ETH No 12380
Identification of the
Oxygen
Reduction
for the
degree
of
presented by
Andreas Mitterdorfer
accepted
on
the recommendation of
examiner
Prof. Dr.
Dr. B.
L.J. Gauckler,
Elsener, coexaminer
1997
Identification of the
Oxygen
Reduction
ZURICH
for the
degree
of
presented by
Andreas Mitterdorfer
accepted on the
Dr. B.
recommendation of
Elsener, coexaminer
1997
written in:
on
Microsystems.
and
were
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mitterdorfer.html
electronic mail:
mitterdorfer@nonmet.mat.ethz.ch
Acknowledgments
I wish to express my
deep gratitude
to
to entrust
so
project nity
to
to
my
judgement.
In
particular,
present
as
the world.
I wish to thank Dr. B. Elsener from the Institute of Corrosion Science for
acting
giving
as
as
on
Sabbat
ical from
Pennsylvania University,
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 statespace 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
job
from
me.
I also wish to thank the members of Sulzer Innotec in Winterthur and the
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
November,
1997
Andreas Mitterdorfer
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
1.1.2 The
12 13
References
Part
2
II
Theoretical
Analysis
of the Pt,
Oz(g)
I YSZ
System
19
Introduction
20
24
General Framework
2.2.1 2.2.2
The Process of
Modelling Hypotheses
24
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
56 60 61 66
Conclusions
References
Appendix
2A.l
2A.2
3
Space Description of an Electrical Circuit Calculation of tpb length from microstructural data
and Validation
State
...
66 68
71
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
Simulation Procedures
3.3.1 3.3.2
Sensitivity
81 82 86
The
Digital
Aspects
91
Simulation Results
92 92
.
3.5
ChargeTransfer 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
3A.l
3A.2
136
Determination of
3A.3
3A.4
of Model Ml of Model M2
139 148
VI
Part
III
YttriaStabilized Zirconia
4
Introduction
4.1.1
160
General
160
4.1.2 Microstructure
on
Electrochemical
4.2.2
4.2.3 4.3
168
169 170
....
Results
4.3.1 4.3.2 4.3.3
4.4
Oxygen
Reduction Kinetics at
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
Modelling
and Simulation
Materials and
236
239
Curriculum Vitae
vii
viii
List
of
Figures
Chapter 1
1.1
Schematics of
an
ionic
7
conductor in contact
1.2
electrolyte surface
at
1.3
10
Chapter 2
2.1
Schematic view of the oxygen reduction process at interfaces between noble metals and solid oxide
ionconducting electrolytes
2.2
25
Secondary
Pt
on a
Electron
(001) YSZ
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
the tpb
2.6
Schematics of
porous Pt electrodes
2.7
Twocompartment model
for structural
investigation
53
in the
of reaction mechanism M2
2.8
complex plane
2.9
57
in
representation
58
2.10
2A1.1
Frequency
responses of Ml in Bode
representation
59 66
RC electrical circuit
2A2.1
Simplified morphology
interface
of noble
metal/electrolyte
68
Chapter 3
3.1
Simplified
78 83
3.2
Temperature dependence
Electrical
of 0)max for
3.3
3.4
fitting experimental
EIS data
89
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
Steadystate /f(tj)
Deviation of Simulated
behaviour of Model M2 at T
/F(r)
/f(t))
analysis
i0 values
Comparison
atr
=
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
ZF(j(o)
from simulated
noisy Z(jco)
data
108 109
3.16
function of
temperature
Ill
partial
pressure
3.17
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
/F(r) relationships
118 120
Simulated cathodic
limitingcurrent behaviour
=
of M2
Simulated
973 K
(700C)
at
121
=
3.23
123
3.24
IZFI
IZFI
with
respect
to the unknown
parameters
3.25
124 with
Sensitivity
of
respect
area
to the
3.27
3.28
Correlation between
and
klc
Sensitivity
of
IZFI
129
3A2.1
responses of
equivalent
139
3A3.1
Simulink block
diagram
for the
adsorption/desorption
140
....
dynamics
3A3.2
3A3.3
141
Simulink block
diagram of Ml
in order to extract
143
3A4.1
diagram diagram
compartment of
M2
....
152
3A4.2
3A4.3
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
of LSM
cathode
layers
171
on
4.3
profile
of
Larich surface
layer
173
4.4
images
(001)
a
174
4.5
AFM of
layer covering a
YSZ
176
single crystal
4.6
AFM
with
4.7
images of a (001) YSZ single crystal surface covered cubeshaped islands of lanthanum zirconate
178
growth kinetics
at 1373 K between
LSMq 98
180 182 183
Bright
on
(001)
YSZ surface
after
sintering with
184
4.11
AFM
image
longterm
186 187
4.12 4.13
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
of electrode
194
4.18
of the electrochemical
195
xii
4.19
interface
199
LSMq 95
and YSZ
4.20
growth
growth
at
LSMq 98 LSMj 02
and YSZ
at
202
4.21
and YSZ
205
4.22
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
Table 4.1
Characteristics of the
used in this
screenprinting pastes
167
study
Leer
Vide
Empty
xvi
Summary
The
high temperature
electronically conducting
cathode materials
number of
cathode network,
adsorption of oxygen
Steadystate currentvoltage
are
impedance spectroscopy
chemical
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
application of this
A method is
developed
for
dealing
performing
mathematical and
analysis
of the
equations,
implementation, steadystate
dynamic simulations,
a
and parame
ter estimation
single
framework. The
from
models
are
described
is considered
as
investigated
identifiability
of unknown parameters.
Oxygen adsorp
tion
on
threephase 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
be estimated from
impedance spectroscopy
can
working
demonstrated
be well
applied
to other
metal electrode/solid
electrolyte systems.
La0 8sSr015Mn03, 02(g) I Zr02 system
are
microstructural and
characterizations.
formation
of
the
foreign phase
means
La2Zr207
at the
cathode/electrolyte
interface is
investigated by
of
high
microscopy
perovskite
Asite
growth
rate of
La2Zr207.
deficiency
La2Zr207
properties
of
strongly
influenced
by La2Zr207
islands at the
threephase
cal
impedance investigations.
xviii
ZUSAMMENFASSUNG
Die
HochtemperaturReduktion Festelektrolyten
von
Sauerstoff
an
Grenzflachen zwischen
oxidischen
aus
verschiedenen Teilschritten
dem
Transport
von
gasformi
gen Sauerstoff im
Porensystem
Grenzflachenreaktionen.
Statische
zu
StromSpannungsMessungen
am
und
Impedanzmessungen
mischen
ten
zahlen
den
Untersuchungsmethoden.
Kathoden verbessern
Um die elektrochemischen
zu
Eigenschafder
von
konnen,
ist
die
Kenntnis
notwendig.
tifikation
allgemeine Methode
zur
Iden
von
Reaktionsmechanismen
heterogener
Elektrodenreaktionen
Anwendung
Systeme
zu
demonstrieren.
zur
Behandlung
von
mikrokinetischen Modellen
ermoglicht
die mathematische
Behandlung
der
statischen und
dynamischen Verhalten,
sowie ParameterSchatzun
gen mit ein und demselben Formalismus. Die Modelle werden dabei mittels
woraus
die Ubertra
Als wird
ModellSystem
02(g) I cZr02System
von
betrachtet. Dieses
beziiglich
der Identifizierbarkeit
Sauerstoffadsorption
elektrochemische Reduktion
von
adsorbiertem Sauerstoff
der
Dreiphasengrenze miteinbezogen.
Es wird
aus
gezeigt,
einer
Kombination
mathematischer
Behandlung,
elektrochemischen
Messungen
und numerischer
vom
Bedeckungsgrad abhangige
aus
elektrochemischen
Impedanzmes
vorgestellte
Grenzflachen zwischen
und elektrochemi
an
La0 85Sr015Mn03
und
cZr02
wird mit
mikroskopischen
der
Bildung
Fremdphase La2Zr207
der Grenzflache zwischen der porosen Kathode und dem wird mittels hochauflosender
Festelektrolyten
und
TransmissionsElektronenmikroskopie
Der
Atomkraftmikroskopie
beeinflusst
untersucht.
ManganGehalt
auch die
vom
Perowskit der
sowohl
den
Zeitpunkt
als
Geschwindigkeit
La2Zr207Bildung.
werden durch
Die elektrochemischen
an
Eigenschaften
der Grenzflache
betrachtlich
von
ver
La2Zr207Inseln
der
Dreiphasengrenze
die Dissoziation
schlechtert. Der
LadungstransferSchritt,
adsorbierten
atomarem
molekularen Sauerstoffionen und die Oberflachendiffusion Sauerstoff werden als relevante Reaktionsschritte bestimmt.
aus
von
Impedanzmessungen
xx
Parti
Front Matter
Chapter
Introduction
Abstract
operating principles
and
into
of solid
ionics
electrochemical devices
electrochemical
(SOFC),
presented.
that
is
Some
occur
emphasis
at
is
processes
materials
"overpotential"
explained.
knowledge
given.
It
are
given.
scopic
and
in this thesis.
1.1
1.1.1
Background
Solid State Ionics Electrochemical Devices
ducting electrodes which are separated by a gas Y203stabilized Zr02 (YSZ) has been employed by far conducting electrolyte
for its
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], 8Bi203 [3], or per
Introduction
have been
investigated
for
use as
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
and references
therein).
A pro
found review
can
on
technology
(SOFC)
[7,8].
currentproducing 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
the anode,
respectively,
is
F is the
Faraday
at
sidered.
reduced
the solid
the
io2(g)
where
2e
O2electrolyte,
and
e
(1.2)
O
2_
denotes
occupied
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 nonohmic). The understanding of these interfacial resistances has been a driving force for
currentproducing
electrochemical device, i.e. the science of electrochemical kinetics.
By contrast,
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
(see Chapters
8 and 9 of
[9]
as a
starting point,
as
well
as
Refs
[1014]).
1.1.2
The
Origin
a
of Potential Differences
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
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
measure
an
the
an
interface
.
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
by
not
an
electrical current.
that
are no
equilibrium does
mean
flow of
properties
one
can
type of interface
of
Eeq,
quantity i0
can
not be
directly
and
different
possibilities
a
to determine
i0,
some
methods
(and
its
limitations)
will be discussed.
We
can
obtain
net current
density
if
magnitude
i
=
ifib.
potential
(13)
It is easy to
see
that this
implies
=
difference must
depart
Let
us
from
Eeq.
potential
and
as
introduced above.
briefly consider a platinum oxygen electrode to understand the physi cal significance of overpotentials (Fig. 1.1). The halfcell reaction is written as
02(P)02,Pt(oc)
where the notations determined
(1.4)
in
by the
Fig.
1.1. The
potential
is
^02
because the electrons
are
2e"^02",
(1.5)
only chargecarriers 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
migrate
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)
phase
must
pass with
number of
steps until
it arrives
as
atomic oxygen
near
the
tpb.
Because every
elementary
reaction
proceeds
finite rate,
species
Pt
e~
Pore
<
o2(g)
O(ad)
YSZ
02"(P)
O(p)
2e"
Fig.
a
1.1
Schematics of
an
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
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
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)
tpb
it must be electroan
incorporated into
the solid
electrolyte. Certainly,
an
incorporate
oxygen ion
act
on
the
The term
chargetransfer
differ
phenomena.
ence
It is
readily
seen
that
applied potential
gen
species
negatively charged.
1.1.3
Oxygen
shows The
a
Reduction
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
good
electronic conduc
conditions.
as
high temperatures
or
oxidizing
Pt, Au,
or
Ag,
Srdoped LaMn03
Eq. (1.2).
of them
LaCo03,
The overall reaction of the oxygen reduction at SOFC cathodes is This reaction is made up of
a
given by
occur on
elementary reactions, some the surface of the cathodes, others take place near the inter cathode and the electrolyte, i. e. at the triplephase bound
Which processes in detail
occur
couple
of
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)
Charge
atomic oxygen
species
near
and the
1.1
Background
fined to the
vicinity
of the
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
probable
than
single twoelectron transfer step. In relatively little known about the actual
species.
either of two processes:
charge
supplied by
of
atomic
adsorption
or
and
subsequent
surface
diffusion
oxygen.
Note
that
the
are
chargetransfer
supply
of atomic oxygen
Fig.
was
1.2
electrolyte surface.Secondary
cathode
on
Electron
Micrograph (SEM)
gen
La0 8sSr015Mn03
and
YSZ
polycrystal.
The cathode
in air.
subsequent sintering applied by screenprinting molecules may diffuse through the porous network
i.e. are
at 1373 K
(1100C)
Oxy
towards the
triple phase
and the gas
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 Srdoped 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 Srdoped LaMn03 cathodes, the supply rate of adsorption/dissociation is too low to account for the rela tively high currentdensities 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)
on
(3)
the
tion process
be
accompanied by
(5)
an
be followed
are
adsorp by an
is
(4)
Atomic oxygen
species
considered to
diffuse
along
The final
charge
transfer and
incorporation step
are
believed to take
YSZ and
place
at the
tpb,
where
Oq
denotes
occupied
on
believed to be of
comparable
relevance.
10
1.2
Aim
of the
Thesis
on
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
Obviously,
gen
important,
such
as
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
There
are
are
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
1.2
heterogeneous
cation
on
the
on
one
steps, and
quantitative
estimation of
(electro)
kinetic
parameters.
*)
corresponding
statement in
(i).
11
Introduction
The
followed:
development of a general framework for modelling, struc tural investigation, and implementation of reaction mecha
nisms;
(ii)
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
anisms.
1.3
an
introductory chapter
our
chapter.
we
In the outlook
some
we
give
concise summary of
sions and
give
part
consists of three
or
publication
in the
present form
with
an
in
They
an
are
organized
an
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
developed.
are
"statespace modelling"
a
explained.
of
a
are
exemplified by
thorough
treatment
kinetic model
describing
the
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.
Stepbystep
instructions
given
appendix.
are
Simula fre
steadystate currentvoltage
behaviour
are
smallsignal
quency
dependent
to
respect
reported experimental
procedure
identification of unknown
parameters
proposed.
Chapter 4.
YSZ
La0.8sSr015Mny03
a
cathodes and
tech
single crystal
and
surfaces is
investigated by
number of
microscopic
is
niques
La0 85Sr015Mny03
investigated
at the inter
La2Zr207
properties
steps
discriminated.
References
[1]
B. C. E. Steele.
Oxygen
ion conductors. In T.
Singapore,
[2]
M. Godickemeier. Mixed Ionic Electronic Conductors for Solid Oxide Fuel Cells. PhD
1996.
[3]
University
[4]
Matsuda, and Y. Takita. Doped PrMn03 perovskite oxide temperature operation. /. Electrochem. Soc, 142:15191524,1995.
as a new
T. Ishihara, T. Kudo, H.
[5]
Oxygen
Proceedings,
[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. 9524, The Elec
[7] [8]
N.
Technology of Ceramic
Science B. V.,
13
Introduction
[9]
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
[12]
[13]
by frequency
response
1984.
analysis.
[14]
1987.
Technical
Report 004/83,
Solartron Instruments,
Farnborough,
New
York,
[15]
R. N. Blumenthal. Electronic
polariza
/. Electro
phenomena
of
perovskite
[17]
M. Kleitz, T.
moxed ConductorsProc
High Temperature Electrochemical Behaviour of Fast Ion and Miof the 14th Ris0 Int. Symp. on Mat. Set, pages 89116, 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,
[20]
J. Mizusaki,
K. Amano, S.
Yamauchi, and K. Fueki. Response and electrode reac sensor. In T. Seiyama, K. Fueki, J. Shiokawa, and
Symposia Se
[21]
F. H.
van
van
erties of Srdoped
ary
area.
LaMn03 on yttria stabilized zirconia. Part I: Threephase bound /. Electrochem. Soc, 1997. to be published.
[22]
J. Mizusaki, K. Amano, S. Yamauchi, and K. Fueki. Electrode reaction and re Soc. Jpn, 6:11601166, 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, 8688:11791185,
H. 1996.
14
References
[24]
J.
L.
Gland, B.
face.
Surf.
Sexton, and G. B. Fisher. Oxygen interactions with the Pt(l 11) Sci., 95:587602,1980.
A.
sur
[25]
B. Hammer and
J.
K. Norskov.
Why gold
376:238240,1995.
[26]
K. Fueki. Studies
by
the
complex impedance
A.
3/4:531535,1981.
[27]
M.
J. Verkerk, M.
W.
J. Hammink, and
on
substi
re
tuted
sistance
Zr02, Bi203, and Ce02 electrolytes with platinum electrodes. by DC polarization. /. Electrochem. Soc, 130:7077,1983.
K. Amano,
I. electrode
[28]
J. Mizusaki,
Pt,
S.
Yamauchi,
and
K. Fueki.
Electrode
reaction
at
Oz(g)/stabilized
[29]
J. Mizusaki, H. Tagawa,
K.
Tsuneyoshi,
Lao6Ca04Mn03/YSZ.
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 yttriastabilized zirconia solid electrolytes. Dissociative adsorp
This
tion of oxygen
on
the
a
platinum surface,
surface diffusion of
near
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 finitedifference
incorporates
surface diffusion.
mass
approach
is used for
modelling
trans
are
the time
dependent
*)
Submitted to
/. Electrochem. Soc.
and
Structural Investigation
equations
are
are
investigation
of the
resulting
is well
set of
equations
con some
performed
on
the
corresponding
accepted
in
the
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;
2.1
Introduction
play
an
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 microkinetics 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
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) steadystate currentvoltage investigations [412] and (ii) electrochemical impedance spectroscopy (EIS) investigations [11,1318]. In addition, there are reports of transientsignal (small and large) analyses [1922]. 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. Steadystate 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
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 quasiequilibrium for all steps except the rate determin ing one. With this method, ButlerVolmer type relations are obtained relating the current J to the overpotential n
I
ir
'Ct,,F
ocF
'o
[exp^njexp^n]
current
(2.1)
the apparent
where
i0
is the
exchange
[23],
from
density,
cca and ac
are
transfer coefficients
charge remaining
can
symbols
meaning.
Tafel
If A is known,
i0,
ac, and aa
be
uniquely estimated
sible to include
most
versus
n).
It is further pos
mass
transport processes
boundary conditions can be treated [7, 8,9,24, 25]. In addition, the steadystate method offers the possibility of predicting the qualitative dependence of the exchange current density, iQ, or the limiting
simple
situations and
21
and
Structural Investigation
partial pressure, tempera ture, or overpotential [8,10,14,15,25]. However, steadystate 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
as
oxygen
dynamic
methods
are
methods is limited to
i.e. where
one
indispensable. Furthermore, the use of steadystate 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
large
errors.
Interpreting
these data
might lead
[1,12,26,27]).
impedance spectroscopy (EIS) lies in the fact that it is a smallsignal 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
[12,31].
This
approach
has been
increasingly
compli
[32, 33].
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 [3436]. The method allows for the treatment of multistep reaction mechanisms. But the multistep
mass
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
quasiequilibrium approach is employed for the treatment of the boundary concentrations at distances larger than 8. However, these simplifications may give different solutions for the frequencydependent
e.g.
[12,16,25]).
behaviour,
as
well
as
for the
limiting
an
behaviour
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
can
knowledge,
chemical literature. We
In Part I of this
give a brief description in appendix 2A.l. paper we provide a general framework for modelling electro
and
investigation, simulation,
tion
state
parameter estimation of heterogeneous reac mechanism possible. First, some general theoretical background about
space
modelling
a
is
given,
quantities
using
fairly
the
influence
of
surface
diffusion
on
(Ml)
we
adsorption
In
second model
on
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 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.
23
and
Structural Investigation
2.2
2.2.1
General Framework
The Process of
a
Modelling
basically determined by the purposes for which the microkinetic 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 physicochemical 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
mathematical model is
tary processes
ideas into
of
a
well
as
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
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 currentvoltage 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.
modelling
applied. Obviously
24
2.2
General Framework
2.2.2
Hypotheses
general agreement
Electrode microstructure.
exists
on
adsorption of oxygen molecules and surface diffu sion towards the triplephase 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
or
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 (0.110 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
scopic data, modelling is complicated by the morphology of the porous elec trode and therefore simplified electrode geometries are employed (see
Fig.
2.1
ionconducting 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 singlestep or a multistep
metals and solid oxide
reaction. The concentrations of oxygen vacancies
e
,
as
well
as
the oxygen
partial
pressure pQ
be constant
over a
wide range of
operating
conditions.
25
and
Structural Investigation
appendix 2A.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 2A.2). However,
an
uncertainty
remains and
large
errors
model
description. Moreover,
how
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
taking place
on
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
dcsputtered
area
during
10 min,
additionally
Esti
painted
mates
paste,
and
subsequently
tpb
(950C)
area
shows the
boundary
length
between the
sputtered
painted
(lower right).
of the
of the
quantitative
image analysis.
26
2.2
General Framework
criminated for
care
is necessary when
employing
they
were
almost
exclusively
obtained from
single crystal
partial
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
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
generally
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 ~103 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
the system
be modelled
using
one
single compartment
species
are
distributed
homogeneously.
species
of the
would
independent
applied
overpotential (i.e. the resulting current). Therefore, the overall electrode reac tion would be entirely chargetransfer controlled. In the second case, diffu
sive transfer of adsorbed oxygen
over
therefore
only
the reaction
zone
must be considered
adsorption
process, the
charge
to
transfer proc
systems of ordi
27
and
Structural Investigation
nary
firstorder
differential
equations,
the
state
equations,
which
are
generally nonlinear.
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
021
YSZ
can
high temperature
open timeinvariant
system [38]
which
be described in the
x(t,p)
f[x(t,p),u(t),t;p]
(2.2)
subject
x(0,p)
In
x0(p).
state variables of the
e
(2.3)
model,
Eq. (2.2)
or
represents the
usually
variable
species; u(t)
the
is
some
external
input
that
can
be varied
or
during
experiment,
e.g. the
potential
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)
the that
response function
are a
assume
parameters
priori independent
or
and g
are
(generally
sets of
parameters.
analytical solutions of this set of differential equations, that would describe the largesignal dynamic behaviour. Although nonlinear 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
some
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
5x(t, p)
A(p)bx(t, p) C(p)Sx(t, p)
system
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 nonlinear 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
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
Structural Investigation
G(s,p)
LZ(s) and Y(s,p)
nal y;
This
are
C(sIA)_1B
D.
(2.12)
the
Laplace
transforms of the
G(s,p)
description
is
input u and the output sig is the appropriate identity matrix. function description" or "Laplace
description". G(s,p) generally a threedimensional matrix in case of a multiinput multioutput (MIMO) system. In case of singleinput multioutput systems
(SIMO), G(s,p)
reduces to
a
transform
case
of
sin
gleinput singleoutput (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
Jfc2
,s x +
...
b,s

