk diffusion through the LZO layer. Our findings about the stoichiometry of the LZO islands are in excellent
agreement with the results of Clausen
LZO in
et al.
[18]. Y substitutes for La
in the
significant
amounts. This is known to enhance the concentration of
oxygen vacancies
order of
[38] which
at 1173
increases the ionic
magnitude
K) and
conductivity (approximately one transport numbers. Y-doped LZO is
203
La2Zr207
Formation
and
02
Reduction Kinetics
considered
as
mixed
In
p-type and
ionic conductor in air at
temperatures
above -1000 K
[38].
addition, the Zr/Y
ratio in the LZO is about two times
higher
Let
us
than in the YSZ,
indicating
that the YSZ
facing
the LZO must be
enriched in Y.
finally compare the behaviour of LSMq.95 and LSMq 98. In the first case, thin and dense LZO layers are obtained after short sintering periods, whereas in the second case large islands are obtained. We want to address the ques tion why LSMq 98 does not form dense layers immediately, too? This might be due to traces of La203 in the original powder which reacted immediately with hardly any inhibition with the YSZ surface to form LZO. In the case of LSMq 98, only solid state reactions between manganese deficient LSM and YSZ or LZO occur. Accordingly, higher amounts of Mn should further inhibit
the formation of LZO.
Retardation of nucleation and
LSM102
amount
was
prepared
from
delayed growth. Keep in LSMg98 powder by adding
mind
that
the
the
appropriate
of manganese nitrate, i.e. the additional manganese is expected to be distributed on the LSMo98 surface and within the organic part of the
expected that the incorporation of excess manga nese into the perovskite phase takes place to a certain extent when the tem perature is raised. Accordingly, the manganese deficient perovskite grains are doped with manganese and change stoichiometry. Certainly, manganese also diffuses into the YSZ single crystal surface at elevated temperatures. In any case, the manganese activity is raised at the interface between the cathode grains and the YSZ. Similar arguments were given by Clausen et al. [18] who
screen-printing paste.
It is
stated that the
excess
Mn must not to be contained within the
perovskite
to
develop its efficiency in suppressing LZO formation (cf. Fig. 4.21). Although we know from the previous results that Zr4+ heavily diffuses
the YSZ surface towards the
on
tpb
to
decrease the free surface energy of the
interface, it is surprising
after
to see
how the
magnitude
of
transported
YSZ
even
only (2
to
4) h
at 1373 K
(cf. Fig. 4.10a). The result of Zr4+ surface diffu

4.10b. The YSZ diffused towards the
sion is
excellently
seen
in
Fig.
sintering
leaving a easily imaginable that a single LSMX 02 grain was positioned within the zirconia ring before dissolu tion. This can also be seen in SEM images of the interface (cf. Fig. 4.1b). The Zr/Y ratio within the formed Mn-doped YSZ rings is almost equal to the nominal ratio of the YSZ, indicating that the surface diffusion of Y is not sigbehind
neck which formed between the LSM
particle
and the YSZ surface,
lowered and faceted YSZ surface. It is also
204
4.4
Discussion
Fig.
4.21
Schematic view of LZO island formation and
growth at the
interface between
YSZ.(a) Nucleation of epitaxial (Mn)-YSZ starts near the LSM102 grains. Zr4+ and Y3+ diffuse along the surface of YSZ. Excess Mn from the LSMj 02 is incorpo
LSM102
and
rated into the

to form LZO.
sintering
(c)
necks until
La203
forms which
(b)
reacts
with the YSZ
tip
necks
Further
growth
of LZO islands is retarded.
nificantly hindered,
as one
could have concluded in the

no
previous
case
where
the LZO islands contained
Y. Cubic stabilization of the
with the presence of Y. In contrast to the situation with
rings is explained LSMq 98, manganese

takes
dissolution
from
the
perovskite
into
the
YSZ
heavily
place
can
(cf. Eq. (4.1)).

be
The concentration of -7.4% Mn is close to the value which

at 1373 K in
expected (-7%
air) from the thermodynamic calculations of
205
La2Zr207
Formation
and
02
Reduction Kinetics
Yokokawa [20]. These
large
amounts of Mn at the
tpb
may have
beneficial
the inter
effect upon the oxygen reduction and face. Note that the Mn concentration
incorporation properties of
corresponds to the equilibrium concen tration. Higher concentrations could only be obtained by increasing the sintering temperature (which would adversely increase the LZO formation tendency)
The
or
with
non-equilibrium methods,
topographic
information obtained from
ion-implantation [39]. plan-view TEM is in full agree

such
as
ment with the AFM measurements.
Nucleation of LZO islands is also
con
firmed from the
[001]
SAED pattern from the shown in
plan-view
a
(Fig. 4.12).
the SAED
The SAED
pattern
Fig.
4.12b shows
sample superposition of
TEM
patterns from the YSZ matrix, the Mn-YSZ islands, and the LZO
strong reflections
are
nuclei. The
due to YSZ. Its variation of the reflection
intensity
that
is characteristic for the fluorite structure
type.
It further is known
Mn-doping
nm.
of YSZ contracts the YSZ unit cell
slightly.
From the results

=
given by
-0.513
Yamamoto et al.
[5]
we
estimate
decrease of a0
0.514
nm
to
This
change
does not become apparent in the SAED pattern. Sur
prisingly,
the lattice constant of the LZO nuclei is
only
~2 times
larger
than
the lattice constant of YSZ

tern shown in
(instead of
almost
2.09
times).
From the
[001] SEAD pat
Fig. 4.12b,
an
perfect overlay
of both the YSZ and LZO be observed. This indi
pattern
cates
can
be seen; however, the misorientation
can
that the interface between YSZ and LZO nuclei is
although not strain-free. The minimization of the interfacial bly achieved through the slight misorientation of both lattices.
between the two lattices is obtained This value is small, and
as
fully coherent, energy is proba

The misfit
=
(ciLZq/2
aYSZ)/'flysz
4.88%.
accordingly, the mean distance between misfit dislo cations is expected to be large. Indeed, misfit dislocations can be observed in the cube-shaped LZO grains (cf. Fig. 4.8). But in this case, the lattice constant
of the LZO islands
was
estimated to be close to the theoretical value.
During sintering
This leads to
soon as a
at 1373
K, the zirconia rings grow in diameter and height.
further decrease of the Mn concentration in the
the critical Mn concentration
only be maintained by the reductive Eq. (4.3)). This leads to the nucleation of LZO grains on top of the Mn-YSZ rings, as observed in the AFM (Fig. 4.11) and HRTEM (Fig. 4.13). The further growth of these LZO islands was significantly retarded with respect to the LZO islands in the case of LSM0 98. This can be explained with the rate con trolling factor which in this case must be the reductive decomposition of the
perovskite. As is attained, a further Mn supply can decomposition of the perovskite (cf.
206
4.4
Discussion
perovskite,
images of
took
i.e. the
the
supported by the HRTEM tips of the Mn-YSZ rings (Fig. 4.13b). Although LZO formation
supply
of La. This is also
place
at the
tips, relatively large regions
of
c-Zr02 can be
seen.
4.4.3
General.
Oxygen
Reduction Kinetics at LSMn

a
98/YSZ
Interfaces
experimental studies (see e.g. [28, 40-46] YSZ have on the oxygen reduction of Sr- or Ca-doped LaMn03 cathodes on been performed, there is still relatively little known about the actual reaction mechanism at equilibrium potential. It is generally accepted that the overall reaction is composed of a multi-step reaction [45-47]. Adsorption of oxygen
Although
number of
[46], ing
dissociation of adsorbed molecular oxygen
[40,45,48]
and surface diffu
sion of oxygen
species [42, 45, 49] have been considered

of the
to be rate determin
the overall reaction rate. It has been found that the kinetics of the oxygen
reduction is
whereas
morphology of perovskite cathodes, the reaction rate has been found to be essentially proportional to the
literally independent tpb [42].
on
length
of the
It has also been
argued
that the electrode behaviour of
LSM cathodes
02(g) I YSZ system [1], where it has been shown that the dissociative adsorption of oxygen mole cules and/or the surface diffusion of atomic oxygen are rate limiting [50],
YSZ is similar to the behaviour of the Pt,
on
depending comparing
[51].
the
operating
conditions. However,
care
must be taken when
these two systems, because the oxygen
adsorption
process
on
on
oxide materials at
high temperatures impedance
is
completely
different from that
Pt
Our electrochemical
measurements of the
LSMq 98,02(g)
I YSZ
sintering at 1373 K in air and that the frequency response changes markedly (Fig. 4.15 and Fig. 4.16). From the tem R~ we conclude perature dependence of the electrode conductivity, ce that the rate-limiting reaction steps are different at low and high tempera tures. It is suggested that the formation of the LZO islands at the tpb due to
system show that
Rp
increases due to
sintering
oxygen
is the main
cause
for the
change
of the electrode
partial
pressure
dependence
of oe may therefore
properties. The provide more infor
mation about the reaction mechanism.
Cathode microstructure,
conductivity,
and
tpb length.
From
the
SEM
(Fig. 4.1) we see that the perovskite/YSZ interface corresponds to an actual cathode/electrolyte interface of a SOFC. The oxygen activity at the interface can therefore be compared to a
images
of
the
cathode
microstructure
207
La2Zr207
Formation
and
02
Reduction Kinetics
real cell. One
might expect that the electronic conductivity of unsintered cath
odes is insufficient and orders of
magnitude
it
below the electronic conductiv
ity
we
of sintered cathodes; therefore,

