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Diss.

ETH No 12380

Identification of the

Oxygen

Reduction

at Cathodes of Solid Oxide Fuel Cells

A dissertation submitted to the

SWISS FEDERAL INSTITUTE OF TECHNOLOGY


ZURICH

for the

degree

of

Doctor of Technical Sciences

presented by
Andreas Mitterdorfer

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

accepted

on

the recommendation of
examiner

Prof. Dr.
Dr. B.

L.J. Gauckler,

Elsener, co-examiner

1997

Diss. ETH No 12380

Identification of the

Oxygen

Reduction

at Cathodes of Solid Oxide Fuel Cells

A dissertation submitted to the SWISS FEDERAL INSTITUTE OF TECHNOLOGY

ZURICH

for the

degree

of

Doctor of Technical Sciences

presented by
Andreas Mitterdorfer

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

accepted on the
Dr. B.

recommendation of

Prof. Dr. L.J. Gauckler, examiner

Elsener, co-examiner

1997

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

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Acknowledgments

I wish to express my

deep gratitude

to

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

head of the chair of Nonmetallic Materials, for his

encouragement and sup


opportu

port, and for his willingness

to entrust

so

much of the advance of the

project nity
to

to

my

judgement.

In

particular,

I wish to thank him for the


over

present
as

my results at international conferences all well

the world.

I wish to thank Dr. B. Elsener from the Institute of Corrosion Science for

acting
giving

co-examiner of this thesis

as

as

Prof. Dr. D. Bonnell, of the

on

Sabbat

ical from

Pennsylvania University,

valuable comments, and

reading most parts improving the language.

for

manuscript,

I wish to thank the members of the SOFC group at the chair of Nonmetal

Christoph Kleinlogel for many helpful discussions and support as well as their company during confer ences; Julia Will for continuing the processing of ceramic foams; Anja Bieberle and Roger Stadler for carrying on state-space modelling of electrochemical systems and making the method more known to others; Wal ter Tobler for his contributions during his diploma work and his assistance after the diploma. colleagues at the chair of Nonmetallic Materials: Prof. Dr. G. Bayer for giving time and attention to my questions about crystallography and ceramics processing; Dr. Marco Cantoni for his support in HRTEM analysis and his excellent support in operating the AFM and SEM; Dr. P. Bohac for helpful scientific discussions; Peter Kocher for his
am

lic Materials: Dr. Martin Godickemeier and

further indebted to many

technical assistance, his PC cult times;

support, and his encouragement during the diffi


the

Bengt Hallstedt for sharing

job

of UNIX network management

and Frank Filser for

taking this job

from

me.

I also wish to thank the members of Sulzer Innotec in Winterthur and the

members of the Swiss Federal Institute of


in SOFC R&D for their

Technology

in Lausanne involved

support and

interest.

family, my family, and my friends for their support and encouragement during my education. I also wish to thank Daniel Jurt for his support in typographical questions. I finally wish to express my gratitude to Dr. Leo Dubai from the Swiss Federal Department of Transportation, Communications, and Energy for his
continual interest and financial

I wish to thank my wife Denise and her

support of the project.

November,

1997

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

Solid State Ionics Electrochemical Devices

1.1.2 The

1.1.3 1.2 1.3

Origin of Potential Differences Oxygen Reduction

Aim of the Thesis

Structure of the Thesis

12 13

References

Part
2

II

Theoretical

Analysis

of the Pt,

Oz(g)

I YSZ

System
19

General 2.1 2.2

Framework, Modelling, and Structural Investigation

Introduction

20
24

General Framework
2.2.1 2.2.2

The Process of

Modelling Hypotheses

24

General Considerations and

25 28

2.2.3

Modelling

Reaction Mechanisms

2.3

Identifying G(s) with Electrochemical Quantities 2.2.5 Working with Frequency Responses 2.2.6 Identifiability of Linear Reaction Models Reaction Models of the Pt, 02(g) I YSZ System
2.2.4

30

35 37
38 38

2.3.1

Introduction

2.3.2 Basic

Equations

and

Assumptions

39
42 45

2.3.3 Electrode
2.3.4

Overpotential
Behaviour
. .

2.3.5
2.4

Properties of the Models Qualitative Analysis of Frequency Response


Structural

56 60 61 66

Conclusions

References

Appendix
2-A.l
2-A.2
3

Space Description of an Electrical Circuit Calculation of tpb length from microstructural data
and Validation

State

...

66 68
71

Computer Implementation, Simulation,


3.1
3.2

Introduction
Model
3.2.1 3.2.2

72

Implementation Computer Tools and General Procedure Heterogeneous Chemical and Electrochemical
Transport

73 73

Kinetics

74
77 81

3.2.3 Surface Mass 3.3

Simulation Procedures
3.3.1 3.3.2

Model Initialization and


Penetration

Sensitivity

81 82 86

3.3.3 3.3.4 3.4

The

Depth and tpb Width Double Layer Capacitance


Simulation and Numerical

Digital

Aspects

91

Simulation Results

92 92
.

3.5

Charge-Transfer Controlled Kinetics 3.4.2 Competition Between Surface Diffusion and Adsorption 3.4.3 Sensitivity Analysis and Practical Identifiability Summary and Conclusions
3.4.1

110
124

129

References

131
136 Reaction Model Constants and Parameters

Appendix
3-A.l
3-A.2

136

Determination of

Cd\ by Potential Step


137

3-A.3

3-A.4

Chronoamperometry Implementation and Simulations Implementation and Simulations

of Model Ml of Model M2

139 148

VI

Part

III

The Interface between

Lao 85Sr015MnyO3+s and


Oxygen
Reduction Kinetics
159

Yttria-Stabilized Zirconia
4

Lanthanum Zirconate Formation and


4.1

Introduction
4.1.1

160

General

160

4.1.2 Microstructure

and-Chemistry Properties Aims of the Study

161 163 165 166


166

4.1.3 Influence 4.1.4


4.2

on

Electrochemical

Open Questions and Experimental Procedures 4.2.1 Sample Preparation

4.2.2
4.2.3 4.3

Investigation of Surfaces and Interfaces Electrochemical Investigation

168
169 170
....