bn
k~l
(k<n)
(2.13)
+...
+bls
a0
are
where
is the
Laplace
variable and
constant coefficients
Eqs. (2.12) and (2.13) are fundamental results from theory (see e.g. [38]). Gabrielli and Tribollet first used a
description
as
presented
chemical systems
The state space
[35].
is the most reliable linear
representation
use
timeindependent
(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 illconditioned. Nev ertheless, this representation is often used for testing the identifiability of
algorithms properties of
for
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
impedance.
=
30
2.2
General Framework
is
applicable
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(sIA)_1B
obviously
Accordingly,
impedance
transfer function
ZF(s,
Frequency
^.
[30]
(2.18)
response.
imposes
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
domain is
given by
y(t)
=
ycos(cof
(p)
(2.20)
where

The
YF(;co)
andcp
ZyZn
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
description. Note that it would be more natu than the impedance data because EIS is nor
31
and
Structural Investigation
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 smallsignal excitation. If the nonlinear 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 largesignal response since the nonlinear model equations must be employed for these purposes. Let us identify some useful quantities that can be generally obtained from the statespace 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 nonreversibility 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
overpotential we find
Kt1
(225)
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)
ZF(jco)
were
data and
(b)
plot
of the
same
data.
ZF
and
in the
denote the
frequencies
obtained from
simulation of model M2
(fully
ance,
[1]).
=
denotes the

polarization
resist
Rt
resistance.
Ze(jco)
denotes the
ZF(jco).
33
and
Structural Investigation
where
were
mining step,
is of
and
v as
importance
can
gives
iQ/
which
be obtained from
can
and
Rt,
which
Polarization resistance.
its
gain
s
of
system
=
transients have
=
decayed.
0 in
To find the dc
gain of an
jco
Eq. (2.17)
^
YF(0)
DCA_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
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^ ^sia^b]
+
(2.28)
ZF(s)
i,
=
YF (s)
we
further have
ZF(s)
D
=
D(D
D
C(sIA)
l,
B)
B
i, D + C(slA) B_
C(slA)
l,
(2.29)
From
Eq. (2.29)
we
obtain
ZF(s)
C(slA)
D
+
C(sIA)_1B.
(2.30)
34
2.2
General Framework
which is
equivalent
to
YF(s)D
<231>
(2.31)
we
finally
obtain
ZQ(s)
and
Rt
^Hr
YF(s)D
Yv(s)
(2.32)
Ze(0)
Eqs. (2.23) quencies and by
From
Re
Rt
^
that
'
Rp Rt

(233)
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
timeindependent 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 handplot frequency responses for several rea sons: simple problems can be dealt with directly and computer results for more complicated cases can be checked. Handplotting is especially useful in interpreting frequency response data that have been obtained experimentally.
35
and
Structural Investigation
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
Z(ja
' Zp(jco)
=
.
l+]CoCdlZF(]to)
(2.34)
uncompensated 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
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
Re
be determined
experimentally
[56]
or
can
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
interpretation
2.2.6
Identifiability
for
identifiability
and
identifiability
easily understood by considering the prob equivalent circuit fitting. There, identical simula
parameters for the
or
equivalent
the
same
circuit
(problem
of structural
global identifiability),
same
the
(with
tural
set
of
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
analyse
the
identifiability of nonlinear
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
[62].
globally
p
can
struc
turally
only if,
unique
set of
parameters
be deter
37
and
Structural Investigation
mined for
locally
identifiable if
parameter
sets is
estimated from
equivalent circuit fitting). Nonidentifiable 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
02(g)
I YSZ
System
problem associated
our
opin
examples.
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
near
the
tpb
line
[25,66]. (Ml),
mass
first model
and
charge
balances
are
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
(~450C) [11])
adsorption process near the tpb. The model Ml is tested for structural identi fiability in the steadystate as well as for electrochemical impedance spectros
copy.
In
our
second
model
is
(M2)
we
include
surface
diffusion.
The
finitedifference
approach
employed
Considering onedimensional,
solution.
are
firstorder
Computer implementation
part
II
illustrated in
[1].
more
system
(M3), accounting
for the
of
02
on
38
2.3
Reaction Models
of the
2.3.2
Model
Basic
Equations
and
Assumptions
exchange
of oxygen at
equations.
by
=
^02
represents occupied
the electrons within the Pt.
V0 + 2e"
00
(2.35)
00
electrolyte,
and e~
represents
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
occurs
obeys
(ii)
area
which
occupied by Oad
is characterized
by N0;
39
and
Structural Investigation
(iii) The
rate of
adsorption /cad
Vq
and
are
desorption kdes
are
independ
ent of surface
coverage and
(iv) The
concentrations of
and
00
stant;
(v)
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
(in
2);
n
T where
eq
is the
equilibrium potential
and
is
the For M2
we
overpotential.
assumption:
on
(i)
Surface diffusion
depends only
concentration
gradients.
No interaction of adsorbed
species
is
considered;
(ii)
data;
(iii)
Mass and
D is
independent of the
charge balances.
=
For Ml
mass
^[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
40
2.3
Reaction Models
of the
Fig.
2.5
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
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
the surface
diffusion.
Complete
malized
model structure.
nor
or
scaled to
improve
is
accom
of surface
and [s]
and
(2.41)
are
rewritten
/i=
dt
2*adPo N0 (i
e)2 ^desN0 e2

(2.42)
*i[Vo]e
*r[C&](l6)
41
and
Structural Investigation
gl:
IF
(2.43)
which is
simply
representation
of
Eqs. (2.2)
and
(2.4)
x(t,p),
the
input
Q(t,p)
x(t,p),n(t)
y(t,p).
(2.44)
parameters
given by
(2.45)
reac
[fclc(T),Pc,fcIc(T),PJ.
Eqs. (2.42)
To
and
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
threeterminal
electiode
(CE)
a
are
exposed
ence
to the
atmosphere.
We should be
of how
polarisation
refer
potentiostatic
mode
potential
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
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?
following halfcell
reaction
02_(P)02,Pt(a)
where
(2.48)
Pt
(phase a)
not to be
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
indicated.
43
and
Structural Investigation
^
jL(y)
=
2^(00
ji02(P).
potential
of
(2.50)
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)
+
=
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)
=
is in
equilibrium
=
electrolyte
surface
=
Mo^lk^P)
conveniently
we
anc^
a0(P)
fl0(g)
JPo /*/p~
we
set
1 atm.
for
ae(P)
potential
difference
Acpeq
where
we
Acp
=
ln(^) ln[flo2.(P)]