are
is
expected
that the
polarization
resistance of unsintered cathodes
below those of sintered cathodes. First,
have shown that the difference in electronic
conductivity
of unsintered
and sintered
LSMy
cathodes is
(cf. Fig. 4.2). Second, from

even a
considerably less than one order of magnitude the conductivity measurement we can see that
as
heat treatment at temperatures
low
as
1223 K
(950C)
is sufficient to
increase the electronic
conclude that the electrochemical
conductivity compared to electronic conductivity has only

because the
unsintered cathodes. We
a
minor influence
on
the
polarization resistance R of sintered cathodes is markedly higher than the polarization resistance of unsintered cathodes, in contiast to what might be expected. Our numerical estimates of the tpb length are in agreement with results reported in the literature from comparable cathode microstructures [42, 49]. We would like to point out, however, that the approach we employed per mits a rather accurate estimation of the tpb length. Similarly, the SEM can be used to obtain this information from electrolyte surfaces, as recently shown by others [52]. It is surprising that the tpb length of LSM0 981 YSZ interfaces reaches its maximum value (-5-106 m/m2) already after -30 min of sintering (cf. Fig. 4.7a). We have observed a similar behaviour for the LSM} 02 cath odes. With increasing sintering time at 1373 K (1100C) the tpb length decreases, although only by about a factor of two within 10 h. There have
properties,
been
some
attempts
in the literature to demonstrate
correlation between the
polarization resistance of perovskite cathodes (see e.g. [52-54]). Despite it is experimentally very difficult to obtain samples where the only difference is the length of the tpb. From the results discussed above we see that increasing sintering times or increasing sintering tempera tures not only influence the microstructure, but also lead to second phase for mation with altered microchemistry at the interface. In addition, one must be aware of the fact that slight differences in the stoichiometry of the LSMy (as it might be the case when using different powders of different grains sizes) may have a pronounced and unexpected (and unnoticed) effect, as we see from the comparison of the three perovskite compositions. It is, therefore, important to characterize the raw materials sufficiently. length
of the
tpb
and the
208
4.4
Discussion
Towards
reaction mechanism of unsintered interfaces.
At
873 K
(600C)
we
find
pQ
dependence
of oe for the unsintered
LSMq 98
cathode
(cf. Fig. 4.17a). In the literature a variety of pQ dependencies can be found (values from 1/4 to 1 have been found for the oxygen pressure exponent; see
references cited
above). Most reported

K is
measurements
were
obtained at tem
peratures between 1073

p0
(800C) and 1273

attributed to
K
a
(1000C).
one-quarter power
reac charge tion, where the dissociative oxygen adsorption obeys the Langmuir isotherm [55]. The same pQ dependence has been often found with Sr-doped LaCo03 perovskites (see e.g. [40]). In contrast to these conclusions we have to assume
dependence
generally
transfer controlled
from
our
EIS measurements that the cathodic reaction at 873 K
(600C)
is not
charge transfer controlled, but that it is controlled by a surface diffusion proc ess. Let us analyse our experimental results presented in Fig. 4.18 a in more
detail.
impedance spectroscopy of solids it is often assumed that a double layer capacitance Cd\ is associated in parallel with the Faradaic impedance ZF(jco) (cf. Fig. 4.22 and e.g. [56, 57]). We have discussed the possible reasons for the occurrence of Cd\, its consequences on the electrochemical impedance, and its order of magnitude elsewhere [58]. Typical values for Cdl are in the range of (1...20) pF/cm2. Usually, Cdl is esti mated by fitting equivalent circuits to experimental data. Unfortunately, this procedure requires an a priori choice of such a circuit which itself influences the result of Cdl. Berthier et al. [59] have presented a method for estimating Cdi without the need to assume an equivalent circuit for the electrode reac tion. The authors have also presented some illustrative examples. We briefly summarize the main concepts in the following. Electrochemical impedance spectroscopy has been considered as a promising tool for identifying complex reaction mechanisms in solid state electrochem istry (see e.g. [56] and references therein). However, the interpretation of spectra is generally difficult and it is further complicated by the influence of the double layer capacitance. There is nowadays no generally accepted method for dealing with this problem. EIS spectra of electrode processes have been interpreted for a long time in terms of equivalent electrical circuits and it has been only recently, where micro-kinetic models have been employed to
In the
theory
209
La2Zr207
Formation
and
02
Reduction Kinetics
c<11
*e *t
-
Ze(joo)
ZF(j(o)
"Equivalent circuit" of an electrode/solid electrolyte system and correspond ing frequency responses.(a) Equivalent circuit which may give rise to the spectra shown in (b). The Faradaic impedance ZF(s) is obscured by an electrical double layer capacitance Cdl in parallel and an electrolyte resistance Re in series. ZF(ja>) comprises a series combination of the transfer resistance Rt and the concentration impedance Ze(ja)). Ze(joo) often depends in a complicated way on the frequency. Only in very simple cases Ze(j(o). can be approximated with an electrical equivalent circuit. Note that the (measur able) frequency response Z(jco) depends on ZF(jCfl), Cdl, and Re and that the intrinsic dynamic behaviour of the electrochemical interface is exclusively described by its Faradaic impedance ZF(jco) (which is not directly measurable).
Fig.
4.22
describe the
dynamic properties electrodes in solid state electrochemistry [58,60-62]. In the general theory of EIS a number of quantities are of interest
some
and
important
the
relations
can
be derived
[63, 64]:
(i)
polarization resistance R of an electrode is a characteris tic measure of electrode performance. Its value corresponds to the small-signal dc resistance of the considered elec trode/electrolyte system. Accordingly, there is no need to obtain impedance spectra if one is only interested in the
polarization resistance. R is defined for arbitrary operating points on the current-overpotential curve, Ip(T|). R shows as the low frequency intercept with the real axis in a complex plane plot of impedance data Z(jco) (cf. Fig. 4.23).
210
4.4
Discussion
-i
7=873K
80
Z(JQ
<N
Zf0<o)
I40
650
ZQa
39 160
*>
1.4
..o
% A1
0
R.
/?c
Ze(0)
R_
40
80
120
160
Re(Z/Qcm2)
Complex plane plot of Impedance Z and Faradaic impedance ZF of unsin 105 Pa. The double layer capaci tered LSMo981 YSZ interface at 873 K (600C).p0 tance Cdi is obtained by applying the method from Berthier et al. [59]. We estimate Cdl 1.34 pF/cm2, Rt 7.32 Q cm2, Re 3.42 Q cm2, and Rp 141 Q cm2. Both Z and ZF are shown with the electrolyte resistance Re subtracted.
Fig.
4.23
=
=
(ii)
charge-transfer resistance Rt is a further important quan tity. The well known exchange-current density, i0, is related to Rt by i0 RT/(2F) 1/Rt. However, Rt is defined for arbitrary operating points, i.e. overpotentials, whereas i0 must be considered as an steady-state quantity [58]. Unfortu nately, Rt is not directly accessible from electrochemical measurements, but it must be extracted from EIS data by esti mating the associated double layer capacitance Cdl (see Fig. 4.23 and Refs [58, 59]).
The
=
(iii) The difference between the polarization
resistance and the
charge-transfer
resistance is attributed to the concentration

=
polarization, Rc
to chemical
Rp Rt. The origin of Rc

-
can
be attributed
or
processes
on
on
the electrode surface,
to mass
transport processes
the electrode surface 'or in the gas
phase.
211
La2Zr207
Formation
and
02
Reduction Kinetics
(iv) Once Cdl and Rt

can
are
known, the Faradaic impedance
be obtained from the
Z(jco)
raw
data. It is
ZF(jco) important to
dynamic properties of an electrode/elec trolyte system are entirely described by ZF(jco), and not by Z(jco). A discussion of EIS data should, therefore, always be performed on the ZF(jco) data (cf. Fig. 4.23).
understand that the
We
now
apply
these concepts to the
present data. Fig.
4.23 shows both the
impedance ZF(jco) of the LSM0 98 cathode in oxygen at 873 K. It is readily seen that the polarization resistance Rp is not dominated by the transfer resistance Rt, but that Rp is controlled by a concentration polarization Rc. Therefore the idea of a charge transfer controlled reaction must be abandoned. The value for Cdj was esti
electrochemical
impedance Z(jco)
and the Faradaic
mated
as
-1.3
pF/cm2 and
it
was
virtually independent of the

we
oxygen
an
partial
pressure. This result is in agreement with what
expect for
unsintered
(i.e. unbonded) interface, where

about 70%
we
guess the actual electrode /electrolyte
coverage to be less than -10%. After
sintering,
i.e. when the contact