Results
4.3.1 4.3.2 4.3.3

Conductivity Interface Development During Sintering Electrochemical Properties LSMq 98 Cathodes


General

Cathode Microstructure and Electrical

170 172 190 197 197 198

4.4

Discussion 4.4.1 4.4.2


4.4.3

Lanthanum Zirconate Formation

Oxygen

Reduction Kinetics at

LSM0 93/YSZ Interfaces.

207 223
224

4.5

Conclusions

References

Part
5

IV

End Matter
233

Outlook
5.1 5.2 5.3 5.4 5.5

General

233 234 235 236

Identification of Reaction Mechanisms

Modelling

and Simulation

Materials and

Samples Electrochemical Investigation Techniques

236
239

Curriculum Vitae

vii

viii

List

of

Figures

Chapter 1
1.1

Schematics of

half cell with Pt and

an

ionic
7

conductor in contact
1.2

Interface between cathode and solid


Schematic

electrolyte surface
at

1.3

diagram of predominant reaction steps electrode/electrolyte interface

10

Chapter 2
2.1

Schematic view of the oxygen reduction process at interfaces between noble metals and solid oxide

ion-conducting electrolytes
2.2

25

Secondary
Pt
on a

Electron

(001) YSZ

Micrograph (SEM) of porous single crystal surface


response of first-order

26

2.3

General Faradaic

frequency
an

electrochemical systems
2.4
2.5

33

"Equivalent

circuit" of

noble

metal/electrolyte system
area near

36
41

Schematic view of the active electrode

the tpb

2.6

Schematics of

three-electrode cell with identical


43

porous Pt electrodes
2.7

Two-compartment model

for structural

investigation
53
in the

of reaction mechanism M2
2.8

Qualitative frequency response of Ml shown

complex plane
2.9

57
in

Qualitative frequency response of Ml shown


Bode

representation

58

2.10
2-A1.1

Frequency

responses of Ml in Bode

representation

59 66

RC electrical circuit

2-A2.1

Simplified morphology
interface

of noble

metal/electrolyte
68

Chapter 3
3.1

electrode geometry and one-dimensional finite element model

Simplified

78 83

3.2

Temperature dependence
Electrical

of 0)max for

3.3
3.4

equivalent circuits partial


pressure
the

fitting experimental

EIS data

89

Relation between the


the oxygen

exchange current density i0 charge


at

and
94

3.5 3.6

Dependence of i0

on

transfer coefficient S

95

Isobaric Arrhenius

plot of /0

different oxygen

partial
98 1123 K 100 101 102

pressures
3.7 3.8 3.9 3.10

Steady-state /f(tj)
Deviation of Simulated

behaviour of Model M2 at T

/F(r|)

from theoretical Tafel behaviour

/f(t))

behaviour and Tafel

analysis
i0 values

Comparison
atr
=

of theoretical and estimated

1123K

103

3.11 3.12

Simulated

Z(j(o)

of M2 shown in the

complex plane
on

105

Influence of double
of

layer capacitance

appearance
106 107

Z(jco) spectra

3.13 3.14 3.15

Complex plane plot of simulated impedance data


Determination of Determination of

ZF(j(o)

from simulated

noisy Z(jco)

data

108 109

Rp and Rt after subtraction of CdJ


as a

3.16

Electrode conductivities and oxygen

function of

temperature
Ill

partial

pressure

3.17

Oxygen partial pressure dependence of electrode


conductivities of model M2
112

3.18

Isobaric Arrhenius

plots

of electrode

conductivity

115

3.19

Simulated temperature dependence of the oxygen partial pressure where the maximum of the electrode

conductivity occurs
3.20

116

Simulated

partial
3.21 3.22

under different oxygen pressure conditions at 973 K (700C)

/F(r|) relationships

118 120

Simulated cathodic

limiting-current behaviour
=

of M2

Simulated

impedances at T different overpotentials T|


Simulated

973 K

(700C)

at

121
=

3.23

impedances at T 973 K (700C) and different cathodic overpotentials


Sensitivity
of

123

3.24

IZFI
IZFI

with

respect

to the unknown

parameters
3.25

124 with

Sensitivity

of

respect
area

to the

length of the tpb


125

and the width of the active


3.26

Sensitivity of IZFI with respect to condition w-lc const


=

with under the


127
128

3.27
3.28

Correlation between

and

klc

with respect to the activation energy of the surface diffusion of Oad

Sensitivity

of

IZFI

129

3-A2.1

Comparison of potential step


circuits

responses of

equivalent
139

3-A3.1

Simulink block

diagram

for the

adsorption/desorption
140
....

dynamics
3-A3.2
3-A3.3

Simulation results for model Ml at reference conditions

141

Simulink block

diagram of Ml

in order to extract

linearized state-space models


3-A3.4

143

diagram of Ml current-voltage behaviour


Simulink block Simulink block

for simulation of 147

3-A4.1

diagram diagram

for the tpb

compartment of

M2

....

152

3-A4.2
3-A4.3

Simulink block
Simulink block
M2

of M2 with four
for

compartments
two of

....