(2.53)
used
Acp
Au
RT
+
ln[K(02IO )]
2
is defined
as
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 nonequilibrium potential difference
ference Acp from the
Acp
A9
ln[ao(P0]f^m[ao2_(P')].
44
(2.54)
2.3
Reaction Models
of the
potential for
2
we
obtain
gln[flo2.(P')] ^[ii02(P')lio2(P')lio20]+<P(P')
=
(255)
and jj,
similar
=
result
we
for
2(P)
by
replacing
P'
with
p.
With
2(P)
M^n2(P')
overpotential
AcpAcpeq
[io2_(P)
+
jio2_(P')]
[<P(P)
cp(P')]
(256)
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: chargetrans
shows that the
and to the deviation of
fer
overpotential),
fl0(P)
frm
me
equilibrium value
overpo
at the
term: concentration
2.3.4
Structural
Properties
of the Models
determining
physical process
of
a
and with
estimating
(coupled)
question
differential of whether
equations. it is possible
on
question
a
to obtain
unique
eters of interest
question
If the
is often referred to
that of
can
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 noisefree 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
Structural Investigation
be
overpotential measurements. We first describing the steadystate IF(n) behaviour. Starting from this result we prove in a second step the global structural identifiability of the mechanisms in the steadystate. 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 )
=
=
eq
,Po>)
2/'
ta[*ic<T)'[o^'lVT,p0z)J
in this way E
(2.57)
where
(T, pQ ) depends
on
the tem
perature
as
on
the oxygen
partial
equilibrium
surface concentration of
Oad
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/
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
are
temperatures
from T
we
make the
following
formulation for
rate constants:
klc(T)
*lc.exp[El/(RT)]
klcexp[El/(RT)]
46
klc(T)
(2.60)
2.3
Reaction Models
of the
where
the_preexponential 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
57hl
fclc
we
fcic [V0]
*lc
=
[Oq]
and
+tf
kl(
=
hl<^5)
(261)
where, by definition,
With
fclc(T)
p020
1 atm
find
klc
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 steadystate 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
Steadystate IpCn)
behaviour.
In the
Mm, T, p0)
2N0FAaklc[Vo]
x
(2.63)
K(T) (i fi)
i.e. the
.e2<lW<*i>_. f*f<****r
surface coverage of the
where 9
at the
of the
47
and
Structural Investigation
currentvoltage 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 transfercontrolled 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)
currents densities
therefore
given
as
i0
i0a
e2(1_P)/eq
and
(2.65)
i0
(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(l90)]1/27K(7^je(1"2P)/e<'
and
(2.67)
with
by replacing
(T,p0 )
i0(T, POi)
With
2N0F*lc[Vo]
*<^>
and Pq
Po2(1"P)/2
(268)
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
=
The oxygen
partial
i0(T,po)
occurs
is
given by
Po2*(T)
The
Jjl2PPL
P2[K(T)r
(2.69)
expression
for the
gen
partial
pressures
and oxy
48
2.3
Reaction Models
of the
i0(T,Po2)
2N0Ffclc[Vo]
lVA + (AHad)/2 J+ lr R 2KfWX:
na
tj
(i
x
aH2
(2.70)
JK(T)K(T)
:=
1+K(T)Jp^2
where
=
Po,
(iP)/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
Un.T.PoJUT.fo,).A.le^Me**}
As
soon as
(2.71)
an
to
applied
over
Ip(T) will deviate from the ideal ButlerVolmer behaviour described by Eq. (2.71) and the reaction can not be considered as chargetransfer 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
surface
diffusion).
use
Identifiability
give
an
in the
We
now
the result of
Eq. (2.71)
to
intelligible
are
and M2
said
prove of structural
measurements
hip)
It is
lpip*),
if and
only
if p
p*
controlled
current
(2.72)
reactions
are
wellknown
that
two
described
by only
(note that
we
49
and
Structural Investigation
instead of
p,
which
we use
for
elementary reactions)which
vs.
can
be
uniquely
in
determined
our
by
Tafelanalysis (log(ip)
n) (see
e.g.
fclc and P can be uniquely determined if the reaction is entirely chargetransfer controlled. It is rather troublesome to show analytically that Ml is globally structurally identifiable in the general case, because the (nonlinear) 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
problem
uniquely identifiable in the steadystate, even if the reaction is not chargetransfercontrolled. (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 leastsquare fit of Eq. (2.63) to the experimental data. A Tafelanalysis of experimental data would give
incorrect values for the unknown
parameters.
M2. We
in
We
can
use
expect
the
steadystate,
Therefore,
similar. In addi
Oad
on
Pt
was
assumed to be known.
into the
new
parameter
problem.
is
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
(Ml).
a
that such
electrode
likely
to
exhibit
description.
We
will
first
rewrite
the
nonlinear
rate
Eqs. (2.42)
and
and
Eqs. (2.39)
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
(2.75)
[00].[l9(f,p)].)cfe2(1pW)
[
gl:
IF
2N0FAa
(2.76)
[oJ][ieaP)].]fc?c'e2(1p)^)]
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
We obtain
5/i
=
39
a(p)
*kadpoN0 (1
9)
4kdesN0
(2.77)
[VG] h
[00] kx
d/i
=
3t1
b(p)
[V0]2B/fci9
+
(2.78)
[00]2(lP)/fcr(l9)
39
c(p)
2N0FAa
[[00] kx
[VQ] fci]
(2.79)
51
and
Structural Investigation
dn
d(p)
2N0FAax[[Oo]2(lP)/r(l8) +
[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
(A, B, C, D) quadruple
dealing with scalars (firstorder 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(lQ)
4kdesNQQ
(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
equations
any :
Rt
R*
[oD] fca
[vQ] h
[oG]
T*
[vG] i*
(2.83)
^ad^oPo,
Keep
be
at T
(1
8)
4fcdesN0
=
4kadN0pO7
=
(1
9*) + 4fcdesN0 9H
in mind that 9
9(p, T, pQ ), k\
pQ . We obtain
expressed
=
in terms of
=
T and pQ
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.
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
firstorder process
constant
%
1
CO
=
J\

h

e(t)
t=i
YSZ
tpb
investigation
of reaction mechanism
=
Fig. 2.7
Twocompartment
place
in the
tpb compartment (i
1). The
con
partment.
At
distance
z >
8,
is considered to be
diffusion flux is
proportional
to the
within
a com
The surface
53
and
Structural Investigation
/i(0
"e0e(o"
"9
and/'^f)
(f)90
(2.85)
The
mass
tpb compartment is
=
obtained from
('tpb8)^(*)
which results in
(>Wi>ztpb
(2.86)
24.Jr9(r)
where
909(f)
(2.87)
Td
(8
process
tration
depth [7]).
length of Oad [25] or the pene mass balance of Eq. (2.75) and
reevaluate
ZF(s,p).
given by
ZF(s,p)
Rt
1s +
([Oolfci
T+
tVolfci)

(2.88)
9
AKdN0Po7
(1
8)
4kdesN0
no
which
means
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,
M2, when
skip
our
assumption
w
that the
i.e. when
we assume
that
is unknown and
as men
we
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 chargetransfer controlled reaction under steadystate investigation. The IF(T) behaviour is given by Eq. (2.71) where we put Aa lt b w. Thus, from a Tafelanalysis, P and the parameter product klc w are uniquely identifiable, but klc and w are not individu [P, k^0,w] is unidentifiable in the ally identifiable. Thus, Ml with p steadystate.
tioned before, there is
=
An
important point
n
to note is
that, for
+
classical EIS
experiment
on a
system
with
is
equations
in the
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;.
Tafelanalysis, 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 steadystate. 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
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
requirement
two
or more
is not
sufficient, however,
the
sensitivity
of
combination of
sensitivi
55
and
Structural Investigation
ties,
indicating point
high
part
parameters [69].
We will illus
trate this
in
2.3.5
expression
for
ZF(s,p)
(Eq. (2.82))
is
'
ZF(s,p)
which
be
Rt(p)
general
s +
1
bp(P)
s +
(2.89)
can
rearranged
to
the
form of
ZF(s)
where
on
Rt
(a0b0j
s + a
(2.90)
we
actually
mean
that
Zp, Rt,
and the
polynomial
coefficients
depend
polarization resistance
b0 RtRt =
is found to be
fUjco)
We also
lim
JO)
ZF(jco)
(flo"&o)
(2.91)
and
Eq. (2.89)
that
Rt
'o
s + a,
(2.92)
o
an
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
,
ao
>
ana<
^p
^t
^e
can
furmer
see
that if the
is much
larger
adsorption
and
desorption
process
faster than the electrochemical reaction step, then this second term will
almost
disappear
chargetransfer
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
in the
complex plane
R )
.The The
num
impedance
witch
Rp(a0,b0).
We have
(Rt <
V(jco).
figure
frequencies
Rt
are
were
obtained
increasing
so
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
By
l
xx
coj
a0b0
and
obtain
jou, +1
(2.93)
which is
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
Structural Investigation
logZF(JG))
We
can
log
(2.95)
of
identify
independent
the
frequency.
2.9.
terms is shown in
Fig. by
frequency
occurs
is not
given
is
the inverse relaxation time of the process, l/x*, but that this
frequency
inO
10
^^^^
'"
,.
N* 102
r
a)
in4
^_
:
. .
'
10*
10J
0)/s
l
1(T
103
100
'
'
pit'
"""*
"r
*r
o
00
50
^^***"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 Joi^a^ 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
all
phase
be
obtained
electrode reaction.
58
2.3
Reaction Models
of the
//(27CS1)
b)
Fig.
2.10
h
//(27CS"1)
Frequency
responses of Ml in Bode
phases
of
ZF(jco)
representation.(a) Magnitudes and (b) aQ/bQ. Note that the slope of ZF(j<o) only by
about
one
emerges
clearly
as
are
different
order of
magnitude.
given by
tance,
J^
u)2 (cf.
Fig. 2.9).
The
imaginary part
Im[Yp(jco)],
kept
in mind when
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
Structural Investigation
one.
frequencies
These facts
as are
introduced in
in
given by tOj/o^
same
lbQ/aQ.
Fig.
2.8
are
data
as
in
given
in
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 (nonlinear) state space models. In the cases where the reaction mechanisms are simple, analytical solutions for the steadystate and frequency response behaviours
The present
can
can
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 easytouse 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
must be
tackled before
experi
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
Despite
proposed
be treated
on
the computer
efficiently
and in
straightforward way.
Acknowledgments.
portation,
thank
sions. In
The financial
and Telecommunication is
gratefully acknowledged.
on
present colleagues
particular,
we are
sabbatical from
Pennsyl
vania the
University,
laboratory,
for
carefully reading
60
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A. M.
rous
Svennson, S. Sunde, and K. Nisancioglu. A mathematical model of the po SOFC cathodes. Solid State Ionics, 8688:12111216,1996.
S. Primdahl. SOFC anode kinetics. In
[27]
M.
and MetalsProc
of the
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J. Van Herle,
A.
J. McEvoy,
and K. R.
Thampi. Oxygen
dense cathodes for solid oxide fuel cells. Electrochim. Acta, 39:16751680,1994.
[30]
analysis.
1984.
Technical
Report 004/83,
Solartron Instruments,
[31]
B. A.
van
Hassel.
bilized Zirconia.
Transport and Oxygen Transfer Properties of Ion Implanted PhD thesis, University of Twente, 1990.
on
[32]
Nipoint electrodes: Measurement and modelling of impedance. In High Temperature Electrochemistry: Ceramic and MetalsProc of the 17th Rise Int. Symp. on Mat. Sci., pages 339344, Roskilde, Denmark, 1996. Rise National Laboratory.
kinetics of the oxygen reduction SOFC cathodes. In
[33]
High Temperature Electro chemistry: Ceramic and MetalsProc. of the 17th Rise Int. Symp. on Mat. Sci., pages 229234, Roskilde, Denmark, 1996. Rise National Laboratory.
on
[34]
electrochemical
impedance techniques:
Multitransfer function
[35]
approach
for
generalized
trochemical
impedance spectroscopy. /.
investigation
[36]
impedance spectros
copy
to
the
41:957965,1996.
[37]
Phasengrenzreaktionen an Perowskitelektroden auf stabilisiertem Zr02: Implikationen fur die Abgassensorik. PhD thesis, Universitat Tubingen, 1994.
G. Reinhardt.
T. Kailath. Linear
[38]
Systems. PrenticeHall,
[39]
J. D. Powell, and A. E. Naeini. Feedback Control of Dynamic Systems. AddisonWesley, 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, 16:447451,1996.
L. R. Velho and R. W. Bartelett.
[40]
[41]
Diffusivity
and
solubility
of oxygen in
platinum
and PtNi
alloys.
Met.
Trans., 3:6572,1972.
on
[42]
N. L. Robertson and
zirconia cells:
platinum
/.
electrodes in
Electrochem.
Soc,
137:129135,1990.
63
and
Structural Investigation
[43]
of
La^S^MnO^yttriastabilized
40:17411753,1995.
zirconia
electrode
Acta,
[44]
J.
L.
face.
Gland, B. A. Sexton, and G. B. Fisher. Oxygen interactions with the Pt(lll) Surf. Sci., 95:587602,1980.
sur
[45]
sticking of 02 on a Pt(lll)
sur
face. /. Chem.
[46]
[47]
A. N. and
Artsyukhovich, V. A. Ukraintsev, and I. Harrison. Low temperature sticking desorption dynamics of oxygen on Pt(lll). Surf. Sci., 347:303318,1996. Somorjai.
Introduction to
[48]
G. A.
Surface Chemistry
and
&
Sons,
[49]
In
Proceedings on
the
[50]
C. G.
Vayenas,
S.
activity:
electrolyte
[51]
algebra aspects
of control
design computations.
IEEE
[52]
identifiability.
[53]
K. R.
Mathematical
[54]
Frequency analysis
of
temperature per
electrochemistry. /.
[55]
R. D.
Armstrong.
The metalsolid
electrolyte interphase.
[57]
interruption
technique
for
[58]
F. Berthier,
faradaic
impedance
electrode reaction:
Application
measurements.
Corros., 51:105115,1995.
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References
[59]
J. N. Michaels. Double layer capacitance of porous platinum electrodes in zirconia electrochemical cells. /. Electrochem. Soc, 138:14941499,1991.
E. Walter.
N. L. Robertson and
[60] [61]
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, 30:265276,1994.
[63]
Berthier, J.P. Diard, B. Le Gorrec, and C. Montella. Choice of experimental by structural properties of mechanisms. /. Electroanal. Chem., 399:16,1995.
F.
method induced
[64]
F.
structurelle de la reaction de
volmerheyrovsky. /.
Chim.
Phys., 90:20692081,1993.
[65]
Steadystate investigation and electro impedance spectroscopy: Identifiability and distinguishability of metal dissolution and passivation mechanisms. /. Electroanal. Chem., 362:1320,1993.
chemical
K.
F.
[66]
over
solid
electrolyte
1989.
interfacial
impedance.
[67]
J. Gauckler. Reaction kinetics of the Pt, 02(g) I cZr02 sys tem: state and parameter estimation. To appear in Proceedings of the I lth Interna tional Conference on Solid State Ionics, Hawaii, 1997.
H.
A. Mitterdorfer and L.
[68]
T. Kudo.
Study
a
num
through
observation of
exchange
current in
[69]
M. Knudsen. A
tem
sensitivity approach for estimation of physical parameters. Identification, pages 533538, Copenhagen, Denmark, 1994. IFAC.
In
Sys
65
and
Structural Investigation
Appendix
2A.l
State
Space Description of an
space"
Electrical Circuit
by means of a simple example. Consider the electrical circuit shown in Fig. 2Al.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.
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)}
(2Al.l)
^[UyWU^t)]
and
Kt)
^[Llu(0lli(0]
(2A1.2)
/(0
o o2
Rl
O
R2
ua(t)
Uy(t)
o
o
Fig.
2Al.l
are
given
66
Appendix
We
put
L7y(f)
(ground).
We solve
Eq. (2Al.l)
for
L7a(f)
^i(')
and
4(h^]"i(^
C
Ul
R2
CRl
U(0
(2A1.3)
=.Ul(t)
Rl
Rl
rUu(t).
(2A1.4)
Eq. (2A1.3) is called state equation and Eq. (2A1.4) is called output equation. Form Eq. (2A1.4) 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. (2A1.3) and (2A1.4) in matrix form as
x
=
Ax
Bu
(2A1.5) (2A1.6)
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. (2A1.3) to
=
(2A1.6)
LCRlJ
(2A1.7)
Statespace 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
Structural Investigation
2A.2
Calculation of
tpb length
of
the total
well
as
be obtained from
as a
length
of the
tpb,
can
I tib, We
parameters.
assume
facing
the solid
electrolyte
be
A characteristic
as
length,
Fig.
2
defined in
consider
Then
/char
we
dp
be the
only
free
parameter.
length
of the
'tpb
4rfP T^
char
CA21)
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.
2A2.1
parametrized
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.
coverage
Acov
(/char
)/lchaT
which
solve for
dp we find
(^A22)
'tPb
4/^VriA7,char
Typical values for noble metal electiodes are in the range of 210 pm for l^j. and in the range of 0.40.85 for the coverage A^ (cf. Fig. 2.2 and e.g. [7,10,17,
20]).
69
and
Structural Investigation
70
Chapter
Computer Implementation,
Simulation,
Abstract
In
and
Validation
part
I of this paper
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 finiteelement
transport
is devel
oped.
The
origin
of the double
layer capacitance and its influence impedance (EIS) is discussed. The prob
and numerical
aspects
are
steadystate currentvoltage
ance
imped
is simulated for
(500C) Pa to 105
to 1173 K
regimes
discriminated.
Above
overpotentials the reaction kinetics is essentially determined by the chargetransfer step. With increasing cathodic overpotentials, and/or decreasing pQ surface diffusion is in competition with chargetransfer. At tem
(850C), high pQ
*)
Submitted to
/. Electrochem. Soc.
Implementation, Simulation,
and
Validation
peratures between
dominated
essentially
supply of atomic oxygen (Oad) via surface dif fusion and dissociative adsorption of 02(g) near the tpb. The chargetransfer coefficient, the electrochemical rate constants, and the activation enthalpy of the chargetransfer reaction can be uniquely estimated from EIS data. The activation enthalpy of the
by
the
dissociative oxygen
adsorption on Pt can be
on
depend
a
microkinetic models is
powerful technique
in order to obtain
deeper understanding
Keywords.
double
of reaction mechanism.
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 YttriaStabilized 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
atomic oxygen
on
the Pt surface
was
only one electrochemical rate constant and one chargetransfer 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,
steadystate transfer controlled reaction. Expressions describing the behaviour as well as the smallsignal frequency response behaviour were also given. However, we have not yet described how the theoretical results
rigorous
case
treatment of the
behaviour in the
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
parameters
the model
equations
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 reimplementation 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 steadystate 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
as
primary software
an
imple
ordinary
program
ming language,
with numerical
such
as
or
Fortran. Matlab is
dealing
sci
analysis,
matrix
a
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
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
finitedifference models
Simulink
dealing
with
function, the
73
Implementation, Simulation,
and
Validation
dynamic
behaviour of
system
can
be
investigated
models
can
in time and
frequency
(LTI)
be converted between
commonly used in ordinary programming languages, uses the system of equations directly. Explicit statespace 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
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
in
(ii)
physical and kinetic constants available to the Mat workspace. Estimate some reasonable values for the
unknown parameters.
(iii)
Determine the
steadystate
=
the condition
dx(t)/dt
(initial conditions).
in
(iv)
Run
largesignal
simulations
nonlinear model
(Simulink
or
Matlab
function),
or
(v)
generate
nal time
frequency
response
or
the
smallsig
dependent
behaviour.
3.2.2
Heterogeneous
The
primary objective
balance
concern care
of these
procedures
is to
implement
the
mass
and
is
charge
no
equations
into the
need to
equations
for Matlab
the
takes
entirely
precisely
74
3.2
Model Implementation
nature
of the numerical
may be
helpful
in
basic
knowledge
for simulations in
gramming
environment
[35].
systems
are
gramming environment we put some emphasis on the actual implementation the model. Implemen process in order to facilitate the reimplementation of tation details specific for Matlab and Simulink will be given in the appendices
3A.3 and 3A.4.
We
use
developed
in
part
I of this
cation
as
starting point
obtained
as
for the
implementation [1].
The
mass
and
publi charge
balances
were
h
^eC>P)
2kadpoN0[lQ(t,p)]22kdesN0Q(t,p)2
(3.1)
[Vol^t.p).^.^^
+
[00][ie(t,p)] fc!qe2(1p)/n(0
gl:
IF
k? e~2mn
(3.2)
[00][le(i,p)].^e2(1p)/,1(f)]
unknown
with
the
vector
of
the
parameters
[klc, (3],
and
fc^q
A.l. Let
us
rewrite
=
Eq. (3.1)
with
quantity), kt
*
=
[Vq]
k\q, and kb
(1"
"
[00] keq
as
2kadPo2M0
*)2 2*:desN0 x2
+
(3.3)