to be about
one
area
is
(cf. Fig. 4.7a),
we
expect the value for Cdi
order of
magnitude higher. We would like to point out that we understand the origin of the double layer capacitance to be entirely caused by the contact of an elec tronic conductor (the perovskite grains) and a dielectric material (the YSZ single crystal). We neither interpret the double layer capacitance as a "pseudo-capacitance" [65], nor is it ascribed to the heterogeneous electrode reaction [1]. The dynamics of the oxygen reduction are completely described by the Faradaic impedance, and it is this contribution in which we are actu ally interested [64]. More information about the type of the concentration polarization is there fore obtained by looking at the frequency dependence of |ZF|. In the log(|Z|) vs. log((o) plot of Fig. 4.18a a slope close to -0.5 is found. This is better seen from the numerical derivatives of log(|Z|) and log(|ZF|) with respect to over a broad log(co) (Fig. 4.24). |ZF| is approximately proportional to corange of frequencies even in pure oxygen atmosphere. With decreasing pQ the concentration polarization increases and |ZF| is almost perfectly propor 8 Pa (Fig. 4.24). tional to co"1/2 from 10 Hz to -5 kHz at pQi It is well known that at high frequencies under surface diffusion control of atomic species, the following holds (see e.g. [66], or [67])
=
212
4.4
Discussion
T=873K
1
JO
-0.2
B
n
#
S
pn u2
=105Pa
D a
8
i
88o0
^
CN
-8 Pa
oo0
aa
-0.4
po2"8Pa
*.g
oSQV0
D
-0-6
. ...^ /.
a
g1
-0.8
ZF(j(D)
ZCjco)
-1.0
10"1
10
101
102
103
104
105
Q)/(2tc-s"1)
Fig.
Frequency dependencies of IZ I and IZFI of the unsintered LSMq 981 YSZ interface at 873 K (600C).The Faradaic impedance ZF is obtained as described in the
4.24
text and the
partial pressures are given within the figure. decreasing impedance measurements with increasing fre quency. At high frequencies |ZF| should reach its limiting value Rt, and therefore the frequency dependence of |ZF| should diminish. Generally, this is only partially the case due to the influence of the electrolyte impedance upon the electrode impedance at high frequencies.
legend of Fig.
4.22. The oxygen
Note the
accuracy of the
ZF(j)
Kwaf1/2x(l-j)
RT
=
\n F
CqJ2D
a>1/2x(l-j)
(4.4)
species, C0 is its equilibrium surface concentration, Kw is called the Warburg constant, and the other symbols have their usual meaning. Obviously, the experimentally determined to dependence of |ZF| supports the hypothesis of a surface
diffusion controlled kinetics. follow the
a
where D is the surface diffusion coefficient of the mobile
By
contrast, it has been
p02
dependence
if surface diffusion is rate
argued that oe should limiting [40, 68]. But at

were
same
time it should be mentioned that those results
obtained for the
213
La2Zr207
Formation
and
02
Reduction Kinetics
Pt,
Oz(g)
I YSZ system. We know that it is
misleading
to
use
results obtained
for noble metal/solid
electiolyte systems directly

e.g. at 1123 K
for the
interpretation
3/8 a
of
perovskite cathodes.
depend above -102 Pa (Fig. 4.17a). By consideration of ZF(jco) and ence of oe at p0 10 Pa if is seen mat the polarization resistance Z(jco) at p0 Rp is to a large extent due to the charge transfer resistance Rt (Fig. 4.25). With decreasing Pq the concentration polarization Rc increases, but the contribution from Rt remains significant. At pQ lower than 10 Pa, surface diffusion becomes dominant as described above, although less pronounced in contrast to the sit
we
At
higher temperatures,
=
(850C),
find almost
pQ
uation at 873 K
(600C).
At pQ
5 Pa
co-
dependence
of
|ZF|
a
is found
from -100 Hz to -5 kHz. The pQ pressures is in

tion between
dependence
of ae at low oxygen
agreement with this observation. We conclude that
partial competi
charge
transfer and surface diffusion dominates the electrode
behaviour at oxygen
partial
pressures between
(103...105)
Pa and
tempera-
......
7= 1123 K
II
II
rn
i
1 1
Z(jw)
L-H /?,
1- z80
S
o
a
N N
Zp(J<B)
3k
,
XZ,<joJ)
I3k#
#750

oooOoooOOoVS0
*t
45k
*p_
1 1
12
Re(Z,
Fig.
4.25
ZF/(a-cm2)
=
unsintered
Rt
Complex plane plot of Impedance Z and Faradaic impedance ZF of the LSM0 981 YSZ interface at 1123 K (850C). We obtain Cdl 5.1 pF/cm2, 2.17 Q cm2, Re 0.32 Q cm2, and Rp 4.88 Q cm2. Both Z and ZF are shown with
=
=
the
electrolyte
resistance
Re subtracted.
214
4.4
Discussion
partial pressures below 102 Pa, surface diffu sion of atomic oxygen becomes rate deternuning again, as at lower temperatures over the entire oxygen partial pressure range. Note that we have assumed that atomic oxygen species are diffusing and that the preceding reaction steps, i. e. adsorption and dissociation, are not playing a significant role in the overall reaction path. Let us consider the conse quences of these assumptions. Only if the elementary reactions are in
hires above -1100 K. At
oxygen
sequence,
can we
expect that the slowest

in
reaction
step determines the overall
reaction rate. But, surface diffusion of atomic oxygen and dissociation of oxy
parallel on the perovskite surface. Obviously, if the dissociation rate near the tpb is much slower than the surface transport rate towards the tpb (which is normally the case a high temperatures), the overall reaction will be dominated by the faster supply rate, i.e. the surface diffusion
gen molecules
occur
step. This
cathodes
were
is in
agreement with the results obtained with unsintered LSMq 98
on
YSZ.
By
the
contrast, if
we
assumed that molecular oxygen
species
perovskite surface, we would expect that the necessary dissociation step near the tpb (before the incorporation step) would be rate limiting, which is experimentally not observed. It is finally seen from the complex plane plot in Fig. 4.14 a that the low frequency part has no circular shape, but that the impedance starts as a straight line with almost a -135 angle with respect to the real axis. This is observed over a broad range of tem peratures and may be explained with the phenomenon of spherical surface diffusing on
diffusion
[69].
Influence of
sintering
on
electrochemical
1373 K for 2 h in air,
we
still find almost
properties. After a dependence pQ
sintering
at
of ae at 1223 K
(950C) (Fig. 4.17b). The change of the oxygen partial pressure dependence
readily explained by oxygen gas diffusion in the electiode pores [41]. In the complex plane a second semi-circle develops (Fig. 4.26) at low frequencies (from 1 mHz to -1 Hz) with decreasing pQ The resistance
is
.
towards pQ
related with this low
showed almost
no
frequency dispersion was proportional to temperature dependence from 1223 K to 1273 K,

partial
=
pQ
and
which is
distinctive for gas diffusion limitation. The contribution from gas diffusion
decreasing temperatures. < At T 1123 K (850C) it became apparent (but not significant) at pQi 10 Pa. At T 1123 K (850C) and T 1093 K (820C) a p* dependence of oe is found at high oxygen partial pressures. With decreasing pQ a slight change towards a pQ dependence is found. This change is also shifted to lower
was
= = ,
shifted to lower oxygen
pressures with
215
La2Zr207 Formation
and
02
Reduction Kinetics
ou
r=1223K
40
~
s
o
CI
?5
i
20
\
_J
P02
93Pa
_J
20
40
60
80
100
Re(Z/Q-cm2)
Impedance Z of sintered LSM0 981 YSZ 1223 K (950C) and low oxygen partial pressures.The numbers within denote the frequencies in Hz. The frequency range was limited to 20 mHz.
Fig.
4.26
Complex plane plot
of
interface at the
figure
decreasing temperatures (cf. Fig. 4.17b). It would be most straightforward to conclude from the pQ dependence of oe that a competition between charge transfer and surface diffusion exists, as is
oxygen
partial
pressures with
the
case
for the unsintered interface. However,
we
have shown that islands of
during sintering (cf. Fig. 4.6) and we know that the frequency response of sintered LSM098/YSZ interfaces is significantly different from that of unsintered interfaces (Fig. 4.15). It is, therefore, obvious
lanthanum zirconate formed
to ascribe these
idea,
we
changes further analyse
to the presence of the LZO islands. Based
on
this
and discuss the
impedance
results of the sintered
interface.
Towards reaction mechanism of sintered interfaces. both the
Fig.
4.27
shows of
a a
complex plane plot of sintered LSMq 981 YSZ

shows almost
a
impedance
an
the Faradaic
impedance
At
interface at 893 K
(620C)
in oxygen. The 20
spectrum
perfect quencies, ZF displays a -45 angle
semi-circle at low
frequencies (<
(cf.
Hz).
high
fre
with the real axis
inset in
Fig. 4.27). Rt
216
4.4
Discussion
is
extremely low, therefore the overall reaction rate is limited by concentra tion polarization, as in the case before sintering at 873 K (600C) (cf. Fig. 4.23). Let us now again analyse the co dependence of |ZF|. If the reaction was surface diffusion limited,
a
clear
co
Fig.
can
4.28 it is
seen
that this is not
dependence should be noticeable. From undoubtedly found. Nevertheless, a co~

frequency range.
1 kHz to 20
be observed from -1 kHz to -10 kHz, which is also reflected in the -45 the real axis in this
It
seems
angle between ZF and
that the
co
dependence
quency
ent
from the unsintered cathode is contained within the
spectrum of
a
the sintered cathode
(compare
from
co
kHz). The stronger fre

differ
to
dependence of |ZF|
between 10 Hz and 500 Hz indicates that
process than surface diffusion must be
contributing
is
a
the overall
electiode resistance.
A
slope
of -1 in the
log(|ZF|)
chemical
versus
log(co) plot
on
clear indication of
surface
first-order
(electro-)
means
reaction
the
perovskite
[64].
"First-order"
that
single
1
adsorbed
species
1
is relevant and
responsi-
200
7=893K
18