152

diagram (subsystem)

compartment

153

xi

Chapter 4
4.1
4.2

SEM of sintered

LSMj 02 cathode

on

YSZ

single crystal

170

4-probe electrical conductivity


in air

of LSM

cathode

layers
171
on

4.3

XPS sputter depth YSZ single crystal TEM


on a

profile

of

La-rich surface

layer

173

4.4

images
(001)
a

of lanthanum zirconate islands grown YSZ single crystal surface

174

4.5

AFM of

lanthanum zirconate surface

layer covering a

YSZ
176

single crystal
4.6

AFM

with
4.7

images of a (001) YSZ single crystal surface covered cube-shaped islands of lanthanum zirconate

178

LZO island and YSZ

growth kinetics

at 1373 K between

LSMq 98
180 182 183

4.8 4.9 4.10

Bright

field TEM of LZO island

on

(001)

YSZ surface

HRTEM of LZO island surface

images of (001) YSZ surface La0.85Sr0 isMn! 02O3 cathode


AFM

after

sintering with

184

4.11

Density sliced sintering

AFM

image

of YSZ surface after

long-term
186 187

4.12 4.13

Plan-view TEM of YSZ surface

Bright-field TEM of cross ring-shaped island

section of

188

4.14

Typical complex plane plot of the electrochemical impedance of a LSM0.981 YSZ interface during heat
treatment in air

190

4.15

Bode

plots

of

LSMg 98

cathodes

on

YSZ

during heat
192

treatment

4.16
4.17

Arrhenius

plot of conductivity ae

of

LSMq 98

cathode

193

Oxygen partial pressure dependence conductivity of LSM0 98 cathode

of electrode
194

4.18

Oxygen partial pressure dependence impedance of LSMq 98 cathodes

of the electrochemical
195

xii

4.19

Schematic view of the LZO of

layer formation at the

interface
199

LSMq 95

and YSZ

4.20

Schematic view of LZO island formation and the interface between

growth
growth

at

LSMq 98 LSMj 02

and YSZ
at

202

4.21

Schematic view of LZO island formation and


the interface between

and YSZ

205

4.22

"Equivalent circuit" of an electrode/solid electrolyte system and corresponding frequency responses


Complex plane plot of Impedance Z and Faradaic impedance ZF of unsintered LSMq 981 YSZ interface
at873K(600C)

210

4.23

211

4.24

Frequency dependencies of IZI and IZFI LSMq.98 I YSZ interface at 873 K (600C)

of the unsintered
213

4.25

Complex plane plot of Impedance Z and Faradaic impedance ZF of the unsintered LSMq 981 YSZ interface
'

at 1123 K

(850C)

214

4.26

Complex plane plot of Impedance Z of sintered LSMq.98 I YSZ interface at 1223 K (950C) and low oxygen partial pressures Complex plane plot of Impedance Z and Faradaic impedance ZF of the sintered LSMq 981 YSZ interface
at 893 K

216

4.27

(620C)

in oxygen

217

4.28

Frequency dependence of IZI and IZFI of the sintered LSMo981YSZ interface at 893 K (620C) at different oxygen partial pressures
Model of the oxygen reduction at unsintered and sintered LSMq 98/YSZ interfaces

218

4.29

220

xiii

xiv

List

of

Tables

Table 3.1

Parameters and Constants used in Model Ml and M2


136

Table 4.1

Characteristics of the
used in this

screen-printing pastes
167

study

Leer

Vide

Empty

xvi

Summary

The

high temperature

reduction of oxygen at interfaces between solid oxide

oxygen ion conductors and


consists of
a

electronically conducting

cathode materials

number of

elementary steps: transport


on

of oxygen in the porous

cathode network,

adsorption of oxygen

the cathode, and electrochemical


measure

and chemical interfacial reactions.


ments and electrochemical

Steady-state current-voltage
are

impedance spectroscopy

the main electro

chemical

investigation techniques employed improve

for electrode characterization.

In order to be able to

the electrochemical

performance

of cathodes

the reaction mechanisms and the associated kinetic rate constants must be known. The purpose of the present the identification of

study

is to

provide a general

method for

heterogeneous

electrode reaction mechanism. The

application of this
A method is

method is demonstrated with two different systems.

developed

for

dealing

with micro-kinetic models. This

methods allows for model

performing

mathematical and

analysis

of the

equations,

implementation, steady-state

dynamic simulations,
a

and parame

ter estimation

(numerical optimization) within

single

framework. The
from

models

are

described

by time-independent state-space equations

which the Faradaic admittance transfer function is obtained. The Pt,

02(g) I Zr02 system


for its

is considered

as

model system and is

investigated

identifiability

of unknown parameters.

Oxygen adsorp-

tion

on

Pt, surface diffusion of atomic oxygen, and the electrochemical reduc

tion of adsorbed oxygen at the

three-phase boundary

is considered. It is
can

shown that the unknown rate constants and parameters estimated from
a

be

accurately

combination of mathematical

analysis,

electrochemical
surface
meas

measurements, and numerical data diffusion coefficients


can

analysis. Coverage dependent

be estimated from

impedance spectroscopy
can

urements. The method of

working

demonstrated

be well

applied

to other

metal electrode/solid

electrolyte systems.
La0 8sSr015Mn03, 02(g) I Zr02 system
are

The relevant reaction steps in the discriminated from electrochemical


an

experimental study, comprising


The

microstructural and

characterizations.

formation

of

the

foreign phase
means

La2Zr207

at the

cathode/electrolyte

interface is

investigated by

of

high

resolution transmission electron

microscopy

and atomic force micros

copy. The manganese concentration in the


nucleation and the

perovskite
A-site

affects the onset of


in the per

growth

rate of

La2Zr207.

deficiency

ovskite may prevent the interfaces


are

La2Zr207

formation. The electrochemical

properties

of

strongly

influenced

by La2Zr207

islands at the

three-phase

boundary. Charge transfer,

dissociation of adsorbed molecular oxygen ions,


are

and surface diffusion of atomic oxygen

discriminated from electrochemi

cal

impedance investigations.

xviii

ZUSAMMENFASSUNG

Die

Hochtemperatur-Reduktion Festelektrolyten

von

Sauerstoff

an

Grenzflachen zwischen

oxidischen
aus

und elektronisch leitenden Kathoden setzt sich


zusammen:

verschiedenen Teilschritten

dem

Transport

von

gasformi-

gen Sauerstoff im

Porensystem

der Kathode, der

Adsorption von Sauerstoff

auf der Kathodenoberflache, sowie elektrochemischen und chemischen

Grenzflachenreaktionen.