krx exp[2p/u]
kb (1 x) exp[2(l
p)/w]
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
75
Implementation, Simulation,
and
Validation
2N0FAa[k(
(3.4)
can
<f2P/M + kh
(1 x)
2(1P)/m
(3.4)
implemented into a Matlab function or into a Simulink block diagram. Appendix 3A.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. 3A.3). The time dependent behaviour of the system from any starting point towards the steadystate 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 statespace descriptions of the models can be obtained by following either of two routes. First, analytical expressions for the statespace 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 multicompartment models. From linearized statespace models (SSM) the frequency response and the smallsignal time dependent behaviour can be obtained at the corresponding operating point. Note that the linearized SSM can not be used to simulated the largesignal time dependent behaviour, such as potentialstep responses or cyclic voltammetry. The second approach circumvents these limitations. The function "linEq. (3.3) numerically
x
=
for
0. If
0,
from the
approach has the advantage that both smallsignal behaviour of the model can be
and without the need to obtain
diagram (cf. 3A.3). This the largesignal behaviour and analysed with one representation
(lengthy) analytical expressions for the statespace 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 steadystate equilibrium points from (nonlinear) sys tems in block diagram representation (cf. 3A.3). This is especially useful when the steadystate 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
Model Implementation
these conditions it is
generally
as
not
possible
to solve
=
equations
or
systems of
equations
Simulink block
diagram of Ml
The
complete
3.2.3
Surface Mass
Transport
different methods to deal with
There
are
basically
two
partial
differential
[6].
it
approach [7].
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]
I ^35
In
D>S alH!i)2
"
D>8dz'
(3'5)
part
we
depend
on
ingly,
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
approximated
with
into
compartment
/i
1, i
DicrNA
N0
xi 1
Az;
xi
il
Az,
2 )
and/'i,i
DaT
v
xi
AZ:
xi +
AZ;
1
+
(3.6)
1
V 2
77
Implementation, Simulation,
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 onedimensional finite element model. (a) 3dimensional view of porous Pt on solid electrolyte according to the 2dimensional
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
Model Implementation
of surface sites
on
Pt
Oad in compartment i, N0 is the number (atoms/m2), NA is the Avogadro constant (mol1), and
mass
Azj
is the width of
balance
(mol/s)
for
com
partment
i is obtained
Ai7n
dc.
~
ldt
*'
Oil,l/i,i l)
+
(3.7)
where
A{
is
Azf
xi
is the
area
of
compartment i,
of
mass
and
Cj
the
surface concentration
we
Oad
in
compartment
i. i
With
ci
N0/NA
dxi
finally
balance of
compartment
a Az
D
=
dt
Az./2
(3.8)
x
Az;
*il"
+
il
Az
V
AZ:
il
AZ;
xi
+
1
/
Az
AZ:
AZ:
AZ;
or
in short form
Az;
dc
1
~
dX:
rp
1
"
~2D~'Tt
where
rTt
il.i^il 'fli,ij:i
ai,i + la:i + l
(3.9)
T{
Az{ /(2D)
com
partment /, and the ai are numerical factors which and the boundary conditions.
The
statespace model is realized by writing the mass and charge balance equation for every compartment using the following initial and boundary
conditions:
(i)
Oad
is homo
geneous before
79
Implementation, Simulation,
and
Validation
(ii)
Boundary
conditions at
an
infinite distance
a
co
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
=
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 statespace description of M2:
=
=
of the
dx.
2kadpoN0 (1
krx1
dx{
Tt
+
xx)2
2kdesN0 x2
(3.10)
kh.(lxl)
^Tlqx1 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
+
(312)
q
+
TuKl
where denotes
q**1
2q
_
l+qXa>
X> +
1)
co
=
the
outmost
compartment
facing
the
region
with
* +
xo
80
3.3
Simulation Procedures
The
by putting Eqs. (3.10) to (3.12) into a Simulink block diagram (see appendix 3A.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 3A.4.
3.3
3.3.1
Simulation Procedures
Model Initialization and
Sensitivity
the numerical values of all constants
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 3A.l).
These values
are
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
were
chosen while
in
taking
Appendix 3A.l). Note that the activation enthalpy of the electro chemical reaction is also reasonably known [9,10].
Table 3.1 of
In order to be able to
run
simulations,
=
some
[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
= = =
reaction rates
can
be estimated in
81
Implementation, Simulation,
and
Validation
Once the
estimates
priori
known
are
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
of the
of
ZF(jco)
each
parameter p{
is
easily
S1(0)
.to(^ZF(i.)Kg55).
parameters
(3.13,
tigated frequency
range.
3.3.2
Penetration
Depth
and
tpb
Width
Consider
we
have
only
approach will
But
we
employed
we
equation [1214].
up to which
we
have
of the surface
not
should
use
question is generally treated with the concept of the Nernst diffu sion layer thickness or penetration depth, 8 [1416], 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
=
perturbations
at the
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 timedomain simulations but may it also help for simulations in the fre quencydomain, i.e. for electrochemical impedance simulations?
=
82
3.3
Simulation Procedures
77C 900
800
700
600
500
l(f
T=973K
\ \
\
10 20
30
10i
ReCZp/QcrrT)
SH
102
com
/(rads1)
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
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
parameters given
in the
ence
in Table 3.1
complex plane
obtained at T
973 K and pQ
temperatures from
773 K
(500"C)
to 1073 K
(800C)
(not shown).
83
Implementation, Simulation,
and
Validation
Analytical
sional
impedance
are
available if onedimen
is
surface
diffusion
Warburg impedance is obtained at high frequencies and a perfect semicircle 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
=
773 K
w
=
(500C)
10
nm.
to 1173 K
fixed value of
Pa is
shown in
Fig.
3.2. A pQ
dependence
was
of comax is found
found
by
others
we
having
found
as
an
expression
zation to 68
described above.
we are
Once 8 is determined,
question
com
size of the
tpb compartment.
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
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.
tpb
of
Srdoped
LaMn03
trode
cathodes
on
YSZ
is
conductivity of the
[21]. Similarly,
propor
tionality
conductivity
can
ae and the
on
length
of the
tpb
has
YSZ
[22,23].
It is clear that
tpb
of
electronically conducting
metals)
are
(LaMn03
at
equilibrium potential
and noble
sparse.
Wang
and Nowick
[24]
84
3.3
Simulation Procedures
proposed a model where oxygen is supplied by surface diffusion towards the tpb and subsequently diffuses laterally in the twophase 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
on
or
whether
combination of
possibilities
area
takes
place.
irrespec
to the
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
R1
It is
w
M0Fzvltpb[(lP)fkh(lx)
Wkrx]
(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.
=
.
85
Implementation, Simulation,
and
Validation
we
set
10
nm
to be
independent
area
of
With
/^b
in the order of 1
pm/pm2,
of the
apparent electrode
examined
which
to be in
problem will be
numerically below.
3.3.3
The Double
Layer Capacitance
capacitive behaviour,
little
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 'pseudocapacitance'. We believe that equivalentcircuit 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
electrolyte) [2730].
[28]
capacitance
generally
estimated from
(316)
Acov
is the
electrolyte
e
coverage
permittivity
r
of vacuum,
is
an
effective die
lectric constant
(of order (1
1),
and
(a few tenth of
It is
nanometer). Q should
10) uF/cm2.
of interfacial
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
Simulation Procedures
completely blocking electrodes without specific adsorption (of the diffuse double layer oxygen ions at the metalsolid electrolyte interface), is described by (z+ z_) [31]
For the
case
of
c<A4<*{m)
where
=
=
(317)
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
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
experimental
results
in disa
greement
in YSZ is
theory.
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
on
YSZ solid
electrolytes.
can
in the range of 30
to 1073 K
uF/cm2
to 350
uF/cm2
at
temperatures between
obtained
673 K
(400C)
were
by fitting equivalent
circuits to
experimental
Obviously,
87
Implementation, Simulation,
and
Validation
these values
are
too
high to
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 currentdecay 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
(see 3A.2).
Higher
termed
capacitances (between 0.1 mF/cm2 to lm F/cm2, usually "pseudocapacitances" [19]) are usually obtained by fitting experi
equivalent
circuits of the
type shown
in
Fig.
3.3 b
(see also
to the
[32],
a
and
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
are
cm2 (thickness
<
50
pm).
Vayenas
have
proposed
that
is established due to
backspillover
in the
These ions
Oad are accompanied by their com metal, thus forming surface dipoles [36].
Pt
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
Simulation Procedures
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 semicircle or one broad semicircle 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 semicircles or broad semicircles in the complex plane.
Fig.
3.3
Electrical
89
Implementation, Simulation,
and
Validation
esses
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 chargetransfer 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 steadystate 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 "pseudocapacitances" (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
tance,
as
we
discussion of the
properties
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
Simulation Procedures
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
Cdl
without
assuming
(ii)
an
equivalent circuit.
is to
The second
recognize
that
an
accurate
accu
estimation of
rate
is
mandatory prerequisite
to obtain
estimate of
estimation
Rt
on
chargetransfer resistance Rt. An accurate required if one aims to carry out a parameter
experimental
are
the
we
have
not
globally
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.
be
3.3.4
Digital
Aspects
ver
The simulations
were
obtained
by nmning
on a
Sun SPARCstation 20
running
can
ating system.
ble
The Matlab
Optimization
and Control
System
be
Toolboxes with
were
run
reasona
midrange 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 3A.3 and 3A.4 it should be possible to reimplement 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
Implementation, Simulation,
and
Validation
stability problems during simulation of the time dependent behaviour when using an inappropriate integration (e.g. RungeKutta 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. Steadystate 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
was
used for the extraction of linearized statespace models with the Simulink function "linmod" at the bation level of
The default
pertur
for the
10"5
was
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
generally
below
104, indicating
that the
prob
lem
was
well conditioned
([40], p. 166). Frequency response data were functions "bode" or "nyquist". Numerical esti
resistance R~
were
polarization
conveniently obtained
"dcgain".
3.4
3.4.1
Simulation Results
ChargeTransfer Controlled
current
Kinetics
results obtained
K
Exchange
Pt,
density i0.
Experimental
on
the system
02(g)
to
zero
charge
transfer controlled
expect such
the
tpb
is
independent
to
through
if the
rate of surface
adsorption
assume
is fast
compared
the
tpb.
We
chargetransfer
controlled
over a
range of temperatures.
92
3.4
Simulation Results
chargetransfer
=
tpb,
then the
2 and
[1]) (32)
'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
(321)
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
onequarter 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
K(T)Jp^
under the
limiting condi
on
tions of 9
0 and 9 1
on
oxygen
are
adsorption
Pt it is
questionable
whether these
limiting
conditions
experimental situations considered [33]. However, the onequarter 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 chargetransfer coefficient P. This property has
reached under the
not
i0(po )
value of
The oxygen
partial
decreases with
p0 *,
P2
^K(T)
1P PK(T)
(3.22)
93
Implementation, Simulation,
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
seen
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
exchange
given
current
density i0
partial
pres
con
sure.The
stants
temperatures (K)
in Table 3.1
are
within the
were
figure.
The
parameters
and rate
given
(appendix 3A.l)
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
parameters
in
Fig.
partial
occurs.
to the value of
p0*
p0
*
P (cf. Fig. 3.5). Eq. (3.22) simplifies K(T)~2 with p 1/2 [44].
=
In the
was
AHad
on
ad
and
Edes
are
i0
occurs
is
given by
9*
._ =
*<T>^ l+W)JPo2
the
(3.23)
which
gives by
use
of
Eq. (3.22)
simple
1p.
result of
9*
(3.24)
95
Implementation, Simulation,
and
Validation
Only
in
case
where
1/2
we
have 9*
0.5
AHad
good
becomes almost
independent of surface
coverage
[48]
and
we can con
*
Arrhenius
coverages, i.e. at 9
mined for
AHad by
Okamoto et al.
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
Mizusaki et
,
AHad
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
.
Finally,
the
temperature dependence of i0
AHct*
where
(1P)a + PEa
energies
The
(3.25)
Ea
and
Ea
are
the activation
electrochemical
reaction,
respectively.
Eq. (3.25)
is
easily
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
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=
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
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,
reported
values for
is attributed to the
AHad. Using
a more
probable
adsorption
diminishes
kj/mol [48],
this
discrepancy
kj/mol.
experimentally. The chargetransfer 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 chargetransfer reaction, Ea and Ea It is expected, how AHct*
can
be obtained
are
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
broad
and the
chargetransfer coefficient P determine the overall electrode characteristics. In solid state electrochemistry it has been common practice to obtain both values from a Tafelplot analysis of Ip(T) data. However, the parameters obtained from this analysis are only meaningful, if one chargetransfer (or one chemical) step is actually rate determining the overall electrode reaction
[1,50,51].
But how
can we
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 chargetrans
fer step
or
not. We
=
use
fications:
klc
2105 m3/(mols)
important
modi
Ed
110
kj/mol.
97
Implementation, Simulation,
and
Validation
77C
900
t
800
i
700
i
600
i
500
r
io1
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
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
, ,
parameters of Table3.1
were
*(1100 K)
10
Pa.
Compare
Fig.
3.4.
98
3.4
Simulation Results
general
definition of the
charge
transfer resistance
^?)*.
where x{ denotes the
(328)
steadystate 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
= =
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].
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 chargetransfer controlled behaviour occur at larger overpotentials. The deviation from Tafel behaviour is shifted to lower
Fig.
cathodic
curves
overpotentials
an
with
decreasing
pQ
It is further
seen
that the
follow
ip(T) overpotential
a
competi
chargetransfer
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
recognize
seen
given
curve.
The inset of
Fig.
tpb.
It is
99
Implementation, Simulation,
and
Validation
of
Oad
near
the
tpb strongly
a
decreases with
increasing
Note that
to
cathodic
overpoten
a
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
io1
.
X
\
**
^
i\
\
\.
'a
*\
\
\
*
,s
^io2 5
\
\
A
i
\
A
\
\
\
1(T3