<<T
100
,6
S
C!
0
51/
30 283.
.
/-26k
ZQa
2
730
\/0.4'
.*
10
1.5k
o%
-100-
//v
0 10
20
30
4()
100
200
300
400
500
Re(Z/Q-cmz)
Fig.
4.27
tered
Complex plane plot of Impedance Z and Faradaic impedance ZF of the sin LSMq 981 YSZ interface at 893 K (620*^) in oxygen.The interface was sintered in
set
air at 1373 K for 2 h before
data
is
shown
in
=
cooling to measuring temperature. A Bode plot Fig. 4.18d. We obtain Cdl 5.5 pF/cm2, Rt
=
of the
4.5 Q
same
-cm2,
Re
2.5 Q
-cm2, and Rp
455 Q
cm2.
217
La2Zr207
Formation
and
02
Reduction Kinetics
ble for the electrode
dynamics.
are
Due to
coupling
between surface diffusion

are
and the chemical reaction, i.e. the relaxation between -1 and -1/2
frequencies
too
close, slopes
expected. This is what is seen in Fig. 4.28a and what gives rise to the "depressed" semi-circle, i.e. that the semi-circle has its centre below the real axis (cf. Fig. 4.27). We now would expect that a slope of -1 could be reached upon lowering the oxygen partial pressure. Fig. 4.28b 0 8 behaviour 10 Pa. It is clearly seen that a a) shows the analysis for pQ predominates over more than one order of frequency magnitudes. This sup ports the hypothesis that surface diffusion is in competition with a chemical reaction on the cathode surface. In addition, by comparing the graphs in Fig. 4.24 with the graphs in Fig. 4.28 it is seen that the relaxation frequencies contained within the surface diffusion process are spread over a wide range of frequencies, in particular at low p0 It is concluded therefore that the sur
'
face diffusion process interferes with the chemical process in the spectrum
and therefore neither
a
distinct (o~
dependence
nor a
distinct co"
depend-
s
11
r=893K,/> u2
o
o o
=105Pa
o
/""Xy
3,
60
-0.2
JD
'O
o o
^
<N
-0-4
o
o
E
o
-0.6
o
o O
O
g(izi
o
V
-0.8
w
v.
o
o.'.
**
5
Ô
ZpCJW)
Z(ja>)
"
IO"1
a)
10
IO1
IO2
IO3
IO4
10-
CO/(27C-S_1)
Fig.
face
4.28
Frequency dependence of IZ I and IZFI of the sintered LSMq q8 IYSZ inter 10 Pa and (b) at 893 K (620C) at different oxygen partial pressures.(a) pQ
= =
pO2
10Pa.
218
4.4
Discussion
0
o
"-r
Zp(jC0)
Z(jo>)
7-=893K,p0
10 Pa
3,
-0.2-
^
B
o
-0-4
-o
g
o
-0.6
o0 o
-0-8
00o OoO#<
O
i
0
*
-1.0
10 ,-1
10''
101
102
103
104
10!
CO/(27C.S_1)
b)
Fig.
4.28
(continued)
ence
of IZJ is measured. We find
similar behaviour of the sintered interface

-1/2
higher temperatures. However, the co dependence is closer to a co dependence than to a co~ dependence. This indicates that the surface diffu sion process predominates and that the supply of oxygen by the chemical process plays a minor role. Using the same arguments as above concerning
at
the nature of the chemical step

not
we
conclude that the dissociation step, and

is
the associative
seen
adsorption step,
spectra.
responsible
for the concentration
impedance
in the
It is, however, not
yet clear why the electro

cathodes differs
so
chemical behaviour of unsintered and sintered
LSM0 98
we
strongly, especially question.
at low
temperatures, and
will
finally
address this
Discrimination of reaction steps.

unsintered
We have
seen
that the overall reaction of
by surface diffusion of an atomic oxy gen species at T < 1123 K (850C). With increasing T, a competition between charge-transfer and surface diffusion develops. This is easily explained with the difference in activation enthalpies of surface diffusion, AHd, and
LSMq 98
cathodes is limited
219
La2Zr207
Formation
and
02
Reduction Kinetics
charge-transfer, AHct. From the experimental results it is concluded that AHd is higher than AHct, which is comparable to the situation in the Pt, 02(g) I YSZ system (see e.g. [55, 70]). Obviously, the adsorption and dissociation processes take place in parallel to surface diffusion on the cathode surface close to the tpb [42]. Furthermore, the surface diffusion rate of Oad towards the tpb is much larger than the direct supply rate of Oad from the adsorption/dissociation near the tpb (Fig. 4.29a). We assume that the surface diffusion coefficient of Oad on LSM is in the same order of magnitude as for Oad on Pt [66]. Accordingly, we find that the Nernst diffusion layer thickness 8, i.e. the distance where perturba tions of Oad near the tpb are propagated, is in the order of (50 to 150) nm at temperatures between 823 K (550C) and 1273 K [58]. The supply of ofd within 8 is realized by the surface diffusion process of atomic species and to a
LSM
Pore
O8" ^ 0*-(ad)
(D
|
(4)
e~
^
(2)
^^
,
02(g)
O5- zl
(3)
0f"(ad) ^^
O5"
YSZ
o2-
Fig. 4.29 Model of the oxygen reduction interfaces.(a) Oxygen adsorbs (1) on the
at unsintered
and sintered
LSMq 98/YSZ
step (2)
is
LSM surface. The dissociation
expected
O
at
are
to be slow. Both the
transfer. The LSM surface above the
adsorption tpb
and dissociation
acts
as a
step
are
coupled
reservoir for atomic oxygen
the
supplied by tpb. Note that
surface diffusion
(3)
and
the Nernst diffusion
finally layer 8 is
electronated and
in
charge species. incorporated (4)
with
expected
to be in the order of
100
nm.
220
4.4
Discussion
LSM
Pore
O8"
ofrCad)
LZO
0^
offCad)
2<g)
e~
O8"
YSZ
\
o2at the
i
1
i
I
100
nm
Fig.
4.29
(continued) (b) LZO islands
tpb
hinder both the dissociation
step and the

of
final electron-transfer
step (denoted with the smaller arrows). In consequence, the equi

on
librium concentration of O
O is
on
the LZO is smaller
compared
to the concentration
the LSM above. Surface diffusion of O
from the LSM surface towards the
tpb
considerably retarded,
the direct
because the thickness of the LZO islands is in the order of 8.
Accordingly,
supply
of O
via the
adsorption/dissociation
process becomes
dominant. See the main text for further
explanations.
minor
part by the adsorption/dissociation process. Note that the adsorp tion/dissociation process also takes place near the tpb, but the rate of this
supply is generally far below the surface transport rate (compare with the Pt, 02(g) I YSZ system [50, 58, 64]). It is furthermore important to recognize
that the electrode material
completely
determines the rate
(and type) of oxy
adsorption magnitude for

gen Oxides:
In the
case
and dissociation and that the rates may vary many orders of
different cathode materials (see e.g. for Pt: [71], Au: [72],
[51, 73]).
of sintered
LSM0 98 cathodes,
8 is in the order of the thickness of the
the lanthanum zirconate
(LZO) islands which formed between
LSM0 98
grains
and the YSZ surface after 2 h surface diffusion and

on
Accordingly,
sintering (see Fig. 4.6a and Fig. 4.7c). adsorption/dissociation take place pre
surface
dominantly
the
lanthanum
zirconate
after
sintering
(see
221
La2Zr207
Formation
and
02
Reduction Kinetics
Fig. 4.29b).
cient of
From YSZ it is known that it has
low surface
exchange
coeffi
02(g) [74]. It is expected that the surface exchange properties of LZO are comparable with those of YSZ, because LZO and YSZ are of similar struc ture. Accordingly, the rate of adsorption/desorption near the tpb decreases
due to the presence of LZO. We suppose that the surface diffusion coefficient
of adsorbed atomic oxygen is not altered
drastically. However,
because the
large reservoir of Oad on the LSMq 98 surface is -100 nm apart from the tpb it is expected that the Oad supply by surface diffusion strongly decreases. Accordingly, the direct supply of Oad through the adsorption/dissociation process becomes increasingly significant. This interpretation is in agreement with the experimental observations. It is further supported by the fact that
the differences
in
ae, unsintered and sintered cathodes, increase with
decreasing temperatures (Fig. 4.16). This can be explained with the decreas ing supply rate of Oad by surface diffusion, because 8 decreases with decreasing temperature. Having discriminated the relevant reaction steps of the oxygen reduction at LSM/YSZ interfaces, we give the following model description
(i)
02(g)
adsorbs
on
the LSM surface
according
to
[73] (4.5)
02(g)
where
s
e"
+ s <^
02(ad)
and
e
denotes free
adsorption sites,
electrons from
the electrode.
(ii)
The adsorbed
02(ad) species subsequently turns 02(ad)

+
into O"
e"
20"(ad)
(or LZO) surface, before
reaction
near
(4.6)
it is
(iii) and may diffuse
on
the LSM
in the
finally incorporated tpb according to