Statische
zu

Strom-Spannungs-Messungen
am

und

Impedanzmessungen
mischen
ten

zahlen

den

meisten verwendeten elektroche

Untersuchungsmethoden.
Kathoden verbessern

Um die elektrochemischen
zu

Eigenschafder

von

konnen,

ist

die

Kenntnis

Reaktionsmechanismen sowie die der relevanten kinetischen Parameter

notwendig.
tifikation

Das Ziel dieser Studie ist es, eine

allgemeine Methode

zur

Iden-

von

Reaktionsmechanismen

heterogener

Elektrodenreaktionen

bereitzustellen und deren

Anwendung

anhand zweier unterschiedlicher

Systeme

zu

demonstrieren.
zur

Es wird eine Methode

Behandlung

von

mikro-kinetischen Modellen

entwickelt. Diese Methode

ermoglicht

die mathematische

Behandlung

der

Bilanzgleichungen, die Computer-Implementierung der Modelle, die Simula


tion
vom

statischen und

dynamischen Verhalten,

sowie Parameter-Schatzun-

gen mit ein und demselben Formalismus. Die Modelle werden dabei mittels

zeitunabhangiger Zustandsgleichungen beschrieben,

woraus

die Ubertra-

gungsfunktion der Faraday-Admittanz erhalten werden kann.

Als wird

Modell-System

wird das Pt,

02(g) I c-Zr02-System
von

betrachtet. Dieses

beziiglich

der Identifizierbarkeit

unbekannten Parametern unterauf Pt, die Oberflachendiffusion

sucht. Es werden die


von

Sauerstoffadsorption

atomarem Sauerstoff auf Pt und die


an

elektrochemische Reduktion

von

adsorbiertem Sauerstoff

der

Dreiphasengrenze miteinbezogen.

Es wird
aus

gezeigt,
einer

dass die unbekannten kinetischen Konstanten und Parameter


von

Kombination

mathematischer

Behandlung,

elektrochemischen

Messungen

und numerischer
vom

Datenanalyse mit grosser Genauigkeit ermittelt


Diffusionskoeffizient

werden konnen. Der


von

Bedeckungsgrad abhangige
aus

atomarem Sauerstoff auf Pt kann

elektrochemischen

Impedanzmes-

sungen bestimmt werden. Die


andere

vorgestellte

Methodik kann ohne weiteres auf

Metall/Festelektrolyt-Systeme iibertragen werden.


an

Der Mechanismus der Sauerstoffreduktion

Grenzflachen zwischen
und elektrochemi
an

La0 85Sr015Mn03

und

c-Zr02

wird mit

mikroskopischen
der

schen Methoden charakterisiert. Die

Bildung

Fremdphase La2Zr207

der Grenzflache zwischen der porosen Kathode und dem wird mittels hochauflosender

Festelektrolyten
und

Transmissions-Elektronenmikroskopie
Der

Atomkraftmikroskopie
beeinflusst

untersucht.

Mangan-Gehalt
auch die

vom

Perowskit der

sowohl

den

Zeitpunkt

als

Geschwindigkeit

La2Zr207-Bildung.
werden durch

Die elektrochemischen
an

Eigenschaften

der Grenzflache
betrachtlich
von
ver-

La2Zr207-Inseln

der

Dreiphasengrenze
die Dissoziation

schlechtert. Der

Ladungstransfer-Schritt,

adsorbierten
atomarem

molekularen Sauerstoffionen und die Oberflachendiffusion Sauerstoff werden als relevante Reaktionsschritte bestimmt.
aus

von

Impedanzmessungen

xx

Parti

Front Matter

Chapter

Introduction

Abstract

The reader is introduced into the


state

operating principles
and
into

of solid

ionics

electrochemical devices

electrochemical

kinetics. The differences between Solid Oxide Fuel Cells

(SOFC),

oxygen sensors, oxygen pumps, and oxygen


branes
ous
are

presented.
that
is

Some
occur

emphasis
at

is

separation mem given on the heterogene


interfaces.
The
term

processes

materials

"overpotential"

explained.

The present status of

knowledge
given.
It
are

about the oxygen reduction kinetics at SOFC cathodes is

References to the most relevant literature in the field

given.

is assumed that the reader is familiar with most of the micro

scopic

and

spectroscopic techniques employed

in this thesis.

1.1
1.1.1

Background
Solid State Ionics Electrochemical Devices

Solid state ionics electrochemical devices consist of two

ducting electrodes which are separated by a gas Y203-stabilized Zr02 (YSZ) has been employed by far conducting electrolyte
for its

electronically con tight solid electrolyte.


most
as

oxygen ion

relatively high ionic conductivity at high tem peratures, its structural stability in both oxidizing and reducing atmospheres, its capability of being easily produced, and its relatively low price [1]. A number of other ionic conductors, such as doped Ce02 [2], 8-Bi203 [3], or per-

Introduction

ovskite-type LaGa03 [4]

have been

investigated

for

use as

solid oxygen ion

conductors. Neither of these materials has reached the role of YSZ up to the present time. The reader interested in new ceramic oxygen conductors is
referred to recent literature

(see e.g. [5, 6],

and references

therein).