Po2=15pa
2
a
1
:
104Pa
103Pa
i
>
'
in4
<
0.5
0.4
0.3
0.2
0.1
n/Vvs.eq(r=1123K)
Fig.
3.7
Steadystate 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
=
(i.e. pure
Tafel
behaviour).
overpotential
1123 K.
as
Parameters:
110
kj/mol;
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
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
lated
IF(n)
from
=0.15 V to 0.35 V
Fig.
3.9 shows
some
results. It is
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)
=
plot
of the data
shown in
Fig.
3.7 at pQ
M2 and the solid line denotes the ideal Tafel behaviour. The inset shows the
ing
surface concentrations
n
.
as a
tpb
and the
correspond applied
overpotential
gradient extends
over
~10 pm.
101
Implementation, Simulation,
and
Validation
line
over
the range of
overpotentials
=
coefficient
0.62.
decrease with p0
and
are
all
Fig.
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
VI
X
,1
10
7
'VV (049,6.5)
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\)
analysis.The
The value for
Tafel
analysis
was
are was
/F(t)
given
as
within the
figure.
in the simulation
0.62. The
parameters
as
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
analysis.
an
following
does not
conclusions: first,
apparent
JF(T)
curve
assure
chargetransfer 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
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
by
parameters
as
Fig.
3.7
were
used.
103
Implementation, Simulation,
and
Validation
methods, such
as
electrochemical
of this
publication [1]).
Electrode
impedancesdetermination of Rt
and
Cdl.
As
mentioned
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
= = =
cuit and
interpret
capaci
fail in
tances. This
more
might complicated
simple
certainly
as
described
below.
Fig. 3.12 shows two series of spectia, each points of M2 but with different values for
The
the double
spectra show the Faradaic impedances ZF(jo)) (thick lines) of a purely chargetransfer controlled reaction kinetics (figures on the left), a kinetics
where
chargetransfer
and
a
is in
competition
centre),
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
lH
a)
0
3.1
3.2
3.3
3.4
10
12
Re(Z/Qcm2)
1.5
ZF(jw)
Z(ja))
7
0
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
Implementation, Simulation,
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
11
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
Il
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/acm2)
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
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
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
simulated
impedance
of M2 in the
complex plane.
an
ran
impedance
from the
given
3.13
data without
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
Fig.
107
Implementation, Simulation,
and
Validation
12
'cdl
II
zg<d)
II
I *. f
1
1
i
, ,
ZF0co)
Lr\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
The
electrolyte
=
1.3 Qcm2 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
(equation (26)
ance
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]
shape
Cdl(Ke)
function
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
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
singlestep
ating points).
A discussion of
iQ
seems
reasonable.
as
impedance,
further
following
section.
3.4.2
Competition
Adsorption
to 773 K
Electrode conductivities.
(800C)
(500C) and
electrode
at
oxygen
on
partial
atomic oxygen
kinetics
[10,15,45,47,55,56].
Various
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
and T and
R^
function of pQ
is shown in
Fig.
3.16
(500C)
to 1073 K
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
are some
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^
clear pQ
conductivities, but
109
Implementation, Simulation,
and
Validation
10J
101
E
o
10
,i
10
,3
a)
fl/(Qcm2)
0.8
1.2
1.4
1.6
1.8
/ce/(Qcm2)
Fig.
3.15
Determination of
two maxima for
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
uncompensated
110
3.4
Simulation Results
more
than
one
decade of
pQ^. partial
pressures. The
gen
in
reason
for this
can
adsorption
occur
parallel,
of oxygen molecules and surface diffusion of atomic oxygen the pQ even near the tpb. Analytical solutions describing
105
L_
,_
10
101
102
103
104
105
Pon*
Fig.
3.16
Electrode conductivities
as
function of
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 statespace model M2 ((A, B, C, D) quadruple) at the corresponding operating point. The parameters
given in Table 3.1 were used.
Ill
Implementation, Simulation,
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
therefore also of R
can
be found in
[57]. Simi
,i
pressures
seen
is
obtained,
R
as can
be
in
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
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
[5961]. This
112
3.4
Simulation Results
phase
can
this.
by
Oad
dif
fusion
on
Pt
can
be obtained from
Arrhenius
plot
of Rl
.
(pQ +),
if surface
diffusion of
Oad
R~
1/2
temperature
we
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
maxima is almost
independent of temperature.
*
pendent
of
and Pq
for
R^
at
is
also
decreasing
values for
P (we
by
as
pQ
pQ
parameters
given in Table
3.1.
Fig.
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
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
enthalpy
of R~
(pQ t)
does not
becomes
AHad enthalpy of
R~
(pQ t)
comes
close to
AH^
at
energy of R~ (10
surface coverage
tures. At low
regime)
and
and it T
changes
kj/mol
p0
high
can
(low
surface coverage
kj/mol.
dependence
of the
be
*)
pQl
is the oxygen
partial
we use
this notation in order to avoid confusions with pQ obtained. Note that Mizusaki et al.
use
R^"1
is
the notation
ae*
for
expressing
pQ *.
113
Implementation, Simulation,
and
Validation
parti.
From the
M2
we
find
[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
cases:
(i)
low T and
high pQ (high
remaining
=
coverage: (1
x)
>
Eq. (3.29)).
We
expand
result:
the
fraction of
Eq. (3.29)
with
l/kdes
and
Jkad/kdes
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
obtain:
desd
=
(33D
45
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
enthalpies AH^
are
tures
(158kJ/mol)
and
decreases
with
Pt is
[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
115
Implementation, Simulation,
and
Validation
rather
large
mean
variation
(see Fig.
to
9 in
[45]).
It is
AHad,
as was
done
differences between
our
model M2
investigated by Mizusaki et al. [45, 47]. First, Mizusaki et al. assumed that the chargetransfer 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
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)
=
,
can
be
no
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
experimental
There is
[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
curves
is
seen even
at
overpotentials. Evaluating
slope
.
of small
overpotentials will therefore reveal the electrode not the inverse chargetransfer 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
=
below.
More information about the rate
limiting process is obtained from the pQ dependence of the limitingcurrent I,. For the system Pt, 02(g) I YSZ at high cathodic overpotentials, pQ and pQ dependencies of I{ have bee found [9,
is
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
Implementation, Simulation,
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.
l_i
it
0.1
0.05
0.05
0.1
r/V
Fig.
3.20
Simulated
JpOl) relationships
is
partial
pressure condi
Pa
tions at 973 K
(700C).The pQ
at
given
Pa
figure.
=10
10
dc
analysis
of the
R_
=
obtained:
Rt
10.5
Qcm2,
usually employed smallsignal data in the inset the following results are 29.9 Qcm2. 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 )
(p0J
behaviour
shown above
is dominated
ence
by
the
If
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
expect
pattern
strip width is
(10.. .100)
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
knowledge,
no
high temperatures. To the best corresponding experimental data are reported in the
kj/mol
must be from
literature
wise gas
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 Warburglike) semicircle at intermediate temperatures and at high pQ [15, 42,45,55,56, 61,62]. With decreasing pQ a second semicircle 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
Implementation, Simulation,
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.
limitingcurrent 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
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
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/2cm2)
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/Qcm2)
Fig.
The
3.22
same
Simulated
impedances
as
=
at T
973 K
(700C)
at
parameters
105
different
Pa and
(b) pQ
103
Pa for different
overpoten
121
Implementation, Simulation,
and
Validation
with respect to R
and the
shape
of the
impedance
,
arc,
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
be well
over
by
the
transfer resistance
Rt.
If the p0
is
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).
Rt
and R
obtained at
high
pQ
and
zero over
potential (Fig. 3.22 a) are in full agreement with smallsignal dc analysis in Fig. 3.20.
It
was
parallel process of 02(g) adsorption and Oad sur face diffusion was responsible for the limitingcurrent 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 logZF 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
adsorption process and that real electrodes should not show a firstorder 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
can
be observed in
spectra.
act
chemisorption
of oxygen
proceeds
via
physisorbed
reservoir. A
precursor states
more
dynamic
behaviour
[33].
122
3.4
Simulation Results
a)
co/(2tcs_1)
b)
co/(2rcs
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
Implementation, Simulation,
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 chargetransfer 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 chargetransfer resistp, should be
30
26
^
(S
a

??,
to
0.4
C!
**^
u.

18
14
oV(27ts_1)
Fig.
3.24
were
Sensitivity
of
IZpl
=
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
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
/^b experimentally
small range,
as
long
as
the
30
26
6
03
22
a
N
18
14
10l
101
w1
10J
10<
103
co/(2jcs_1)
Fig.
w
=
3.25
Sensitivity
of
IZFI
with
respect
as
to the
length
of the
tpb
active area.The 10
nm.
same
parameters
Fig.
used with
125
Implementation, Simulation,
and
Validation
high temperatures.
with the
question
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
sensitivity
nm
of
ZF
with
respect
to
(if
klc
const)
we a
can
klc
from EIS
measurements if
area w.
value of
(1...10)
would
w.
Practical cal
identifiability.
we
In
proved
the theoreti
identifiability
However,
sensitivity
must
be also
are
considered.
only
necessary
accurate
a
parameter
estimation. If
a corre can
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 3A.4 for more mathematical and computer implemen
generation
were
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)/(27lS_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
wklc
to 20
const.
the
figure).
different levels of
( ) corresponds
127
Implementation, Simulation,
and
Validation
Fig.
3.27
Correlation between
and
in
Table 3.1
were
used to
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(2Ks')
Fig.
sion
3.28
to the activation
of
operating
conditions.
Accordingly,
we
can
ZF
Oad, D,
is
high and,
can
be estimated
easily
the
dependence
a
of D
on
Oad
be
parameter
estimations.
Fig.
3.28
sensitivity S(Ediii)
ZF
Ediff.
that
frequencies.
3.5
Summary
and Conclusions
computer implemen
describing the oxygen reduction at interfaces between Pt and YSZ. The simulated steadystate and smallsignal 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
Implementation, Simulation,
and
Validation
Although
Oz(g)
I YSZ
seems
to be
quite
well understood
by far not a
analysis we
ability of the unknown parameters which proved ness for the practical identifiability.
We suggest the
ters
following procedure for the estimation of of model M2 describing the Pt, 02(g) I YSZ system:
(i)
Determine the
versus
charge
P from log(R^ )
values should
measurements
log(pQ ) plots
at 1000 K.
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