0"(ad)
+
charge-transfer
the
e"
Vo<^>Oo + ad.
(4.7)
Although the structure of this model complies with our experimental find ings, we know very little about the rate constants and activation enthalpies involved. However, investigating the properties of this micro-kinetic model similarly as described elsewhere [64], could help to obtain more information from experimental data (cf. [58, 64]).
222
4.5
Conclusions
4.5
The
Conclusions
thermodynamic
study
was
limited
to
the
investigation
of
La0 85Sr015Mny03/YSZ
no
interfaces under
equilibrium conditions,
i.e. where
through the interface was flowing. It is well known [21] that cur rent-produced overpotentials at the cathode influence the oxygen chemical potential in the electiolyte in particular in the vicinity of the cathode grains. It is also known from recent TEM studies that the reverse reaction of Eq. (4.3) can take place to some extent, and that therefore initially formed LZO islands
current
may
the
disappear during
cell
operation [75]. However,

can
we
have shown that the
formation of lanthanum zirconate
be
sintering temperatures
excess
to -1373 K and
effectively suppressed by reducing by doping the La0 8sSr015Mn03

excess
with
manganese. We have demonstrated how the
manganese
controls the nucleation and From the electrochemical

were
growth of the lanthanum zirconate. investigation of the LSMq 98, 02(g) I YSZ system
Dissociation adsorbed oxygen ions,
we
able to discriminate the relevant reaction steps of the oxygen reduction
mechanism at
LSMy/YSZ interfaces.
sur
face diffusion of atomic oxygen, and the
polarization resistance, depending

tions. We believe that
a
on
the
charge transfer contribute operating and fabrication

a
to the
condi
successful identification of
reaction mechanism
requires first a detailed microstructural investigation of the cathode /electro lyte interface. We have also shown that the interpretation of the frequency
straightforward and may lead to ambiguous conclusions. We, therefore, suggest that impedance data not be analysed in terms of equivalent circuits but from a more fundamental perspective.
However,
data
we
dependence
of oe alone is not
believe that
we are
still far from
state and
parameter
estima
tion of the
are
LSMy, 02(g) I YSZ

on
system, mainly because little physico-chemical
available
the interaction of oxygen with

is
even more
perovskite
surfaces. Fur
ther work in this
area
necessary than further electrochemical
investigations.
Acknowledgments.
portation,
The financial
much indebted to Dr. M. Cantoni The authors wish to thank present
gratefully acknowledged. The authors are very who performed most of the HRTEM measurements.
many useful discussions. In

batical from
colleagues in the Chair of Nonmetallic Materials for particular, we are indebted to Prof. Dr. D. Bonnell, on sab
our
Pennsylvania University, and Dr. M. Godickemeier, carefully reading the manuscript and giving valuable comments.
laboratory,
for
223
La2Zr207
Formation
and
02
Reduction Kinetics
References
[I]
M.
Kleitz, T. Kloidt, and L. Dessemond. Conventional oxygen electrode reaction:
Mixed ConductorsProc.
de, Denmark, 1993.
High Temperature Electrochemical Behaviour of Fast Ion and of the 14th Riso Int. Symp. on Mat. Sci., pages 89-116, Roskil Ris0 National Laboratory.
interactions at solid oxide fuel cell
[2]
S. K. Lau and S. C.
Singhal. High temperature Elangovan,
interfaces. In Proc. Corrosion 85, Boston, pages 79-80,1985.
[3]
C. Milliken, D. Tucker, S.
erations and
nar,
and A. Khandkar. Thermochemical consid
performance
of solid oxide fuel cells. In Ext. Abs. 1990 Fuel Cell Semi
Phoenix, 22
van
to 25 November
1990, pages 218-221,1990.
[4]
J. A. M.
Roosmalen and E. H. P. Cordfunke. Chemical
reactivity
and interdif-
fusion of
(La,Sr)Mn03 and (Zr,Y)02,
solide oxide fuel cell cathode and
electrolyte
materials. Solid State Ionics, 52:303-312,1992.
[5]
O. Yamamoto, G. Q. Shen, Y. Taked, N. Imanishi, and Y. Sakai. Electrode characterization for SOFC. In
stability High Temperature Elec Symposium Proceedings Materials and Characterization, pages 158-164, Pennington, NJ, 1991. The Elec trode trochemical Society, Inc.
of the
on
[6]
H. Taimatsu, K. Wada, H.
tween lanthanum
Kaneko, and H. Yamamura. Mechanism of reaction be

and
manganite
yttria-stabilized
zirconia.
/.
Am. Ceram. Soc,
75:401-405,1992.
[7]
G.
Stochniol, E. Sysakis, and A. Naoumidis. Chemical compatibility between

lanthanum
strontium-doped
am.
manganite
and
yttria-stabilized
zirconia.
/.
Am. Cer
Soc, 78:929-932,1995.
[8]
A.
Mackor, T. P. M. Koster, J. G. Kraaijkamp, and J. Gerretsen. Influence of La-sub

of Ca-or
-substoichiometry on conductivity, thermal expansion and chemical Sr-doped lanthanum manganites as SOFC cathodes. In Proceed stability ings of the Second International Symposium on Solid Oxide Fuel Cells; Held from 2 to 5 July in Athens, Greece, pages 463-471, Luxembourg, 1991. Commission of the Euro
stitution and
pean Communities.
[9]
O. Yamamoto, Y. Takeda, R. Kanno, and T.
Kojima. Perovskite-type oxides as oxy
gen electrodes for 1987.
high temperature
oxide fuel cells. Solid State Ionics, 22:241-246,
[10]
T.
Setoguchi, T. Inoue, H. Takebe, K. Eguchi, K. Mornaga, and H.
Arai. Fabrication
and evaluation of flat thin film solid oxide fuel cell. Solid State Ionics, 37:217-221,
1990.
[II]
O. Yamamoto, Y.
Takeda, R. Kanno, and T. Kojima.
Stability
of
electrode with stabilized zirconia. In

on
Solid Oxide Fuel Cells, pages 242-253,

Inc.
Proceedings Pennington, NJ,
of the First International
perovskite oxide Symposium
1989. The Electrochemical
Society,
224
References
[12]
H. Kaneko, H. Taimatsu, K. Wada, and E. Iwamoto. Reactions of
La1_xCa.cMn03
cathode with YSZ and its influence
of the Second International

Athens, Greece, pages
Communities.
Proceedings Symposium on Solid Oxide Fuel Cells; Held from 2 to 5 July in 673-680, Luxembourg, 1991. Commission of the European
on
the electrode characteristics. In
[13]
H. Yokokawa, N.
Sakai, T. Kawada, and M. Dokiya. Thermodynamic analysis of interface between perovskite electrode and YSZ electrolyte. Solid State Ionics,
40/41:398-401,1990.
[14]
H. Yokokawa, N. Sakai, T.
Kawada, and M. Dokiya. Chemical
potential diagrams
with
for La-M-Zr-O
zirconia
as a
(M=V, Cr, Mn, Fe, Co, Ni) systems: Reactivity of perovskites function of oxygen potential. Denki Kagaku, 58:489-497,1990.
[15]
H. Yokokawa, N.
Sakai, T. Kawada, and M. Dokiya. Chemical thermodynamic
considerations
nese,
reactivity of perovskite oxide electrodes with zirconia (in Japa figure captions in English). Denki Kagaku, 57:821-828,1989.
on
[16]
H. Yokokawa, N.
reaction
profiles
between
Sakai, T. Kawada, and M. Dokiya. Thermodynamic analysis of LaM3 (M=Ni,Co,Mn) and Zr02. /. Electrochem. Soc,
138:2719-2727,1991.
[17]
D. M. Tricker and W. M. Stobbs. Microstructural
aspects of lanthanum
zirconate
formation. In
ductorsProc.
mark,
1993.
High Temperature of the 14th Ris0 Int. Symp. Rise National Laboratory. Bagger, J.
Electrochemical Behaviour
on
of Fast Ion and Mixed Con
Mat. Sci., pages 453-460, Roskilde, Den
[18]
C. Clausen, C.
B. Bilde-Serensen, and A. Horsewell. Microstructural and
microchemical characterization of the interface between
La^ ggSr015Mn03
and
Y203-stabilized Zr02.
[19]
A. Khandkar, S.
Solid State Ionics, 70/71:59-64,1994.

and M. Liu. Materials considerations for
Elangovan,
application
to solid-state electrochemical devices.
[20]
H. Yokokawa, N.
Sakai, T. Kawada, and M. Dokiya. Chemical thermodynamic
compatibility of solid oxide fuel cell materials. In Proceedings of the Second Interna tional Symposium on Solid Oxide Fuel Cells; Held from 2 to 5 July in Athens, Greece, pages 663-670, Luxembourg, 1991. Commission of the European Communities.
[21]
H.
Yokokawa, T. Horita, N. Sakai, T. Kawada, and M. Dokiya. Thermodynamic
considerations
at
plausible effect of oxygen flow morphology of reaction products the YSZ/lanthanum manganite interface in solid oxide fuel cells. In Proceedings
on
of the First European