A pro

found review
can

on

the science and

technology

of solid oxide fuel cells

(SOFC)

be found in the article and book of Minh


case

[7,8].

current-producing device, such as a SOFC, the electrodes are exposed to atmospheres of different oxygen partial pressures. The electromo tive force (emf) which develops across the cell under equilibrium conditions, i. e. if no current is flowing through the device, is given by the Nernst equa
a

In the

of

tion

emf

Po,
=

4f

low

(1.1)
j

vPo2
partial
an

where

p08

anc^

Vo*

are me

oxygen

pressures at the cathode and at

the anode,

respectively,
is

F is the

Faraday
at

constant, T is the absolute tempera


ideal oxygen ion conductor is
con

ture, R is the gas constant, and where

Oxygen incorporated into


tion

sidered.

reduced

the solid

cathode/electrolyte interface and electrolyte according to the stoichiometric equa

the

io2(g)
where

2e-

O2electrolyte,
and
e

(1.2)
O
2_

denotes oxygen vacancies in the solid

denotes

occupied

oxygen lattice sites in the solid

electrolyte,

denotes electrons

equilibrium the rate of the forward and backward reac tion in Eq. (1.2) are equally fast. At the anode, oxygen ions are oxidized to form either oxygen molecules (backward reaction of Eq. (1.2)) or a different reaction product in the presence of a fuel gas, e.g. H20 in the presence of
from the electrode. In

hydrogen or C02 in the presence of CO. The cell potential generally decreases when the cell produces a current. The deviation of the cell potential from the Nernst potential depends on the cur rent and the internal resistance of the cell. This behaviour is typical for any
*)
Note that in

electrochemistry the

term

"potential"

is

usually

used to ascribe

"potential

difference".

1.1

Background

galvanic cells. The internal resistances are due to the ohmic resistance of the electrolyte and electronic conductors, as well as due to interfacial resistances (generally non-ohmic). The understanding of these interfacial resistances has been a driving force for
current-producing
electrochemical device, i.e. the science of electrochemical kinetics.

By contrast,

current-driven devices, such


are

as

oxygen pumps

or

oxygen separa

operated by imposing an external load. This can either be accomplished by applying a constant current (galvanostatic mode) or by applying a constant potential (potentiostatic mode) across the cell. In the first case, a potential difference develops across the cell which is proportional to the cell conductivity, whereas in the second case, the current through the cell is proportional to the cell resistance (inverse conductivity). Accordingly, low cell resistances are desired to keep internal losses low.
tion membranes, The third type of solid state electrochemical devices, oxygen ther
sensors, are

nei

producing a current nor are they driven by a current. Their purpose is to probe an oxygen partial pressure of interest (cf. Eq. (1.1)). One might there
fore believe that the internal resistance of
cern. an

oxygen
a

sensor

is of minor

con

change in the oxygen partial pressure must be fast, low electrode resistances are required. So far we have briefly summarized the operating principles of solid state electrochemical devices from a macroscopic point of view. We have seen that internal cell resistances influence the properties of these cells. In the follow ing we consider the interfacial processes in more detail. The reader is also
However, if the response of

Eemf

upon

referred to standard textbooks about electrochemical kinetics and electro


chemical methods

(see Chapters

8 and 9 of

[9]

as a

starting point,

as

well

as

Refs

[10-14]).

1.1.2

The

Origin
a

of Potential Differences

If two materials and YSZ


two

and

(5

are

brought

into contact, in

our case a

noble metal

(Fig. 1.1), the electrochemical potential of the electrons within these p." jig. Note that phases will generally not be the same, i.e. aA e
=
-

YSZ is not

pure oxygen ion conductor but that

small electronic

(or hole)

conductivity is always present [15]. As a consequence, elections from one phase will flow to the other phase, leaving a positively charged phase behind. Accordingly, a potential difference develops between these phases, the equilibrium potential difference, Eeq. It is a fundamental property of materi-

Introduction

als interfaces that their

equilibrium potential differences can not be measured


we can

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


between
T|
=

measure
an

the

an

interface
.

apart from equilibrium and


n

potential difference interface at equilibrium,


and

The

quantity

is termed

overpotential

plays

fundament

electrochemistry. This situation is accomplished by measuring the potential difference between two identical electrode/electrolyte interfaces,
where
one

role in

interface is at rest and the other distorted

by
not

an

electrical current.
that
are no

As known from chemical kinetics,

equilibrium does

mean

flow of

electrons occurs, but that the forward and backward currents

equilibrium current is Obviously, i0 reflects the


thus
case

equal. This designated equilibrium exchange-current density i0.


kinetic

properties
one

of the considered interface and


to another. As in the
are

can

be rather different from the

type of interface

of

Eeq,

quantity i0

can

not be

directly
and

measured. However, there

different

possibilities
a

to determine

i0,

some

methods

(and

its

limitations)

will be discussed.
We
can

obtain

net current

density

i if the forward and backward currents,

if

and ib, become different in

magnitude
i
=

if-ib.
potential

(1-3)

It is easy to

see

that this

implies
=

that the interfacial

difference must

depart
Let
us

from

Eeq.

The difference between the actual interfacial


T| E
-

potential

and

Eeq is the overpotential

as

introduced above.

briefly consider a platinum oxygen electrode to understand the physi cal significance of overpotentials (Fig. 1.1). The half-cell reaction is written as

02-(P)|02,Pt(oc)
where the notations determined

(1.4)
in

by the

correspond to those given following reaction

Fig.

1.1. The

potential

is

^02
because the electrons
are

2e"^02",

(1.5)

only charge-carriers that can exist in both phases. Note that the activity of electrons e~ in the electrolyte is related with 02~(B) through the reaction O2" (B) O(B) + 2e~(B). Similarly, the activity of oxygen at the interface between Pt and YSZ, aQ, is determined by the oxy
the
=

gen

partial

pressure.

Accordingly,

the oxygen

partial

pressure pQ

deter-

1.1

Background

potential of the oxygen ions in the YSZ, ji 2_(B), and therefore the equilibrium potential. Note that in equilibrium all activities of the species involved in the overall reaction exhibit its equilibrium value.
mines the electrochemical As
soon as a

current flows

through

an

external circuit, oxygen is removed


current is
so

from the cathode side

(the direction of the

that oxygen ions


is

migrate

from the cathode side to the

anode). On the anode side hydrogen

consumed and water is

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

(i)

Molecular oxygen from the gas


reaction

phase

must

pass with

number of

steps until

it arrives

as

atomic oxygen

near

the

tpb.