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
Ead
and
Edes,
as
well
asfcadand/cdes.
(iv)
From electrode with well known
length of tpb, no porosity, and known Pt surface area), obtain impedance spectra. Use the parameter
estimates obtained in
(i)
to
(iii) and
estimate
klc
with the
(v)
Estimate
D(Oad)
and
Ed
tiodes described in
(iv).
data and model
It is clear that
validation of
experimental continuously.
parameters
130
References
adsorption
and
desorption
of oxygen
a
on
the Pt
twoelectron trans
the
tpb. However,
interaction between
refined model.
02(g)
on
the Pt
detail,
as
magnitude over
the pQ
range considered. To
diffusion
fully describe
diffusion and
mass
(binary
can
be
easily
accom
plished
presented
in this paper.
centration
dependence
Acknowledgments.
The financial
portation,
thank sions. In
and Telecommunication is
gratefully acknowledged.
present colleagues
References
[1]
A. Mitterdorfer and L.
tem. Part I:
J. Gauckler. Theoretical analysis of the Pt, 02(g) I YSZ sys general framework, modelling, and structural investigation. /. Electro
[2]
[3]
Way, Natick,
Mass.
01760,1993.
[4]
[5]
G. N.
GrawHill Book
Vanderplaats. Numerical Optimization Techniques for Engineering Design. Company, New York, 1980.
L. Michelsen. Solution
[6]
J. Villadsen and M.
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Clarendon Press,
[7]
Oxford, 1985.
[8]
131
Implementation, Simulation,
and
Validation
[9]
Wang and A. S. Nowick. Cathodic and anodic polarization phenomena at platinum electrdoes with doped Ce02 as electrolyte: I. steadystate overpotential.
D. Y.
in
vestigated by impedance
[11]
M. Knudsen. A
tem
sensitivity approach for estimation of physical parameters. Identification, pages 533538, Copenhagen, Denmark, 1994. IFAC.
Sys
[12]
S. W.
Feldberg. Digital simulation: a general method for solving electrochemical diffusionkinetic problems. Electroanalytical Chemistry, 3:199296,1969.
S. W.
na:
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T.
Joslin and D. Pletcher. The digital simulation of electrode processes, procedures for conserving computer time. Electroanal. Chem. Interfac. Electrochem., 49:171186,
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[15]
M.
J. Verkerk,
M. W.
on
substi
tuted
ance
and
imped
[16]
D. Britz,
ary values in
ment.
applied
to several
[17]
gases
using
solid
electrolyte
/. Appl.
Electrochem., 5:177,1975.
[18]
Feldberg. Optimization of explicit finitedifference simulation of electro phenomena utilizing an exponentially expanding space grid. Refinement of the joslinpletcher algorithm. /. Electroanal. Chem., 222:101,1981.
S. W.
chemical
[19]
M.
moxed ConductorsProc.
High Temperature Electrochemical Behaviour of Fast Ion and Miof the 14th Rise Int. Symp. on Mat. Sci., pages 89116, Roskil Rise National Laboratory.
[20]
Siebert, A. Hammouche, and M. Kleitz. Impedance spectroscopy analysis of La1_xSr;i:Mn03yttriastabilized zirconia electrode kinetics. Electrochim. Acta,
E.
40:17411753,1995.
[21]
H. Lauret and A. Hammou. Localization of oxygen cathodic reduction zone at lan thanum manganite/zirconia interface. /. Europ. Ceram. Soc, 16:447451,1996.
[22]
1985.
132
References
[23]
T.
Kenjio,
Y.
contact area
Electro
[24]
D. Y.
Wang and
Au
electrodes with
doped
ceria
electrolytes. /.
[25]
Diffusivity
solubility
platinum
and PtNi
alloys.
[26]
N. L. Robertson and
on
platinum
electrodes in
zirconia cells:
J. Electrochem. Soc,
137:129135,1990.
[27] [28]
ing
[29]
solid
Armstrong and R. Mason. The double layer capacity measurements involv electrolytes. Electroanal. Chem. and Interfacial Electrochem., 41:231241,
Electroanal. Chem. and In
1973. R. D.
[30]
W. I. Archer and R. D.
Electrolytes,
[31]
1987.
[32]
N. L. Robertson and
J. N. Michaels. Double layer capacitance of porous platinum electrodes in zirconia electrochemical cells. /. Electrochem. Soc, 138:14941499,1991.
A. Mitterdorfer and L.
tem: state and
[33]
tional
J. Gauckler. Reaction kinetics of the Pt, 02(g) I cZr02 sys parameter estimation. To appear in Proceedings of the 11th Interna Conference on Solid State Ionics, Hawai, 1997.
L.
[34]
T.
Jacobsen, B. ZachauChristiansen,
In F. W. N.
Bay,
and S.
Skaarup.
M. Mogensen, and Poulsen, Bonanos, ZachauChristiansen, editors, High Temperature Electrochemistry: Ceramic and MetalsProc. of the 17th Rise Int. Symp. on Mat. Sci., pages 2940, Roskilde, Den mark, 1996. Rise National Laboratory.
anisms.
B.
S. Lindenroth,
[35]
C. A. Cavalca, G.
cation of
actor.
CH3OH
[36]
C. G.
Vayenas
and S. G.
Controlled Promotion
Neophytides. Electrochemical Activation of Catalysis: In Situ of Catalyst Surfaces, volume 12, pages 199253. 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
Implementation, Simulation,
and
Validation
Chemistry Symposia
Se
[38]
B. A.
van
[39]
F. Berthier,
faradaic
impedance
electrode reaction:
Application
measurements.
Corros., 51:105115,1995.
[40]
System
Way,
Nat
[41]
A.
J.
A.
Burggraaf.
ance
of
Zr02Y203(Bi203)
solid
electrolytes
14:319327,1984.
[42]
J. E. Bauerle. Study of solid electrolyte polarization by a complex admittance meth ode. /. Phys. Chem. Solids, 30:26572670,1969.
M. J. Verkerk, M. W. J. Hammink, and A. J.
[43]
tuted
sistance
and
[44]
through
observation of
exchange
current in a solid
[45]
J. Mizusaki,
Pt,
K. Amano,
S. Yamauchi,
and
K. Fueki.
02(g)/stabilized
analysis.
[46]
adsorption
on a
Pt(lll) surface.
[48]
J. L. Gland,
face.
Sexton, and G. B. Fisher. Oxygen interactions with the Pt(lll) Surf. Sci., 95:587602,1980.
B. A.
sur
[49]
Weppner.
Electrical
re
sponse of oxygen
sensing Ti02
Ionics, 2830:16371643,1988.
[50]
A. K. N.
Plenum Press,
[51]
ture
of
134
References
[52]
Adsorption
of oxygen
on
[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 (SOFCV), page 385, Pennington, NJ, 1997. PV 9740, The Electrochemical Society, Inc.
M.
A. Mitterdorfer and L.
[54]
J. Gauckler.
La2Zr207 formation
systems.
netics in
Lag 85Sr015MrL,03,02(g)
I YSZ
[55]
Raistrick, and R. A. Huggins. AC admittance measurements on sta bilized zirconia with porous platinum electrodes. Solid State Ionics, 1:251271,1980.
T. M. Giir, I. D.
[56]
J. Sasaki,
H.
Jpn., 54:16881692,1981.
[57]
G. Reinhardt.
Phasengrenzreaktionen an Perowskitelektroden auf stabilisiertem Zr02: Implikationen fur die Abgassensorik. PhD thesis, Universitat Tubingen, 1994.
[58]
P.
Fabry
the characteristics of the oxygen electrode reaction J. Electroanal. Chem. Interf. Chem., 57:165177,1974.
on
[59]
T. H. Etsell and S. N.
electrolyte
[60]
T. M.
fuel cells.
Giir, I. D. Raistrick, and R. A. Huggins. Steadystate DC 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. Diffusionlimited charge transport platinum electrodes on doped Ce02. /. Electrochem. Soc, 128:8289,1981.
[62]
H. S. Isaacs and L.
on
J. Olmer. Comparison of materials as oxygen catalytic electrodes zirconia electrolyte. /. Electrochem. Soc, 129:436443,1982.
on
[63]
J. L. Gland. Molecular and atomic adsorption of oxygen Pt(S)12(lll)x(lll) surfaces. Surf. Sci., 93:487514,1980.
A. C.
the
Pt(lll) and
[64]
face. /. Chem.
on a
Pt(ll 1)
sur
[65]
Franklin, J. D. Powell, and A. E. Naeini. Feedback Control of Dynamic Systems. AddisonWesley, Reading, MA, 1994.
C. F. Bernasconi. Relaxation Kinetics. Academic Press, Inc., London, 1976.
R. Gorte and L. D.
G. F.
[66]
[67]
76:559573,1978.
135
Implementation, Simulation,
and
Validation
Appendix
3A.l
Reaction Model Constants and Parameters
Table 3.1
Quantities
Symbols
area
Values
Units
Ref.
Apparent
electrode
104
0.7
m2
1
Electrolyte
coverage
^cov 'char
L
Characteristic
length
pm pm
nm
Electrode thickness
Extension of
20 10
tpb
Azx D0
4.65 155
10*
m2/s
kj/mol
[15] [52]
d
N0
v*d
1.6603
lO"5
mol/m2
s"1
[63]
109 io12
No
[67]
vdes
m2/(mos)
[67]
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]
[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
2106
0.62
m3/(smol)
1
Charge
transfer coefficient
Temperature
650... 1200 1 to
Oxygen partial
pressure
Po2
105
Pa
3A.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 statespace description for the circuit in Fig. 3.3 d
Let
us assume
1/Cdl(l/Re + 1/Rt)
l/(CRt)
l/(CdlRt)
1/C(l/Rt + 1/Rc)
[l/(CdIRe) 0] [1/Re o]
[1/RJ
(3A2.1)
with
x(t)
Uix(t)
m2(o]
"o
l/Re(u(t)ul(t)),
are
transposition.
137
Implementation, Simulation,
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 Qcm2 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"A22)
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. (3A2.2)). The result is shown in Fig. 3A2.1 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. (3A2.2) 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 chargetransfer 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 chargetransfer 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
=
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.
3A2.1
Comparison
of
tive
error
is
a
a
figure).
response to
3A.3
Implementation
In this
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
(Matlab:
are
1.3). The
3A.l
concern
appendix
need to
1 atm. There is
no
139
Implementation, Simulation,
and
Validation
Fig.
3A3.1
Simulink block
diagram
for the
adsorption/desorption dynamics.The
can
integrator
be followed within
any connection
AutoScale
will be most
Graph from the Sinks Block Library interesting to follow x (t)). Set the
parameters
sibility
is convenient in the
early stage
of model
Adsorption dynamics.
First, the
implemented
parameters
in
block
as
adsorption and desorption dynamics is diagram (Fig. 3A3.1; filename: simadsl.m). The
are
defined
p02
NO kad
=
1;
1.6e5;
in
units
of
(10^5
Pa)
1.8888e7;
=
kdes
4.3007e6;
is set to xO
(RungeKutta
fifth
is used with
le3;
=
minstep
le6;
maxstep
le3;
options
xO
=
[tol,
minstep,
maxstep];
0.65;
=
[t,x]
rk45('simadsl', plot(t,x),
1.5e2,
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
g10*
10"
0.2
0.1 etaA/
0.1
0.2
0.2
voltage/V
Fig.
ters
3A3.2
parame
sub
from Table3.1
evaluated
at
1000
and p02
a
atm.
plot (221)
for
equilibrium
ance
impedance and
V
the
imped
A (larger semicircle) double layer capacitance of Cdl 10e6 wasassumed. subplot (223 ) showsthe charge transfer resistance Rt and the polarization resistance Rp as a function of the overpotential eta. subplot (224) shows the currentvoltage behaviour of Ml.
at eta
and eta
0.8
(smaller semicircle).
The
subplot(221)
Graph
of
Fig.
dependence
of the surface
on
the The
AutoScale
block which
can
Library.
integration parameters
submenu.
be set
directly
in the Simulation.Parameters...
equilibrium value
X0
K*sqrt(p02)/(1+K*sqrt(p02))
141
Implementation, Simulation,
and
Validation
where
sqrt(kad/kdes)
The relaxation time for small
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
equilibrium
value, the simulated values for the relaxation time will deviate from the
smallsignal value.
Electrochemical reaction.
We
now
diagram (filename: simmodla.m). See the main text and Table 3.1 for a detailed description of kf, kb and the remaining parameters. Nonlinearities 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.
3A3.3
shows the
corresponding
We define the
following
A
=
constants
ac
0.62;
2.73e7;
8.314;
1000;
96487;
f kf
F/(R*T);
=
2.7474e3;
kb
5.7577e3;
can
not be chosen
independently
It is
good
equilibrium
state
within
(or very low values) due to the constraint linearized statespace 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.
3A3.3
Simulink block
diagram
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
important
recognize
given
argument
to
the function
zero
linmod. If
no
argument
given,
for
a
for
online
description
we
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
use
deliberately
as
"electrochemical
ance" because,
imped impedance" and not just "imped clear, we could analyse different
143
Implementation, Simulation,
and
Validation
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
impedance.
we
changed
the varia
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
=
10e6;
Re
10;
the
Z
w';%
transpose
+
frequency
=
vector!
j*w*Cdl
l./Zf;
Re
l./Y;
Let
us
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
Rp
l/(dc/a*b),
the
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
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*(lX0)
2*ac*f*kf*X0
+
4*kdes*N0*X0
kf
kb;
2*(lac)*f*kb*(lX0);
2*N0*F*A*(kb+kf);
dl=
2*N0*F*A*(2*(lac)*f*kb*(lX0)
2*ac*f*kf*X0);
which Let
us
are
equal to the a, b,
c, d
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',
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.
3A3.2
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 steadystate 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 statespace 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
f solve
from
145
Implementation, Simulation,
and
Validation
the
Optimization Toolbox).
We
see
that it is much
more
steadystate 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
Rt
and Rp
over a
range of
overpotentials
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
Maximum number
iterations
exceeded
increase OPTIONS(14)
In this
case
solution after
options vector
the online
that any
help (help
foptions; help
should be taken
The results
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 steadystate currentvoltage 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.
3A3.4
Simulink block
diagram
of Ml for simulation of
currentvoltage
behav
iour.The
port is
Subsystem contains the block diagram given in Fig. needed to plot the data in an I (U) diagram.
Sequence
Library
is used
as
input
and
second
outport is used for the feedthrough of the input (cf. Fig. 3A3.4; 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
sideration).
dt
100;
du
=
0.3;
TF
4*dt;
TF,
[T1,X1,Y1] [le3,
If
=
gear('simmodlb',
TF/20]);
=
X0,
...
TF/1000,
V
Yl(:,l);
Yl(:,2);
subplot(224),
plot(V,If),
grid
The results
can
ing
The
step response
we
to
an
potential step at the input can be simulated as shown and Re play a significant role in the timedependent
IV
curve
behaviour
must
just
adsorption
near
the
tpb,
play
significant
supply of atomic oxygen. Surface diffusion of atomic oxygen the tpb must be taken into account when investigating the kinetics of
gas electrodes.
147
Implementation, Simulation,
and
Validation
3A.4
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
are
taken from
=
Table 3.1 of
appendix
973 K and
p0z
103
Pa.
SPARCstation 5
operating
were
Programme
ters
initialization.
Aelectrode
Acov
le4;
% %
apparent
electrode
area
=0.7;
=
electrolyte
coverage
Lchar
2e6;
characteristic
*
length
%
tpb
R
F
=
4*Aelectrode/Lchar
%
% % % % % %
sqrt(1Acov);
constant constant
constant
Eq.
(2A2.2)
8.314; 96487;
=
gas
Faraday Avogadro
Na T
=
6.023e23; 973;
=
temperature
in units
of
in
units
of
p02
Voo
le2; 4.65e3;
4.45e4;
(10^5
Pa)
oxygen oxygen
vaccancy
concentration
Oox
ion
concentration
The
penetration depth
=
8 is obtained
as
DO
4.65e4;
=
surface
diffusion constant
energy
Ediff
D
=
155e3;
activation
surface
D0*exp(Ediff/(R*T));%
=
diffusion
coefficient
wmax
exp(21.1114150/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
10e9; 2;
% % % % %
width
of
tpb compartment
guess
qO
n
=
starting
number
of
10;
=
compartments;
dzl
A
=
10e9;
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"(kl);
where
'compart'
f
is
function f
=
compart(x,dxl,delta,n)