1994. U. Bossel.
Solid Oxide Fuel Cell Forum, pages 425-434, Baden, Switzerland,
[22]
E.
Ivers-Tiffee, M. Schiefil, H. J. Oel, and W. Wersing. SOFC cathodes with mixed
conduction:
Advantages
on
and limitations of Co
containing perovskites.
In
Temperature
tional
of Fast Ion and Mimoxed ConductorsProc.
High of
the 14th Rise Int.
Symp. Laboratory.
Mat. Sci., pages 69-87,
Roskilde, Denmark, 1993. Rise Na
225
La2Zr207 Formation
and
02 Reduction Kinetics
[23]
S.
Elangovan, A. Khandkhar, M. Liu, and M. Timper. Solid state interface reactions in SOFCs: An EIS study. In Proceedings on the Symposium on High Temperature elec trode Materials and Characterization, pages 191-199, Pennington, NJ, 1991. PV 91-6,
Society.
air cathode
The Electrochemical
[24]
T.
Kenjo and M. Nishiya. LaMn03
containing Zr02 electrolyte for high
temperature
solid oxide fuel cells. Solid State Ionics, 57:295-302,1992.
[25]
terface.
In
F. W.
J. Gauckler. Oxygen reduction at the La0 85Sr015MnQ 9803 in Poulsen, N. Bonanos, S. Lindenroth, M. Mogensen, and
B. Zachau-Christiansen, editors, MetalsProc.
of the 17th Rise Int.
mark, 1996. Rise
High Temperature Electrochemistry: Ceramic and Symp. on Mat. Sci., pages 357-362, Roskilde, Den National Laboratory.
[26]
J. Gauckler. LSM-Kathoden fu Festelektrolyt-Brennstoffzellen. In Werkstoffwoche '96, Symposium 3: Werkstoffefiir die Energietechnik, 28.-31.5.96, Stuttgart/Germany, pages 460-469, Frankfurt, Germany, 1996. DGM-InformationsA. Mitterdorfer and L.
gesellschaft mbH.
[27]
C. Clausen, C.
Bagger, J.
B. Bilde-Serensen, and A. Horsewell. The
importance
of
Mn-oxide for chemical reaction between
Zr02.
High Temperature torsProc. of the 14th Riso

In
Int. Mat.
La0 85Sr015MnOs of Fast Ion
and
Y203-stabilized
and Mixed Conduc
mark, 1993. Rise
Symp. on National Laboratory.

for
SOFC:
Sci., pages 237-242, Roskilde, Den
[28]
M.
J. L. Ostergard, C. Clausen, C. Bagger, and M. Mogensen. Manganite-zirconia

cathodes Influcence
of
structure
composite
[29]
and
composition.
Electrochimica Acta, 40:1971-1981,1995.
H.-J. Deiseroth and H. Muller-Buschbaum. Ein Beitrag La2Zr207. Z. anorg. allg. Chem., 375:152-156,1970.
R. P.
zur
Pyrochlorstruktur
an
[30]
Ingel
and D. Lewis, III. Lattice
Zr02. /.
[31]
Am. Ceram. Soc,
parameters and density for 69:325-332,1986.
Y203-stabilized
R. S. Roth.
Pyrochlore-type compounds containing

/.
Res. Nat. Bur., 56:17-25,1956.
double oxides of trivalent and
tetravalent ions.
[32]
A.
Mitterdorfer, M. Cantoni, and L. J. Gauckler. Interphase formation between yt

In B.
tria-stabilized zirconia and porous
temperatures.
La0 85Sr015Mn 03 during firing at intermediate Thorstensen, editor, Proceedings of the Second European Solid Ox
Switzerland, 1996. U. Bossel, Oberrohr-
ide Fuel Cell Forum, pages 373-382, Baden,
dorf, Switzerland.
[33]
D. Kuscer,
J. H. M. Hrovat, S. Bernik, Z. Samardzija, and D. Kolar. Interactions be
tween a thick film ature
LaMn03 cathode and YSZ SOFC electrolyte during high temper

a
ageing.
Solid State Ionics, 78:79-85,1995. l'etude des systemes
[34]
A. Rouanet. Contribution
au
voisinage
de la fusion. Rev, Int. Hautes
zircone-oxydes des lanthanides Temper, et Refract., 8:161-180,1971.
226
References
[35]
Brugnoni, U. Ducati, and M. Scagliotti. SOFC cathode/electrolyte interface, parti: Reactivity between La085Sr015Mn03 and ZrO2-Y203. Solid State Ionics,
C.
76:177-182,1995.
[36] [37]
H. E. Exner. Rev. Powder
Metallurg. Phys.
Chem. Ceram., 1:7,1979.
S.
Somiya
and Y.
Moriyoshi, editors. Sintering Key Papers, chapter 3,
pages 87-199.
Elsevier Science, London, 1990.
[38]
J. A. Labrincha, J. R. Frade, and F. M. B. Marques. La2Zr207 formed at ceramic electrode/YSZ contacts. /. Mat. Sci., 28:3809-3815,1993.
B. A.
van
[39]
Hassel.
bilized Zirconia. PhD thesis,
Transport and Oxygen Transfer Properties of Ion Implanted University of Twente, 1990.
Yttria Sta
[40]
Y.
Takeda, R. Kanno, M. Noda, Y. Tomida, and O. Yamamoto. Cathodic polariza
tion
phenomena
of
perovskite
oxide electrodes with stabilized zirconia.
/. Electro
chem. Soc, 134:2656-2661,1987.
[41]
K.
Tsuneyoshi,
1989. H.
K. Mori, and A. Sawata. Kinetic studies

as an
on
the reaction at the
La0 6Ca0 4Mn03/YSZ interface,
SOFC air electrode. Solid State Ionics, 35:263-
268^
[42]
J. Mizusaki,
Tagawa,
K.
Tsuneyoshi,
and A. Sawata. Reaction kinetics and
microstructure of the solid oxide fuel cells air electrode
La06Ca04MnO3/YSZ.
/. Electrochem. Soc, 138:1867-1873,1991.
[43]
A.
Hammouche, E. Siebert, A. Hammou, and M. Kleitz. Electrocatalytic properties
and
nonstoichiometry
of the
high temperature air
electrode
La1_;cSrxMn03. /.
Elec
trochem. Soc, 138:1212-1216,1991.
[44]
G.
Gharbage, T. Pagnier, and A. Hammou. Oxygen reduction at La0 5Sr0 5Mn03 thin film/yttria-stabilized zirconia interface studied by impedance spectroscopy.
J. L. 0stergard and M. Mogensen.
on
/. Electrochem. Soc, 141:2118-2121,1994.
[45]
M.
ac
impedance study of the oxygen reduction
mechanism
La1_xSrxMn03
in solid oxide fuel cells. Electrochim. Acta, 38:2015-
2020,1993.
[46]
Siebert, A. Hammouche, and M. Kleitz. Impedance spectroscopy analysis of La^Sr^MnO^yttria-stabilized zirconia electrode kinetics. Electrochim. Acta,
E.
40:1741-1753,1995.
[47]
M.
Mogensen and S. Skaarup.

Youngblood,
A. S.
Kinetic and
geometric aspects of solid oxide fuel cell
electrodes. Solid State Ionics, 86-88:1151-1160,1996.
[48]
G. E.
at a
Rupaal,
L. R.
Pederson, and J. L. Bates. Oxygen reduction
Y1_x(Ca).cMn03 or La^Sr^MnOg cathode Singhal Proceedings of the Third Interna tional Symposium on Solid Oxide Fuel Cells, pages 585-597, Pennington, NJ, 1993. PV 93-4, The Electrochemical Society, Inc.
materials. In S. C.
and H. Iwahara, editors,
stabilized zirconia interface with
227
La2Zr207 Formation and 02 Reduction Kinetics
[49]
F. H.
van
Heuveln and H. J. M. Bouwmeester. Electrode
LaMn03
[50]
on
1997. to be
yttria published.
stabilized zirconia. Part II: Electrode kinetics.
properties of Sr-doped /. Electrochem. Soc,
J. Mizusaki, K. Amano, S. Yamauchi, and K. Fueki. Electrode reaction
at
Pt,
02(g)/stabilized
[51]
M. Che and A.
zirconia interfaces. Part I: theoretical consideration of reaction
species [52]
F. H.
on
J. Tench. Characterization and reactivity of mononuclear oxygen oxide surfaces. Adv. Catal, 31:77-133,1983.
van
van
Heuveln, H. J. M. Bouwmeester, and F. P. F.
erties of Sr-doped
LaMn03 on yttria
R.
stabilized zirconia. Part I:
Berkel. Electrode prop Three-phase bound
ary
area.
/. Electrochem. Soc, 1997.
to be
published.
current collectors.
[53]
K. S.
J.-P. Wurth,
Gschwend, M. Godickemeier, and L. J. Gauckler. Microstruc-
ture-property relations of solid oxide fuel cell cathodes and /. Electrochem. Soc, 143:530-543,1996.
[54]
Fukunaga, M. Ihara, K. Sakai, and K. Yamada. The relationship between overpotential and the three pahse boundary length. Solid State Ionics, 86-88:1179-1185,
H.
1996.
[55]
Wang and A. S. Nowick. Cathodic and anodic polarization phenomena at platinum electrdoes with doped Ce02 as electrolyte: I. steady-state overpotential.
/. Electrochem. Soc, 126:1155-1165,1979.
1987.
D. Y.
[56]
[57]
N. L. Robertson and
tem. Part II:
[58]
J. Gauckler. Theoretical analysis of the Pt, 02(g) I YSZ sys Implementation, simulation, and validation. J. Electrochem. Soc, sub
mitted.
[59]
F.
Berthier, J.-P. Diard, B. Le Gorrec, and C. Montella. Method for
determining
the
faradaic
impedance
of
an
electrode reaction:
Application
measurements.
Corros., 51:105-115,1995.
[60]
B. A.
van
Hassel, B. A. Boukamp, and A. J.
Burggraaf.
Electrode
polarization at the
Au,
02(g)/yttria
stabilized zirconia interface: Part I: Theoretical considerations of
reaction model. Solid State
Ionics, 48:139-154,1991.
[61]
G. O. Lauvstad, S. Sunde, and R. Tunold. Oxidation of CO
Measurement and
modelling impedance. of the 17th Ris0 Int. Roskilde, Denmark, 1996. Rise National Laboratory.
In
of
Ceramic and MetalsProc.
Ni-point electrodes: High Temperature Electrochemistry: Symp. on Mat. Sci., pages 339-344,
on
[62]
J. Divisek, J. W. Erning, R. Jung,
B.
Steffen, U. Summing, and K. Wippermann. The