Because every

elementary

reaction

proceeds

finite rate,

the concentrations of the

species

involved in the reaction

Pt
e~

Pore

<

o2(g)

O(ad)

YSZ

02"(P)

O(p)

2e"

Fig.
a

1.1

Schematics of

half cell with Pt and

an

ionic conductor in contact.

denotes the Pt

phase

and B denotes the solid oxide ion conductor. Electrons may exist

in the Pt and the ion conductor. Gaseous oxygen is contained within the gas

phase.

Note

that
In

02(g)

may

undergo heterogeneous

chemical reactions with the Pt and YSZ surface.

addition, adsorbed atomic oxygen may be incorporated in the electrolyte. In equilib rium, all elementary reactions are equally fast. The triple phase boundary (tpb) is the
line where YSZ, Pt, and the gas

phase

are

in contact.

Introduction

mechanism will deviate from its The term concentration

equilibrium concentrations. overpotential, nc, is used to ascribe for

phenomena. Furthermore, it is clear from the above that nc may be further split into contributions from the elementary reactions, e.g. gas phase diffusion, adsorption, dissociation,
and surface diffusion.

these

(ii)

Once the atomic oxygen arrived at the


nated and

tpb

it must be electroan

incorporated into

the solid

electrolyte. Certainly,
an

activation energy is necessary to into the YSZ lattice. In

incorporate

oxygen ion
act
on

addition, electrostatic forces


overcome.

the

oxygen ion which must be

The term

charge-transfer
differ

(or activation) overpotential, nct,

is used to ascribe for these


an

phenomena.
ence

It is

readily

seen

that

applied potential

influences the rate of oxygen transfer, because the oxy


are

gen

species

negatively charged.

1.1.3

Oxygen
shows The
a

Reduction

Fig. 1.2 trolyte.


tivity

typical interface between a porous cathode and a solid porosity of the cathode is in the order of 45% and the mean
a

elec

pore

size is ~1 (im. The cathode material should exhibit


at

good

electronic conduc
conditions.
as

high temperatures
or

and it must be stable under


as

oxidizing

Therefore, noble metals, such

Pt, Au,

or

Ag,

and oxide materials, such

Sr-doped LaMn03
Eq. (1.2).
of them

LaCo03,

have been considered

(see e.g. [7,16-19]).

The overall reaction of the oxygen reduction at SOFC cathodes is This reaction is made up of
a

given by

occur on

face between the ary

elementary reactions, some the surface of the cathodes, others take place near the inter cathode and the electrolyte, i. e. at the triple-phase bound
Which processes in detail
occur

couple

of

(tpb) (cf. Fig. 1.2).

depends

on

the

type of

electrolyte material considered. We start our considera tions at the tpb and work along the cathode surface. Three main types of het erogeneous elementary reactions can be distinguished (Fig. 1.3):
(i)

cathode material and

Charge

transfer of electrons from the metal to adsorbed

atomic oxygen

species
near

and the

gen ions into YSZ

subsequent incorporation of oxy tpb. This reaction is certainly con-

1.1

Background

fined to the

vicinity

of the

tpb [17, 20, 21].

An almost linear

dependence of the electrode resistance with the length of the tpb is generally found [22, 23]. In contrast, there is no experi
mental evidence about the actual mechanism of electron
are

transfer. Two one-electron transfer steps to atomic oxygen


more

probable

than

addition, there is also

single two-electron transfer step. In relatively little known about the actual
species.
either of two processes:

charge

of any adsorbed oxygen

The atomic oxygen is

supplied by
of
atomic

adsorption
or

and

subsequent

dissociation of oxygen molecules

surface

diffusion

oxygen.

Note

that

the
are

charge-transfer

process and the

supply

of atomic oxygen

series processes. Therefore the slower of the processes will

control the electrode behaviour.

Fig.
was

1.2

Interface between cathode and solid of porous

electrolyte surface.Secondary
cathode
on

Electron

Micrograph (SEM)
gen

La0 8sSr015Mn03
and

YSZ

polycrystal.

The cathode
in air.

subsequent sintering applied by screen-printing molecules may diffuse through the porous network
i.e. are

at 1373 K

(1100C)

Oxy

towards the

triple phase
and the gas

boundary (tpb), phase

the location where the cathode, the solid

electrolyte,

in contact.

Introduction

(ii)

Adsorption of oxygen on the cathode surface. This may either occur dissociatively (such as on Pt [24]), or associatively (such as on Au [25] or Sr-doped LaMn03 [16]). However, it is of fundamental difference whether the bonding of the oxygen molecule is broken upon adsorption or not and the overall behaviour of the electrode is expected to be different. Obvi ously, the adsorption/dissociation process occurs on the entire cathode surface. It can be taken as a general rule that, at least for Pt and Sr-doped LaMn03 cathodes, the supply rate of adsorption/dissociation is too low to account for the rela tively high current-densities measured. A further process must therefore be responsible for the supply of atomic oxy
gen.

Fig. 1.3 Schematic diagram of predominant reaction steps at electrode/electrolyte interface.(1) 02(g) is supplied by gas phase diffusion through the pores of the cath
ode.

(2)

The oxygen molecules may adsorb


can

on

the entire cathode surface.


can

(3)

the

tion process

be

accompanied by
(5)

an

electron transfer and it

be followed
are

adsorp by an
is

immediate dissociation of the molecule.

(4)

Atomic oxygen

species

considered to

diffuse

along

the cathode surface.