dzl/delta
(1x)/(lxAn);
The
midpoints
of the compartments
are
obtained from:
for
pp=l:length(dz),
=
Zaxis(pp)
end
sum(dz(1:ppl))
dz(pp)/2;
(Eq. (3.9))
are
obtained
as
Tdiff
dz.A2./(2*D);
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*(EdesEad);
enthalpy
We
now
quantities:
149
Implementation, Simulation,
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));
(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((ElfElb)/(R*T))*Voo/Oox*K);
EeqP
=
l/(4*ff)*log(p02);
EeqT
+
Eeq
EeqP;
and
klfEq
klbEq
klfChem*exp(Elf/(R*T))*exp(2*ac*ff*Eeq); klbChem*exp(Elb/(R*T))*exp(2*(1ac)*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
(threeterminal measurement):
1.63e2*exp((0.78*1.602e19*Na)/(R*T))*le2;
*
0.5
l/sigma*0.5e3/le4;
150
Appendix
At
zero
coverage is
xO
x
=
K*sqrt(p02)/(1+K*sqrt(p02));
ones(n,1)*x0;
%
surface
concentration vector
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
dif
partial
pressure.
The
workspace
where
appropriate.
diagram.
In
Simulink block
Eqs. (3.10)
to
(3.12) the
mass
balances
were
given
block
diagram
of Ml
compartments. We start our considerations with the (cf. Fig. 3A3.3). 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. 3A4.1. Note how we
con
added the terms for surface diffusion and that the electrochemical rate
stants
defined
were
slightly
different than in
Fig.
kf and kb
obtained from:
kf
klfEq*Voo;
kb
klbEq*0ox;
Using
as
1000
Kandp02
we
obtain the
same
appendix 3A.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
compartment
to
(i). The
same
(compare
the
(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
an
intermediate sub
remaining part.
151
Implementation, Simulation,
and
Validation
Oad(1)
Oad(2)ad(2)
l*^*"^
eta(t)
Fig.
3A4.1
diagram
for the
tpb compartment
is the
of M2.We
used
the
block
diagram
process
IF
(marked
(t) is the
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
3A4.2
Simulink block
to the block
corresponds
diagram of M2 with four compartments.The tpb subsys diagram shown in Fig. 3A4.2.
152
Appendix
tions of the
integrator
for every
appropriately
subsystem. For clarity the block diagram of subsys tem 2 is given in Fig. 3A4.3. 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
con
(note how
defined the
In order to be able to
run
simulations of M2
we save
create
diagram
mode 12
with ten
.
(n
10) compartments. We
name
m.
Fig.
be obtained.
We
begin
T
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;
+
20e6;
Re
+
j*w*Cdl
l./Zf;
l./Y;
Oad(2) Oad(1)
Oad(3)
Fig.
3A4.3
Simulink block
diagram explanations.
for
compartment
two of M2
(subsystem).See
153
Implementation, Simulation,
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
=
give
the
curve
shown in
resistance
Fig.
for
the
polarization
973andp02
=
(Rp
l/dcgain(a,b,c,d)
of
in
Fig.
It is
eta
3.16forT
more
interesting
to the
to consider
situation where
we can
cathodic
overpotential
is
imposed
system.
Note that
not
eta), because
the
eta
0.035;
=
as
in
Fig.
3.22
options(2)
le6;
options(4)=le8; 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
use
loop
always
find
solution
vec
X, the
input u
and
the output
Y.
by typing:
x
=
0.1278 0.1388
154
3.5
Summary
and
Conclusions
0.1536
0.1718 0.1907 0.2059
U
=
0.035
Y
=
3.2038e04
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,
can
be obtained
follows:
>>
[str,xo,info]
info
'
model2;
>>
model2/Subsysteml/Oad'
'model2/Subsystem3/Oad'
'model2/Subsystem4/Oad'
This order is
obviously
in
X.
The concentration
profile
of adsorbed oxygen is
easily
obtained with:
plot(Zaxis,
sort(X));
We
can now
as
follows:
[al,bl,cl,dl]=linmod('model2',
X,
eta);
155
Implementation, Simulation,
and
Validation
integrator
x
blocks
are
used
by
the
to
plot
the results.
procedure as above can be used Compare again with the curves shown in Fig. 3.22.
xo.
The
same
Similarly, currentvoltage simulations can be obtained as described in appen dix 3A.3. Limiting currents are determined with trim using high cathodic overpotentials (cf. Fig. 3.21).
156
Part
III
La0.85Sr0.15Mnt/3+5
and
YttriaStabilized Zirconia
158
Chapter
Lanthanum Zirconate
Formation
and
Oxygen
Reduction Kinetics
Abstract
growth of lanthanum zirconate (LZO) between (001) single crystals of 9.5 mol% Y203stabiUzed Zr02 (YSZ) and 0.95... 1.10) perovskites were porous La085Sro.i5Mny03g (y investigated. The perovskites were screenprinted on the solid electrolyte and sintered in air at 1373 K for short periods. High
=
Nucleation and
resolution
transmission
electron
microscopy, electrochemical
force
microscopy
were
The manganese
concen
perovskite
growth
LZO
rate
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 Asite deficient perovskite is char acterized by the reductive dissolution of Mn into YSZ in the early
*)
La2Zr207
Formation
and
02
Reduction Kinetics
sintering stage
and
by
pronounced
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
are
triple phase
are
impedance data.
strontium
Keywords.
(SOFC).
Lanthanum zirconate
(La2Zr207); lanthanum
manganite;
oxygen
4.1
4.1.1
Introduction
General
ion
conducting YttriaStabilized Zirconia (YSZ) and perovskitetype Srdoped 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
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
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
(La2Zr207,
abbr.
(SrZr03,
abbr.
SZO)
are
employment
activity for
extent
of Co and Fe
containing perovskites
at
high
electrochemical
SOFC
on
operation
intermediate tempera
or
tures will
the
ability
to
control
4.1.2
Lau and
Microstructure and
Chemistry
Singhal [2] first reported pyrochloretype La2Zr207 formation between diffusion couples of dense Lag 9Sr01MnO3 and (ZrO2)0.8(YOi .5)0.2 single crystals. La2Zr207 and perovskitetype SrZr03 have been found to form at interfaces between YSZ and (La,Sr,Ca)Mn03 at high temperatures in
air
or
[34]. The
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]. Asite 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 Xray 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;
was
raised to
(1300C), lanthanum
found to be
In
considerably less
an
ichiometric material
addition,
induction
period
for zirconate
formation
was
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
Mn3+
in the
perovskite
case
in presence of zirconia.
Thermody
lanthanum
of
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
[1516]
that when
La2Zr207
is formed
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
perovskite phase, whereas the ensures the large solubility into YSZ
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 (1013 to 10"12) cm2/s at
1673 K
(1400C) and
two
orders of
magnitude higher
[2].
This
large
calcu
equilibria
calculations
by
Yokokawa et al.
be dissolved up to 11.4%
(2.1%
as
(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
=
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
to be
Also
migration
perovskite
observed
[6,8].
4.1.3
Influence
on
on
Electrochemical
Properties
type
The literature
and amount of
foreign phases
=
comparison
(1000C)
to thermo
Yamamoto et al.
the
cur
rentoverpotential 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
Xray
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 IversTiffee 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
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
YSZLaMn03
in air.
(1000C)
to 1573 K
(1300C)
They
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 Qcm2) and where it is experimentally difficult to impedance
measurements up to
quencies. Using
more
lower
We will
give
brief review
the present
knowledge
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
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
manganite
activity by
means
doping
rather detailed
picture of the
microstructure and
microchemistry
the
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
these
164
4.1
Introduction
dense
pellets
of mixtures between
tion resistance
ues
upon
increasing manganese
In
developed
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
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 Asite 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
work
was
to
investigate
stoichiometry
in
La0.8sSr015Mny03 (LSMy)
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 screenprinted 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) Xray 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 heattreatment. Electrochemical
was
employed
to monitor the
165
La2Zr207
Formation
and
02
Reduction Kinetics
growth
of LZO
depending on the stoichiometiy of LSMy. Surface diffusion of cations was predominant in case of nearstoichiometric and Asite deficient LSMy. LZO islands formed predominantly at the tpb which caused an increase of the cathode resistance. The chargetransfer reaction was found to be not rate determining at temperatures below 1173 K (900C). The electiode
found
resistance
was
sur
4.2
4.2.1
Experimental
Procedures
Sample Preparation
couples
were
prepared from dense YSZ substrates and porous per ovskite layers. Single crystals of 9.5mol% Y203stabilized 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%) (Furan2carboxylic 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)24H20 (Fluka AG, Buchs, CH) (dissolved in ethanol) in appropriate amounts to the LSM0 98 powder before preparing the
paste. This procedure
ensures
homogene
Table 1
organic paste.
166
4.2
Experimental Procedures
Table 4.1
the cation
Characteristics of the
ratio
screenprinting pastes
to
used in this
cation
(column 3) refers
paste.
the
nominal
that
the the
screenprinting
LSMy
(y
102)
screenprinting
pastes
of
Sample
LSMa95
Description
SSC, Inc., calcined 1223 K for 2 h,
ball milled
Mn/(La
0.95
nSr)
LSM0.98
0.98
LSM102
LSMg 98
with additions of
1.02
Mn(N03)24H20
LSMy (y
>
1.02)
>1.02
summarizes the
were
screenprinting pastes
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
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
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. Homemade 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 curyintrusion measurements (model 2000, Carlo Erba, Italy) on 0.12 g of sintered screenprinting 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
were
stable
against hydrochloric
acid whereas
LSMy
rapidly.
4.2.2
Investigation
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
square
pyrami
dal
Si3N4 tip
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
foreign phases
were
obtained.
analyses were conducted on YSZ surfaces. Electron transparent sam ples were prepared by dividing, polishing, and argonionthinning. Follow ing standard procedure of mechanical prethinning of crosssectional 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. Planview
samples
were
mm
dimpled from the substrate side to a final thickness of 20 pm. In both instances, final thinning to electron transparency was done by argonion beam thinning. Micrographs were obtained with a HRTEM (model CM30, Philips) operating at 300 kV.
diameter
using
an
Energydispersive Xray 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
were
recorded in
=
1253.6 eV). Using an electron takeoff system using Mg Ka excitation (hv angle of 43, the analysed surface area was 1.5 mm2. Sputter depth profiling
was
performed using
sputter
rate
was
calibrated
3.7nmmin1
for
Si02.
The
sputter
Zr02 and Si02 is 0.46 therefore giving a sputter rate of 1.7 nmmin1 for Zr02. The depth profiles were acquired as a set of discrete sputter cycles inter
rupted by
reported
here
were
calculated
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 twocomponent binder (type 1500, Firag, Ebmatingen,
Perovskite
screen
printing paste
in order to have
good
wires
layer
(0.35
mm
diameter)
were
prepared from Pt paste (C 3605 P, Heraeus GmbH, Hanau, FRG) where we first dcsputtered 50 nm of Pt on the YSZ surface (model SCD 040, Baltec, Balzers, FL). The inplane conductivity of unsintered and sintered cathode layers, as well as the conductivity of dense cathode material, was measured with fourprobe measurements. The layers were screen printed on
trodes
were
rods
(3x3x40 mm).
were
Pt wires
were
used
as
Electrochemical measurements
conducted in air
to 1373 K
temperature range of
723 K
(450C)
cooling cycles. Steadystate currentpotential curves and electrochemical impedance spectra were obtained (Model IM6, Zahner GmbH, FRG) in a threeelectrode, fourlead 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
steadystate I(r\)
curve
at rj
0. A further
analysis
of
impedance
data will
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
after
only
15 min of
sintering.
The average
grain
on
depending
the
sintering period.
Fig.
4.1
SEM of sintered
LSMT
02
cathode
on
YSZ
was
sin
tered at 1373 K
(1100C)
in air for 2 h.
(a)
(b)
Necks
02
grains
LSMj
grains
formed
during sintering.
170
4.3
Results
grains,
as
well
as
at the
interface
grains
(Fig. 4.1b). SEMEDX 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
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
LSMQ 9g
LSMQ 9g
i
(+4% Mn)
i
10^
0.8
1.2
1.4
103K/T
Fig.
4.2
of
LSMy
cathode
layers
in air.The
in air, held for 2
screen
printed samples
(950C)
h, and
subsequently cooled to room temperature with 3 K/min. For comparison, the electrical 4probe 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
sintering
=
at 1373 K
=
(1100C),
where the
observed
content
mean
0.32 pm to d
0.5 pm. We
by
higher
their manganese
was.
40% at
excess.
sintering temperatures
study
with y
0.95 to 1.10
were
single
phase perovskites
ther
phase in sintered cathodes by Xray 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 screenprinted 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
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
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
of
sputtering.
(~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
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
(composition
of 'as received'
approximately
constant
over
the first 20
nm
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.
sample)
result. TEM
was
care
must be taken in
interpreting
this
images
4.4
of
as
described above,
shown in
Fig.
4.4
Even under
low of
magnification
a
(Fig.
a)
grains
new
phase
which
cover
entirely. Fig.
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
surface.(a) Bright
field
image
of LZO
grains
of uniform
ulated
(right side)
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
(oxygen parameter:
0.295).
174
4.3
Results
Fig.
4.4
zirconate
grain
in
[Oil]
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
La2Zr207
caused
as
with
region and compares with sim axis of [Oil]. The wide and intense
parameter which
is 2.08
by
fee with
unit cell
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
integer)
present
LZO
weak when
are
is
even
[31]. Although
are
the
in
{200} reflections
the SAED
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)
grains
shown in
Fig.
epitaxially
on
{001}LZO{001}YSZ
<100>LZO<100>YSZ
which is in
(4.2)
the
LZO reflections
splitting of the reveals that the epitaxy is not perfect, but that a slight misoriresults
[17]. Finally,
grains.
It
was
not pos
grains reliably
grains
a were
with
grains; however,
the concentrations of La
adjacent
our
below
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) 2dimensional
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.
profile
and HRTEM
images
of the
grain.
grain
shows
which is
to the
Fig. 4.4c).
investigated
covered with
few atomic
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.
topography of the
same
YSZ
sample
of the
surface. It is
seen
from
the AFM
image
in
Fig.
grains
are
preferen
which is
size
tially
in
orientated with
respect
(001)
average
height
of the surface
layer
shown in
Fig.
4.5b is
(18
3)
nm,
in
Fig.
grain
of the LZO
grains
is about
(120
40)
nm.
Nucleation of LZO
grains
occurred
grains facing
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.
as
function of the
we
sintering
time
=
With
x=(183)nm
at 1373 K.
and
t=2h
estimate
logD/(m2s_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
at 1373 K
(1100C)
layers
of
YSZ. It is discernible that the islands grow in between the cathodes and the YSZ surface towards the cathode. The cubelike 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
cubeshaped
scale,
the
right
denotes the
(a) Epi
nm an
grains (1)
on
top
sintering
at 1373 K
(1100C)
(0.50.1) pm
height
parent
is 35
approximately
phase.
60
nm
relationship
grains
with the
(2)
tpb
178
4.3
Results
Fig.
4.6
(continued) (b)
is
Same situation
nm
as
in
(a) after
12 h of
is
surface level
at
135
height
125
of
cubeshaped
in the
z
(Fig. 4.6b).
ences
figures
Fig.
was
estimated
numerically
from AFM
images
sintering
period.
the
The
of the
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
on
the YSZ
In this way
can
hav corresponds
to
an
be
compared
a
with those of
as
LSM0 95.
case
The
growth
height
follows
different law
in the
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
unr\
"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
Fig.
4.7
were
obtained
by
Fig.
4.8
shows
bright
field TEM of
LZO island. A
as
sharp boundary
dislocation net
com
well
as a
grain boundary,
can
be
seen.
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.
(averaged
islands)
(40.30.1)% for
Y)
ratio is therefore
equal
to 1.14 at
larger
amount 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
compared
with the
original
few also
181
La2Zr207
Formation
and
02
Reduction Kinetics
Fig.
4.8
Bright
on
was
sin
axis
parallel
to the electron
magnification
of the upper
right edge
Fig.
4.9.
investigations.
were case
often
with
hightemperature
a
Again,
as
in the
LSM0 95,
were a
we
(Fig. 4.9)
10
that all
investigated
LZO islands
covered with
layer (<
nm)
of material of cubic
symmetry with
zones
unit cell
are
found to be
1015 atomic
inhomogeneous in thickness. Relatively layers) are found at the top of the islands
grains
and the LZO islands is
can
thick
(up
to
supposed
to the
Very
is
thin
regions (13
Note
atomic
layers)
again
phase
surface
layer
con
dislocations
can
be
seen.
(y
1.02).
a
Fig.
4.10a shows
an
AFM
image
of
was
sintered with
porous
cathode
at 1373K
(1100C)
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
right
area is
of the
Fig
of
a
4 8
covered
thin
layer
cubic
phase
with
of LZO.
183
La2Zr207
Formation
and
02
Reduction Kinetics
phology
can
sintering.
a
From XPS
measure
investigations
we
rings
which formed at
defect
early sintering
obtained
times consisted of
Mndoped
and
YSZ with
high
Mn
density.
over
were
(13.8
0.8)% Y, (78.7
near
1.6)% Zr,
at 1373
(7.4
1.0)%
(average
in
K).
clearly
in
see
Fig.
4.10b.
increasing sintering
was
typically prolonged sintering (> h), we found again cubeshaped islands on top of the zirconia rings (Fig. 4.11). The change in morphology towards the cubeshaped islands can be well observed from this image. After
z
in
(cf.
scale bar
Fig.
the YSZ
~5nm.
After
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
after
sintering with
area.
cathode.Mn nitrate
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
original
YSZ level is at
=0
nm.
two orders of
magnitude
case
of
LSM0 ggwe
From the
morphological
we a
images
supposed
To prove this
hypothesis,
investigated sample
In
some
of these
samples
with the
large
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]
intense diffraction
peaks
reflections index
as
lattice
parameter 1.98
sample
of
sputtering.
probes
in this
case
only partially
field TEM of
Both island
Fig.
4.13a shows
crosssectional
12 h of
bright
ringshaped
show
a
during
and
a
sintering.
tips
sharp boundary
top
different contrast.
185
La2Zr207
Formation
and
02
Reduction Kinetics
From HRTEM
it is
seen
that the
tip
consist
was
mainly
of lan
cZr02.
This
also confirmed
[Oil]
patterns
as
phase
was
determined
parent
was
tively.
In addition,
we >
investigated
AFM
(001) YSZ
with
and
LSMV (y
and
1.02).
at
investigations
no
sintering
LSM}10
12 h
LSMX16
showed almost
1373 K.
of
sintering
Occasionally, cubeshaped
no
Fig.
4.11
02
Density
cathode
z
sliced AFM
image
nm.
longterm sintering.The
of the
a
LSM!
areas
was
at the
typical
orientation rela
tionship
with the
(001)
YSZ
single crystal
surface.
186
4.3
Results
Fig.
4.12
Bragg
on
contours.
4 h at 1373 K.
as
clusters of
with the
rings.
steps
be
clearly
seen
(marked
white
arrow).
corresponding
SAED
pattern.
Fig.
4.13
TEM of
cross
section of
ringshaped
island. The
12 h at 1373 K in air.
(a)
(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/Qcm2)
Fig.
4.14
of
the
electrochemical
impedance
of
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
U^
YSZ
o
o
40
o o
11
3
o
34.
o o
20
"
107
10k^i<^
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 smallsignal ments at equilibrium potential were in accordance with the R
from EIS measurements,
dc
measure
determined
below
that
no
polarization
losses occurred
Fig.
4.16 shows
Arrhenius
plot
of the cathode
below
significantly
are
lower than
AH^
AH^
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
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
dependencies
partial
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)/(2ixs1)
10J
7"=974K
50
10^
101
b)
10l
10
8o
o.o.P..P0.0
1
10
101
10z
10J
10*
10
m/(2ns~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/(2rcs_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.
before
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
<5e
<*=
pQ
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
it
o
m
=
10"
0.38
0.44
'02
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 i5
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
leastsquare
fits of the
experimental
data
over
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
io2 IO2
lO1
10
101
10 11
CO/(27lS_1)
*
IO3
IO4
IO5
(0/(27IS_1)
x
8 Pa
\
"

310Pa
A
'''
S
o
40
105Pa
,''",'''
00
^^~
\\
\\
00
40
f
9
20 20

\
IO2
10"2
IO1
10
IO1
IO3 104 b)
(0/(27tS"1)
a)
(jn/(2ns~l)
Fig.
4.18
of the electrochemical
impedance
of
LSM098 cathodes.Unsintered
cathodes
at
(a)
CO
873 K
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'
..]
.
. . .
2.8103Pa 105Pa
10u
IO4
10"
IO2
10J
10'
IO2
IO3
IO4
IO3
0)/(27ts')h
CO/(27tS_1)
O
m
80