SOFC cathodes. In
kinetics of the oxygen reduction
on
High Temperature
Electro-
228
References
chemistry:
[63]
Ceramic and MetalsProc.
229-234, Roskilde, Denmark, 1996.
Symp. Rise National Laboratory.
of the
17th Ris0 Int.
on
Mat. Sci., pages
C. Gabrielli and B. Tribollet. A transfer function
approach
for
generalized
elec
trochemical
Electrochem. Soc, 141:1147,1994.
[64]
tem. Part I:
J. Gauckler. Theoretical analysis of the Pt, 02(g) I YSZ sys General framework, modelling, and structural investigation. /. Electro
[65]
M. Kleitz. Electrode and interface reactions in solid-state cells. Solid State
Ionics,
3/4:513-523,1981.
[66]
M.
J. Verkerk, M. W. J. Hammink, and A. J. Burggraaf. Oxygen transfer
on
substi
tuted
ance
Zr02, Bi203, and Ce02 electrolytes with platinum study. /. Electrochem. Soc, 130:78-84,1983.
electrodes. II. AC
imped
[67]
F. K.
Moghadam
using
and D. A. Stevenson.
AC
Oxygen
diffusion and
solubility
studies in
Ag [68]
M.
and Pt
Electrochem. Soc, 133:1329-1332,
1986.
J. Verkerk,
M. W.
J. Hammink, and A. J. Burggraaf. Oxygen transfer
on
substi
re
ZrOz, Bi203, and Ce02 electrolytes with platinum electrodes. sistance by DC polarization. /. Electrochem. Soc, 130:70-78,1983.
tuted
I. electrode
[69]
H. Gerischer.
Wechselstrompolarisation
von
Elektroden mit einem

Z.
potentialbes-
timmenden Schritt beim

1951.
Gleichgewichtspotential.
S. Yamauchi,
and
phys. Chem., 158:286-313,

Electrode
reaction
at
[70]
J. Mizusaki,
Pt,
K. Amano,
K. Fueki.
02(g)/stabilized
zirconia interfaces. Part II: electrochemical measurements and
analysis.
[71]

sur
J. L. Gland, B. A. Sexton, and G. B. Fisher. Oxygen interactions with the Pt(lll) face. Surf. Sci., 95:587-602,1980. J. K. Norskov. Why gold 376:238-240,1995.
B. Hammer and A. Bielanski and
is the noblest of all the metals.
[72]
Nature,
[73]
J. Haber, editors. Oxygen in Catalysis. Marcel Dekker, Inc., New
York, 1991.
[74]
B. C. H.
Steele, J. A. Kilner, P. F. Dennis, and A. E. McHale. Oxygen surface
ex
change
1986.
and diffusion in fast ionic conductors. Solid State Ionics, 18&19:1038-1044,
[75]
A.
Weber, R. Manner, B. Jobst, H. Cerva, R. Waser, and E. Ivers-Tiffee. The influ

of A-site-deficiency
on
ence
the
performance of strontium doped lanthanum-man-
In F. W. Poulsen, N. Bonanos, perovskite type S. Lindenroth, M. Mogensen, and B. Zachau-Christiansen, editors, High Tempera ture Electrochemistry: Ceramic and MetalsProc. of the 17th Rise Int. Symp. on Mat.
ganite
SOFC-cathodes.
Sci., pages 473-478, Roskilde, Denmark, 1996. Rise National
Laboratory.
229
La2Zr207
Formation
and
02
Reduction Kinetics
230
Part
IV
End Matter
232
Chapter
Outlook
5.1
General
(SSID) have found application in a large number of the future, solid oxide fuel cells (SOFC) are believed to
for
a
Solid State Ionics Devices different

offer
an areas.
For
produc tion. However, at the present time SOFC technology development and in initial system prototype demonstration state. This is, to our opinion, due to the history of development: a large number of experimental studies have been performed, but most of them were related with the optimization of materials or processing routes, and materials characterization. Considerably less basic studies have been performed, and accordingly, still relatively little is known about the electrode reaction mechanisms, the factors responsible for electiode degradation, and how the electrochemical behaviour depends on the processing steps. This thesis has been concerned with the latter type of questions. Following, a summary of conclusions and some ideas for further
opportunity
more
cleaner and
efficient way of energy

is still in
work in this
area.
Outlook
5.2
Identification of Reaction Mechanisms

just
as an
The identification of reaction mechanisms is from intuition,
art as
science.
a
Apart
persistence,
and luck
we
found that
following
certain route
may
help finding
the solution faster. We would
give
the novice the
following
advice:
(i)
Collect
tem
as
much information any
as
possible
related with the sys
before
experimental
can
work is carried out. Note that
much information
is not
often be found in the literature which
directly related with SOFCs or SSIDs. Try to understand what people have done before and realize the essence. This might be difficult at the beginning, but ask people.
(ii)
Do not hesitate to translate your ideas into models.
ment your
Imple
ideas into the computer and the models of others

as a
run
simulations.
Re-implement
the behaviour of the models
starting point. Study by simulation. Play!
(iii) Start modelling seriously. Define what your models should

account for and what is
beyond.
Collect the
priori
known
qualitative understanding from the overall process and recognize the relevant elementary steps. Translate your qualitative models into a quantitative models.
a
information. Obtain
Transform the structural
quantitative
models into
form suitable for
investigation
and
computer
implementation.
Obtain
Implement
the models into the computer.

structure of the models.
(iv) Investigate the
steady-state and iour, as well as the behaviour under limiting conditions, such as high overpotentials, low oxygen partial pressures, and low or high temperatures. Compare your results with those reported in the literature. From simulations, further relation
expressions describing
the
analytical dynamic behav
ships
may become apparent. Use simulations also in order to
check your
analytical
results
(and the implementation). Is the
model structure in
agreement with the reported data? If not,
why?
234
5.3
Modelling
and
Simulation
(v)
Design
from
your
experiments according
to
the
information
in the models
or
obtained above. Estimate unknown
parameters
experimental
(iv)
data. Validate your results. Refine
reject
the models. Note that steps

iment needs
(i)
to
consume
most of the time available. The ideal exper
no
more
thoughts mentioned
single sample. more closely.

than
a
Let
us
consider
some
of the
5.3
Modelling
and model
an
and Simulation
Modelling learning
difficult steps for that the method
implementation are probably considered as the most experimentalist. However, the pain necessary when
can
these tasks is worth the results which
be obtained. We believe
developed
in this thesis
can
be
applied
without
an
extraordi
nary mathematical
Although
cation
as
the
background. method of digital supposed

in the
simulation of electrochemical systems for this
was
introduced
it
more was
than 30 years ago, the method has not found its wide
The
reason
appli
might lie in early days. the fact that considerable programming skills of a low level programming language have been necessary (e.g. Fortran). This has changed these days. The programming environment of Matlab and Simulink offers a high level programming environment which requires only moderate programming knowledge, as every chemist or materials scientist should possess. This ena
bles to focus model
reuse a on
the actual the
equations,
problems. The straightforward implementation extendability of the Simulink models, the possibility
of
to
programming blocks,
can
and the numerical environment of Matlab, make
strong tool. The complete process of modelling, simulation, and parameter

be
estimation
accomplished
the process
within
presented. However,
gation.
simulation must be considered
as
single environment, as we have of modelling, structural investigation, and the first (and mandatory) step of an investi
one
235
Outlook
5.4
Materials and
Samples
(or badly known) parameters
are
Sintered, porous electrodes have been widely employed for kinetic studies.
However,
a
number of unknown
intro
duced in this way. First, the microstructure, i.e. the
length
of the
triple phase
accu
boundary (tpb)
and the
porosity,
can
not be determined with reasonable
quantitative parameter estimation difficult, as we have shown. Second, during sintering a number of undesired processes may occur. It is therefore very important to monitor every single step in sample fabrica
racy. This makes
tion. If
not
one
is not interested in these reactions,
they
must be avoided which is
always possible. Third, even if a large number prepared, their polarization resistance will hardly
two. This is due to the factors mentioned above.
of "identical"
scatter below
samples
a
is
factor of
To circumvent these
most
problems,
a
number of routes have been

cone
proposed.
The
popular
of them is the
use
of
shaped
or
wire electrodes. However,

a
it is doubtful whether
perfect
contact is obtained with
defined
length
of
employ electiodes with simple geometries, i.e. pattern electrodes. This should work without larger problems for metal electrodes which can be sputtered and subsequently etched. The length of the tpb is determined to high accuracy and the influence of porosity (gas phase diffu
the
tpb.
We propose to
sion) rules
the
out.
However,
one
must be
aware
of the limitations of this type of

is limited to
electrode. First, the electrochemical
investigation
potentials
near
equilibrium potential, because of the relatively high electronic resistance of the thin metal stiips. Second, the temperatures of investigation must be somewhat low, in order to avoid a drastic microstructural change of the metal
pattern. However, the
use
of
one or
another type of electiode is determined
by the kind of information one is seeking for. Starting with simpler geometries is good advice. In addition, use single crystal material if ever available and use high quality materials with well known levels of impuri ties. Always check powders for composition.
5.5
Once
Electrochemical
one
Investigation Techniques
understanding of the materials and their interactions during preparation and operation, electrochemical measurements should be attempted. There has been much praise for electrochemical impedance spec
has
a
sound
troscopy (EIS)
as
the tool for identification of electrode reaction mechanism.
236
5.5
Electrochemical Investigation Techniques
However, there has been made

oretical basis of EIS is not
no
significant
reason
progress in the
investigation
of
SSID electrodes. We believe that the
for this lies in the fact that the the
experimentalists. Therefore, it is generally concluded that the interpretation of experimental data is difficult. Furthermore, fitting data to equivalent electrical circuits does not help to understand the physical processes involved in the electrode reac sufficiently
understood
by
the
tion mechanism. In order to make

use
of the powers of EIS, micro-kinetic models of the
assumed electrode reaction mechanism must be actual
employed.
data,
not
In addition, the have shown. the system
system response
one
must be
extracted from
raw
as we
Any
further
interpretation
and
modelling
aware
must be based
can
on
give answers to any question, and that even conventional steady-state current-voltage investiga tions may give some useful and complementary (and possibly accurate) information. But, be aware of the requirements necessary for a successful application of this method. We propose to consider always a number of dif ferent experimental techniques. Certainly, the choice depends on the preced ing theoretical analysis.
response. However,
should be
that EIS
237
Outlook
238
Curriculum Vitae
Personal
Date and Place of Birth: Marital Status:
February 19,1966, in Winterthur,