The final

charge

transfer and

incorporation step
are

believed to take
YSZ and

place

at the

tpb,

where

Oq

denotes

occupied
on

oxygen lattice sites in


not

denotes oxygen vacancies. Similar processes

the YSZ surface

believed to be of

comparable

relevance.

10

1.2

Aim

of the

Thesis

(iii) Diffusion of atomic oxygen


ess

on

the cathode surface. This proc

generally deliver atomic oxygen towards the tpb with a high transport rate. Because the adsorption/dissociation reaction and surface diffusion occur in parallel on the cathode surface, the faster process will control the electrode behav iour*. At temperatures above ~500C this is usually the sur
may

face diffusion process

(see e.g. [26-29]).

Obviously,
gen

further processes may be the gas

important,

such

as

the diffusion of oxy

phase, or the interaction of oxygen with the YSZ surface. However, it is generally accepted that these types of interactions can be neglected under most operating conditions. Although there is general agreement about the reaction pathway of oxygen at interfaces between electronically conducting cathodes and YSZ, there is still through
little known about the reaction mechanisms. Even less is known about the
kinetic constants of the

elementary

reactions involved in the overall kinetics.

There
are

are

two main reason

for this. First,

interpret and the mean large. Furthermore, rarely an operating condition of the cell is found where the mechanism is dominated by a single step. Second, the reaction mecha nisms are relatively complicated and, therefore, they are difficult to treat mathematically in analytical form. However, it is not always necessary to run through all the mathematics, and a combination of both analytical analysis and numerical simulation may help to solve a particular problem.

difficult to

experimental electrochemical results variation of the results is generally

1.2

Aim of the Thesis provide


general
method for the identification of

The aim of this thesis is to

heterogeneous
cation
on

reaction mechanisms at solid state oxygen electrodes. Identifi

the
on

one

hand includes the discrimination of the relevant reaction

steps, and

the other hand the

quantitative

estimation of

(electro-)

kinetic

parameters.

*)

It is worth to think about this statement and the

corresponding

statement in

(i).

11

Introduction

The

following sub-goals will be


(i)

followed:

development of a general framework for modelling, struc tural investigation, and implementation of reaction mecha
nisms;

(ii)

exemplary validation Pt, 02(g) I YSZ system;


of

of the

proposed

method

with

the

(iii) discrimination

the

relevant
on

reaction

steps

of

La0 85Sr015Mny03
tial; proposal

cathodes

YSZ

near

equilibrium poten

of reaction mechanism;

(iv)

assessment of the

Matlab/ Simulink programming environ

ment for the numerical treatment of models of reaction mech

anisms.

1.3

Structure of the Thesis


by
a

The main part of the thesis is enclosed outlook

an

introductory chapter
our

and the conclu

chapter.
we

In the outlook
some

we

give

concise summary of

sions and

give

ideas for further studies in the field of

ture electrode reaction kinetics. The main

part

consists of three
or

high tempera chapters, each


similar form.

of them intended for

publication

in the

present form
with
an

in

They
an

are

organized
an

in the usual way,

starting

abstiact, followed by

experimental section, a results section, a discussion sec tion, and the corresponding list of references. Nevertheless, redundancy an repetition are kept to a minimum. Following, a brief summary of the contents of the three main chapters:
introduction,

Chapter 2.
tion" and

The

general

framework for

modelling

and structural identifica

tion of reaction mechanisms is

developed.
are

The terms "structural identifica

"state-space modelling"
a

explained.
of
a

The theoretical concepts

are

exemplified by

thorough

treatment

kinetic model

describing

the

Pt, 02(g) I YSZ system.

12

1.3

Structure

of the

Thesis

Chapter 3.
tions for the

The system

explored

in

Chapter 2
are

is

implemented
in the

in Matlab

and Simulink.

Step-by-step

instructions

given

appendix.
are

Simula fre

steady-state current-voltage
behaviour
are

behaviour and the

small-signal

quency

dependent
to

obtained. The results

discussed with for the

respect

reported experimental

and simulated data. A


in the model is

procedure

identification of unknown

parameters

proposed.

Chapter 4.
YSZ

The interface between porous

La0.8sSr015Mny03
a

cathodes and
tech

single crystal
and

surfaces is

investigated by

number of

microscopic
is

niques

by electrochemical impedance spectroscopy.


between YSZ and

The formation of the

foreign phase La2Zr207


on

La0 85Sr015Mny03

investigated
at the inter

the sub-micron to nanometer scale. The influence of

La2Zr207

face upon the electrochemical

properties

is clarified. The relevant reaction


are

steps

in the overall process of oxygen reduction

discriminated.

References
[1]
B. C. E. Steele.

Oxygen

ion conductors. In T.

Takahashi, editor, High Conductivity


1989. World Scientific.

Solid Ionic Conductors, pages 402-446,

Singapore,

[2]

M. Godickemeier. Mixed Ionic Electronic Conductors for Solid Oxide Fuel Cells. PhD

thesis No. 11348, ETH Zurich,

Department of Materials, Switzerland,


Properties of Stabilized
of Twente, Holland, 1991.

1996.

[3]

I. C. Vinke. Electrochemical and Electrode

Bismuth Oxide Ceram

ics. PhD thesis, Technical

University

[4]

Matsuda, and Y. Takita. Doped PrMn03 perovskite oxide temperature operation. /. Electrochem. Soc, 142:1519-1524,1995.
as a new

T. Ishihara, T. Kudo, H.

cathode of solid oxide fuel cells for low

[5]

B. C. E. Steele, editor. Ceramic

Oxygen

Ion conductors, British Ceramic

Proceedings,

London, 1996. The Institute of Materials, The Institute of Materials.

[6]

H. U.

Anderson,

A. C.
on

national.

trochemical

Symposium Society.

Khandkar, and M. Liu, editors. Proceedings of the First Inter Ceramic Membranes, Pennington, NJ, 1997. 95-24, The Elec

[7] [8]

N.