14 Pa

R
H
"v,.*
60

5
^
180)
60
*
^^
80)
/
/
/ K / /
^
/
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
IO1
d)
10
10'
IO2
IO3
IO4
IO5
c)
G0/(27IS')
(0/(27IS_1)
Fig.
at
4.18
(1100C) for
2 h in air at
(c)
1123 K
(850C)
and
(b)
at 893 K
are
given
figures.
4.4
Discussion
4.4
4.4.1
Earlier
Discussion
General
investigations
layer of lanthanum zirconate causes the deterioration of the oxygen reduction properties of the cathode. It was concluded from XRD measurements that Asite 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
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
tpb drastically
properties
of the electrochem
can
ical interface. For the first time it has been shown that the AFM
be
suc
197
La2Zr207
Formation
and
02
Reduction Kinetics
4.4.2
growth.
Sintering
(1100C)
of porous
LSM0 95 cathodes
on
at 1373 K
immediately
finegrained, homogeneous layers of Larich 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
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
LSMy
is
chemically
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
can
be drawn about
growth (cf. Fig. 4.19). phase diagram of the Zr02La203 system [34].
La2Zr207
exists and has
a
At
temperatures below
2100 K,
La203 concentrations, pyrochlore coexists 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
by
or
by
hypothesis
was
vaporizationcon supported
grains
at the
by beginning
rapidly
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
only
to
minor
extent
(ratio 10:1)
bulk
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
result
we
obtained. Nevertheless,
they
than
did, and
et al.
Brugnoni
a)
I
(001) YSZ
200
nm
b)
Zr
4+
Fig.
4.19
layer
LSMq 95
and
YSZ.(a)
Nucleation of
epitaxial
the
LSMq 95 grains.
Growth of
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
Subse
La3+,
199
La2Zr207
Formation
and
02
Reduction Kinetics
region
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
few atomic
phase
on
high resolution images of this surface region with experimentally obtained high resolution images of YSZ, we conclude that the surface layer consists of cubicstabilized Zr02 (cZr02). 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 cZr02 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 35 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+
cZr02 layer
From the
found
on
the LZO
grains:
excess
reacts with
oxygen to intermediate
is
cZr02
when sufficient
La3+
present.
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
growth.
Sintering
(1100C)
on
of porous
LSM0 98 cathodes
a
on
at 1373 K
few minutes
epitaxial, cubeshaped
images
we
LZO
grains
the TEM
between the
LSM0 98 grains
200
4.4
Discussion
clearly
visible cube
shape
on
the
crystal
grains
ance
surface. It is
are
likely
the
of the LZO
parallel
to
depend
on
sample
as an
probe,
i.e. it
we
can
not be
considered
with
polished
YSZ
polycrystalline samples
when the LZO
was
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
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
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 YSZLSM phase boundaries that LZO place at the interface. This does not agree completely with
findings,
but
they
late state of
can
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
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
relatively
low sin
tering temperatures
(see
and
a
occurs
predominantly by surface
and references
diffusion of cations
textbook about
are
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
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 cZr02. 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 cZr02 are seen on the side walls of the LZO grains, whereas a relatively thick region of cZr02 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 cZr02 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 cZr02 of
situation
was
we
would
growth
activity
islands
increasing time,
in the
is
supposed
to increase
markedly
we
vicinity of
growth
near
front
the LZO
distinctly below by
TEM
or
1% and
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
zZr02 + [(5
5')/2
3z/4]02(g)
(4.3)
In order to
(La1_x_2Sry)Mn03_8. + (z/2)La2Zr207
originated
from the Asite
nonstoichiometry.
reacts with
(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
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.
in the
significant
oxygen vacancies
order of
[38] which
at 1173
magnitude
K) and
203
La2Zr207
Formation
and
02
Reduction Kinetics
considered
as
mixed
In
ptype and
temperatures
above 1000 K
[38].
higher
Let
us
indicating
facing
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
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
screenprinting paste.
It is
excess
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
interface, it is surprising
after
to see
how the
magnitude
of
transported
YSZ
even
only (2
to
4) h
at 1373 K
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 Mndoped YSZ rings is almost equal to the nominal ratio of the YSZ, indicating that the surface diffusion of Y is not sigbehind
particle
204
4.4
Discussion
Fig.
4.21
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
sintering
(c)
necks until
La203
forms which
(b)
reacts
tip
necks
Further
growth
nificantly hindered,
as one
previous
case
where
dissolution
from
the
perovskite
into
the
YSZ
heavily
place
can
expected (7%
205
La2Zr207
Formation
and
02
Reduction Kinetics
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
nonequilibrium methods,
topographic
con
[001]
planview
a
(Fig. 4.12).
the SAED
The SAED
pattern
Fig.
4.12b shows
sample superposition of
TEM
patterns from the YSZ matrix, the MnYSZ islands, and the LZO
strong reflections
are
nuclei. The
intensity
that
type.
It further is known
Mndoping
nm.
slightly.
given by
0.513
Yamamoto et al.
[5]
we
estimate
decrease of a0
0.514
nm
to
This
change
prisingly,
only
~2 times
larger
than
(instead of
almost
2.09
times).
From the
Fig. 4.12b,
an
perfect overlay
pattern
cates
can
can
although not strainfree. 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
(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 cubeshaped LZO grains (cf. Fig. 4.8). But in this case, the lattice constant
of the LZO islands
was
During sintering
This leads to
soon as a
at 1373
only be maintained by the reductive Eq. (4.3)). This leads to the nucleation of LZO grains on top of the MnYSZ 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
206
4.4
Discussion
perovskite,
images of
took
i.e. the
the
supported by the HRTEM tips of the MnYSZ rings (Fig. 4.13b). Although LZO formation
supply
of La. This is also
place
at the
of
cZr02 can be
seen.
4.4.3
General.
Oxygen
98/YSZ
Interfaces
experimental studies (see e.g. [28, 4046] YSZ have on the oxygen reduction of Sr or Cadoped 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 multistep reaction [4547]. Adsorption of oxygen
Although
number of
[46], ing
[40,45,48]
sion of oxygen
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
argued
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
adsorption
process
on
on
oxide materials at
is
completely
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 ratelimiting 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
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
magnitude
it
ity
we
is
expected
that the
polarization
conductivity
of unsintered
and sintered
LSMy
cathodes is
considerably less than one order of magnitude the conductivity measurement we can see that
as
low
as
1223 K
(950C)
is sufficient to
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 (5106 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
polarization resistance of perovskite cathodes (see e.g. [5254]). 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
At
873 K
(600C)
we
find
pQ
dependence
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
measurements
were
obtained at tem
K
a
(1000C).
onequarter power
reac charge tion, where the dissociative oxygen adsorption obeys the Langmuir isotherm [55]. The same pQ dependence has been often found with Srdoped LaCo03 perovskites (see e.g. [40]). In contrast to these conclusions we have to assume
dependence
generally
transfer controlled
from
our
(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 microkinetic models have been employed to
In the
theory
of the electrochemical
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 [58,6062]. 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 smallsignal 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 currentoverpotential 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)
chargetransfer resistance Rt is a further important quan tity. The well known exchangecurrent 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 steadystate 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
=
chargetransfer
polarization, Rc
to chemical
can
be attributed
or
processes
on
on
to mass
transport processes
phase.
211
La2Zr207
Formation
and
02
Reduction Kinetics
are
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
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)
mated
as
1.3
pF/cm2 and
it
was
oxygen
an
partial
expect for
unsintered
we
sintering,
area
is
we
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 "pseudocapacitance" [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
06
. ...^ /.
a
g1
0.8
ZF(j(D)
ZCjco)
1.0
10"1
10
101
102
103
104
105
Q)/(2tcs"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(lj)
RT
=
\n F
CqJ2D
a>1/2x(lj)
(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
By
p02
dependence
same
213
La2Zr207
Formation
and
02
Reduction Kinetics
Pt,
Oz(g)
misleading
to
use
results obtained
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
dependence
of ae at low oxygen
partial competi
charge
behaviour at oxygen
partial
pressures between
(103...105)
Pa and
tempera
......
7= 1123 K
II
II
rn
i
1 1
Z(jw)
LH /?,
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/(acm2)
=
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
reaction
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
on
YSZ.
By
the
contrast, if
we
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
we
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 semicircle develops (Fig. 4.26) at low frequencies (from 1 mHz to 1 Hz) with decreasing pQ The resistance
is
.
towards pQ
showed almost
no
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
= = ,
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/Qcm2)
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
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
we
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
on
this
impedance
interface.
Towards reaction mechanism of sintered interfaces. both the
Fig.
4.27
shows of
a a
impedance
an
the Faradaic
impedance
At
interface at 893 K
(620C)
in oxygen. The 20
spectrum
semicircle at low
frequencies (<
(cf.
Hz).
high
fre
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
be observed from 1 kHz to 10 kHz, which is also reflected in the 45 the real axis in this
It
seems
that the
co
dependence
quency
ent
spectrum of
a
(compare
from
co
dependence of ZF
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
firstorder
(electro)
means
reaction
the
perovskite
[64].
"Firstorder"
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/Qcmz)
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
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
dynamics.
are
Due to
coupling
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" semicircle, i.e. that the semicircle 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
04
o
o
E
o
0.6
o
o O
O
g(izi
o
V
0.8
w
v.
o
o.'.
**
5
^O
ZpCJW)
Z(ja>)
"
IO"1
a)
10
IO1
IO2
IO3
IO4
10
CO/(27CS_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
04
o
g
o
0.6
o0 o
08
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
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
we
the associative
seen
adsorption step,
spectra.
responsible
impedance
in the
LSM0 98
we
at low
temperatures, and
will
finally
address this
We have
seen
by surface diffusion of an atomic oxy gen species at T < 1123 K (850C). With increasing T, a competition between chargetransfer 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
chargetransfer, 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
expected
O
at
are
adsorption tpb
and dissociation
acts
as a
step
are
coupled
the
surface diffusion
(3)
and
finally layer 8 is
electronated and
in
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
tpb
final electrontransfer
librium concentration of O
O is
on
compared
to the concentration
tpb
considerably retarded,
the direct
Accordingly,
supply
of O
via the
adsorption/dissociation
process becomes
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
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,
LSM0 98
grains
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
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
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
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
into O"
e"
20"(ad)
(or LZO) surface, before
reaction
near
(4.6)
it is
on
the LSM
in the
chargetransfer
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 microkinetic 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 rentproduced 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
we
be
sintering temperatures
excess
to 1373 K and
with
manganese
growth of the lanthanum zirconate. investigation of the LSMq 98, 02(g) I YSZ system
Dissociation adsorbed oxygen ions,
we
mechanism at
LSMy/YSZ interfaces.
sur
on
the
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
state and
parameter
estima
tion of the
are
available
perovskite
surfaces. Fur
area
investigations.
Acknowledgments.
portation,
The financial
and Telecommunication is
gratefully acknowledged. The authors are very who performed most of the HRTEM measurements.
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
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gesellschaft mbH.
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Tsuneyoshi,
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Tagawa,
K.
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and
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tem. Part II:
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J. Gauckler. Theoretical analysis of the Pt, 02(g) I YSZ sys Implementation, simulation, and validation. J. Electrochem. Soc, sub
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ganite
SOFCcathodes.
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
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
work in this
area.
Outlook
5.2
art as
science.
a
Apart
persistence,
and luck
we
found that
following
certain route
may
help finding
give
following
advice:
(i)
Collect
tem
as
as
possible
before
experimental
can
much information
is not
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
run
simulations.
Reimplement
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
quantitative
models into
investigation
and
computer
implementation.
Obtain
Implement
steadystate 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
ships
check your
analytical
results
model structure in
why?
234
5.3
Modelling
and
Simulation
(v)
Design
from
your
experiments according
to
the
information
in the models
or
parameters
experimental
(iv)
reject
(i)
to
consume
no
more
thoughts mentioned
Let
us
consider
some
of the
5.3
Modelling
and model
an
and Simulation
Modelling learning
implementation are probably considered as the most experimentalist. However, the pain necessary when
can
be obtained. We believe
developed
in this thesis
can
be
applied
without
an
extraordi
nary mathematical
Although
cation
as
the
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
equations,
problems. The straightforward implementation extendability of the Simulink models, the possibility
of
to
programming blocks,
can
estimation
accomplished
the process
within
presented. However,
gation.
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
length
of the
triple phase
accu
boundary (tpb)
and the
porosity,
can
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
they
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
proposed.
The
popular
of them is the
use
of
shaped
or
it is doubtful whether
perfect
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
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
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
236
5.5
no
significant
reason
progress in the
investigation
of
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
employed.
data,
not
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 steadystate currentvoltage 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:
Switzerland
Nationality:
Education
4/822/86:
3/1986:
Kantonsschule Aarau
7/8610/88:
11/8810/92:
11/922/93:
Technology, Abt. Ill D, ETH Zurich Diploma thesis with Prof. Dr. Urs P. Wild, Institute of Physical Chemistry, Department of Chemistry; Topic: "EinzelmolekulspektroskopiePentacen in paraTerphenyl"
tute of
3/93:
Diploma
in Materials Science
6/9310/93:
11/9310/97:
J. Gauckler, Head of
Department
Curriculum Vitae
Publications
[I]
A. Mitterdorfer and L.
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 (SOFCV), pages 421430, Pennington, NJ, 1997. PV 9740, The Electro
chemical
Society,
Inc.
[2]
J. Gauckler. La2Zr207 Formation Between YttriaStabilized 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
A. Mitterdorfer and L.
In
F. W.
J. Gauckler. Oxygen reduction at the La0 85Sr015Mno 9803 in Poulsen, N. Bonanos, S. Lindenroth, M. Mogensen, and
ZachauChristiansen, editors, High Temperature Electrochemistry: Ceramic and MetalsProc. of the 17th Ris0 Int. Symp. on Mat. Sci., pages 357362, Roskilde, Den mark, 1996. Rise National Laboratory.
[4]
J. Gauckler. LSMKathoden fur FestelektrolytBrennstoffzellen. In Werkstoffwoche '96, Symposium3: WerkstoffefiirdieEnergietechnik, 28A. Mitterdorfer
and
L.
Germany,
1996. DGMInfor
[5]
A.
temperatures. In B. Oxide Fuel Cell Forum, pages 373382, Baden, Switzerland, hrdorf, Switzerland.
La0 85Sr015Mny03 during firing at intermediate Thorstensen, editor, Proceedings of the Second European Solid
1996. U.
Bossel, Oberro
[6]
A. Mitterdorfer and L.
kinetics in
[7]
A. Mitterdorfer and L.
tem. Part I:
J. Gauckler. Theoretical analysis of the Pt, 02(g) I YSZ sys framework, modelling, and structural investigation. /. Electro general
[8]
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
mitted.
[9]
A. Mitterdorfer and L.
tem: state and
J. Gauckler.
02(g) I cZrOz
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.
Solid
Oxide Fuel Cell Forum, pages 545566, Baden, Switzerland, 1994. U. Bossel.
"Processingmicrostructureproperty 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
Pennington, NJ,
trochemical
Society,
Inc.
"Processingmicrostructureproperty relations of solid oxide fuel cell cathodes." In Proceedings of the First European Solid Oxide Fuel Cell Forum, pages 475492,
Baden, Switzerland, 1994. U. Bossel.
Presentations
[13]
11th International Conference
on
[14]
5th International
Symposium
on
Aachen/Germany,
(Oral Presentation).
26
[15]
[16]
MRS Fall
Materials
ScienceHigh Temperature
Electrochemistry:
Presentation).
[17]
[18]
Stuttgart/Germany,
2831
June
1996.
(Poster Presentation).
610
European
Oslo/Norway,
May
1996.
(Oral Presentation).
241
Curriculum Vitae
242
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