Married with Denise Swiss
Switzerland
Nationality:
Education
4/82-2/86:
3/1986:
Kantonsschule Aarau
7/86-10/88:
Typus E Military Services

Matura
11/88-10/92:
11/92-2/93:
Student of Materials Science, Swiss Federal Insti
Technology, Abt. Ill D, ETH Zurich Diploma thesis with Prof. Dr. Urs P. Wild, Institute of Physical Chemistry, Department of Chemistry; Topic: "EinzelmolekulspektroskopiePentacen in para-Terphenyl"
tute of
3/93:
Diploma
in Materials Science
6/93-10/93:
Research associate, Chair of Nonmetallic Materi
als, Department of Materials Science,

ETH Zurich
11/93-10/97:
PhD thesis with Prof. Dr. L.
J. Gauckler, Head of
the Chair of Nonmetallic Materials,

of Materials Science, ETH Zurich
Department
Curriculum Vitae
Publications
[I]
J. Gauckler. State space modelling of metal electrodes

In U.
in
solid state
W.
electrochemistry.
Stimming,
S. C.
Singhal,
H.
Tagawa,
and
Lehnert, editors, Proceedings of the Fifth International Symposium on Solid Oxide Fuel Cells (SOFC-V), pages 421-430, Pennington, NJ, 1997. PV 97-40, The Electro
chemical
Society,
Inc.
[2]
J. Gauckler. La2Zr207 Formation Between Yttria-Stabilized Zirconia and Lag ^Stq 15Mn03 at 1373 K. In A. Jacobsen, P. Davies, and T. V. and
A. Mitterdorfer and L. C. Toradi, editors, Solid State
burgh, PA,
[3]
terface.
B.
1997. Materials
Chemistry of Inorganic Materials, Research Society.
volume 453, Pitts
In
F. W.
J. Gauckler. Oxygen reduction at the La0 85Sr015Mno 9803 in Poulsen, N. Bonanos, S. Lindenroth, M. Mogensen, and
Zachau-Christiansen, editors, High Temperature Electrochemistry: Ceramic and MetalsProc. of the 17th Ris0 Int. Symp. on Mat. Sci., pages 357-362, Roskilde, Den mark, 1996. Rise National Laboratory.
[4]
J. Gauckler. LSM-Kathoden fur Festelektrolyt-Brennstoffzellen. In Werkstoffwoche '96, Symposium3: WerkstoffefiirdieEnergietechnik, 28A. Mitterdorfer
and
L.
Stuttgart/Germany, mationsgesellschaft mbH.

31.5.96,
pages 460-469, Frankfurt,
Germany,
1996. DGM-Infor-
[5]
A.
Mitterdorfer, M. Cantoni, and L. J. Gauckler. Interphase formation between yt
tria-stabilized zirconia and porous
temperatures. In B. Oxide Fuel Cell Forum, pages 373-382, Baden, Switzerland, hrdorf, Switzerland.
La0 85Sr015Mny03 during firing at intermediate Thorstensen, editor, Proceedings of the Second European Solid
1996. U.
Bossel, Oberro-
[6]
J. Gauckler. La2Zr207 formation and oxygen reduction

I YSZ
kinetics in
La0 85Sr015Mny03, 02(g)
systems. Solid State Ionics, submitted.
[7]
tem. Part I:
J. Gauckler. Theoretical analysis of the Pt, 02(g) I YSZ sys framework, modelling, and structural investigation. /. Electro general
[8]
tem. Part II:
J. Gauckler. Theoretical analysis of the Pt, 02(g) I YSZ sys implementation, simulation, and validation. /. Electrochem. Soc, sub
mitted.
[9]
tem: state and
J. Gauckler.
Reaction kinetics of the Pt,
02(g) I c-ZrOz
sys
tional
parameter estimation. To appear in Proceedings of the Conference on Solid State Ionics, Hawaii, 1997.
K.
11th Interna
[10]
L.
J.
Gauckler,
Sasaki,
A.
Mitterdorfer,
In
M.
Godickemeier,
and
P. Bohac.
"Processing of SOFC ceramic components."

[II]
K.
Proceedings of the First European
Solid
Oxide Fuel Cell Forum, pages 545-566, Baden, Switzerland, 1994. U. Bossel.
Sasaki, J. P. Wurth, M. Godickemeier, A. Mitterdorfer, and L. J. Gauckler.
"Processing-microstructure-property relations of solid oxide fuel cell cathodes." In S. C. Singhal and H. Iwahara, editors, Proceedings of the fourth International Sym-
240
Presentations
posium
[12]
K.
on
Solid Oxide Fuel Cells, page 625,
Pennington, NJ,
1995. PV 95-1, The Elec
trochemical
Society,
Inc.
Sasaki, J. P. Wurth, M. Godickemeier, A. Mitterdorfer, and L. J. Gauckler.
"Processing-microstructure-property relations of solid oxide fuel cell cathodes." In Proceedings of the First European Solid Oxide Fuel Cell Forum, pages 475-492,
Baden, Switzerland, 1994. U. Bossel.
Presentations
[13]
11th International Conference
on
Solid State Ionics, Honolulu, Hawaii/USA, 16-21
November 1997. (Oral Presentation).
[14]
5th International
Symposium
on
Solid Oxide Fuel Cells,
Aachen/Germany,
(Oral Presentation).
2-6
June 1997. (Poster Presentation).
[15]
[16]
MRS Fall
Meeting 1996, Boston/USA,

Symposium
2-5 December 1996.

on
17th Riso International
Materials
ScienceHigh Temperature
Electrochemistry:
Presentation).
Ceramic and Metals,
Riso/Denmark, 2-6 September 1996. (Oral
[17]
[18]
Werkstoffwoche '96, Second
Stuttgart/Germany,
28-31
June
1996.
(Poster Presentation).
6-10
European
Solid Oxide Fuel Cell Forum,
Oslo/Norway,
May
1996.
(Oral Presentation).
241
Curriculum Vitae
242

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Diss.

at Cathodes of Solid Oxide Fuel Cells

A dissertation submitted to the

SWISS FEDERAL INSTITUTE OF TECHNOLOGY

Doctor of Technical Sciences

Dipl. Werkstoff-Ing. ETH born on February 19,1966 citizen of Wiesendangen, ZH

Diss. ETH No 12380

at Cathodes of Solid Oxide Fuel Cells

A dissertation submitted to the SWISS FEDERAL INSTITUTE OF TECHNOLOGY

Doctor of Technical Sciences

Dipl. Werkstoff-Ing. ETH born on February 19,1966 citizen of Wiesendangen, ZH

Prof. Dr. L.J. Gauckler, examiner

Date of oral examination: October 3,1997, 3 p.m.

FrameMaker 5.1 The illustrations

SPARCstations from Sun done

2.5. The Palatino font

is used for the main

A Portable Document Format

my advisor, Prof. Dr. L.J. Gauckler,

head of the chair of Nonmetallic Materials, for his

encouragement and sup

port, and for his willingness

much of the advance of the

I wish to thank him for the

my results at international conferences all well

co-examiner of this thesis

Prof. Dr. D. Bonnell, of the

valuable comments, and

reading most parts improving the language.

lic Materials: Dr. Martin Godickemeier and

further indebted to many

technical assistance, his PC cult times;

support, and his encouragement during the diffi

Bengt Hallstedt for sharing

of UNIX network management

and Frank Filser for

taking this job

members of the Swiss Federal Institute of

I wish to thank my wife Denise and her

support of the project.

Solid State Ionics Electrochemical Devices

1.1.3 1.2 1.3

Origin of Potential Differences Oxygen Reduction

Aim of the Thesis

Structure of the Thesis

General 2.1 2.2

Framework, Modelling, and Structural Investigation

General Considerations and

Properties of the Models Qualitative Analysis of Frequency Response

Computer Implementation, Simulation,

3.2.3 Surface Mass 3.3

Model Initialization and

3.3.3 3.3.4 3.4

Depth and tpb Width Double Layer Capacitance

Cd\ by Potential Step

Chronoamperometry Implementation and Simulations Implementation and Simulations

The Interface between

Lao 85Sr015MnyO3+s and

Lanthanum Zirconate Formation and

and-Chemistry Properties Aims of the Study

161 163 165 166

4.1.3 Influence 4.1.4