Q. Minh. Ceramic fuel cells. /. Am. Ceram. Soc, 76:563-588,1993.

N. G. Minh and T. Takahashi. Science and

Technology of Ceramic

Fuel Cells. Elsevier

Science B. V.,

Amsterdam, The Netherlands, 1995.

13

Introduction

[9]

J. O. Bockris and A. K. N. Reddy. Modern Electrochemistry, volume London, 1970.


K.

2. Plenum Press,

[10] [11]

J. Vetter. Electrochemical Kinetics. Academic Press, New York, 1967. J. Bard and
L. R. Faulkner. Electrochemical Methods: Fundamentals and &

A.

Applica
2 edi

tions.

John Wiley

Sons, New York, 1980.

[12]

J. S. Newman. Electrochemical Systems. Prentice Hall, Englewood Cliffs, NJ,


tion, 1991.

[13]

C. Gabrielli. Identification of electrochemical processes

by frequency

response
1984.

analysis.
[14]
1987.

Technical

Report 004/83,

Solartron Instruments,

Farnborough,

J. R. Macdonald, editor. Impedance Spectroscopy. J. Wiley-lnterscience,

New

York,

[15]

J.-H. Park and

R. N. Blumenthal. Electronic

transport in 8 mole percent Y203-Zr02.

/. Electrochem. Soc, 136:2867-2876,1989. [16]


Y. Takeda, R. Kanno, M. Noda, Y. Tomida, and O. Yamamoto. Cathodic tion

polariza
/. Electro

phenomena

of

perovskite

oxide electrodes with stabilized zirconia.

chem. Soc, 134:2656-2661,1987.

[17]

M. Kleitz, T.

Kloidt, and L. Dessemond. Conventional oxygen electrode reaction:

Facts and models. In

moxed ConductorsProc

de, Denmark, 1993.

High Temperature Electrochemical Behaviour of Fast Ion and Miof the 14th Ris0 Int. Symp. on Mat. Set, pages 89-116, RoskilRiso National Laboratory.
on

[18]

S. C.

Fuel

Singhal, editor. Proceedings of the First International Symposium Cells, Pennington, NJ, 1989. The Electrochemical Society, Inc.

Solid Oxide

[19]

F.

ond International

Grosz, P. Zegers, S. C. Singhal, and O. Yamamoto, editors. Proceedings of the Sec Symposium on Solid Oxide Fuel Cells; Held from 2 to 5 July in Athens,

Greece, Luxembourg, 1991. Commission of the European Communities.

[20]

J. Mizusaki,

K. Amano, S.

tion of zirconia oxygen gas

Yamauchi, and K. Fueki. Response and electrode reac sensor. In T. Seiyama, K. Fueki, J. Shiokawa, and

S. Suzuki, editors, Chemical Sensors, volume 17 of Analytical Chemistry

Symposia Se

ries, pages 279-284, Amsterdam, 1983. Elsevier.

[21]

F. H.

van

Heuveln, H. J. M. Bouwmeester, and F. P. F.

van

Berkel. Electrode prop

erties of Sr-doped

ary

area.

LaMn03 on yttria stabilized zirconia. Part I: Three-phase bound /. Electrochem. Soc, 1997. to be published.

[22]

J. Mizusaki, K. Amano, S. Yamauchi, and K. Fueki. Electrode reaction and re Soc. Jpn, 6:1160-1166, sponse characteristics of zirconia oxygen gas sensors. /. Chem.
1985.

[23]

Fukunaga, M. Ihara, K. Sakai, and K. Yamada. The relationship between overpotential and the three phase boundary length. Solid State Ionics, 86-88:1179-1185,
H. 1996.

14

References

[24]

J.

L.

Gland, B.

face.

Surf.

Sexton, and G. B. Fisher. Oxygen interactions with the Pt(l 11) Sci., 95:587-602,1980.
A.

sur

[25]

B. Hammer and

J.

K. Norskov.

Why gold

is the noblest of all the metals. Nature,

376:238-240,1995.

[26]

J. Sasaki, H. Mizusaki, S. Yamauchi, and


of stabilized zirconia cells

K. Fueki. Studies

by

the

complex impedance
A.

on electrode processes method. Solid State Ionics,

3/4:531-535,1981.

[27]

M.

J. Verkerk, M.

W.

J. Hammink, and

J. Burggraaf. Oxygen transfer

on

substi
re

tuted

sistance

Zr02, Bi203, and Ce02 electrolytes with platinum electrodes. by D-C polarization. /. Electrochem. Soc, 130:70-77,1983.
K. Amano,

I. electrode

[28]

J. Mizusaki,
Pt,

S.

Yamauchi,

and

K. Fueki.

Electrode

reaction

at

Oz(g)/stabilized

zirconia interfaces. Part I: theoretical consideration of reaction

model. Solid State Ionics, 22:313-322,1987.

[29]

J. Mizusaki, H. Tagawa,

K.

Tsuneyoshi,

and A. Sawata. Reaction kinetics and

microstructure of the solid oxide fuel cells air electrode

Lao6Ca04Mn03/YSZ.

/. Electrochem. Soc, 138:1867-1873,1991.

15

Introduction

16

Part

II

Theoretical

Analysis
I YSZ

of

the Pt,

02(g)

System

18

Chapter

General Framework,

Modelling,

and

Structural

Investigation

Abstract

study aims to provide a general framework for modelling and structurally investigating complex heterogeneous electrode reaction mechanisms. The necessary theory is derived from classi cal systems and control theory. Relationships between abstract expressions and measurable electrochemical quantities are estab lished. The procedure is illustrated by means of the oxygen reduc tion the interface between at platinum electrodes and yttria-stabilized zirconia solid electrolytes. Dissociative adsorp
This
tion of oxygen
on

the
a

platinum surface,

surface diffusion of
near

atomic oxygen, and

two-electron transfer step

the

triple

phase boundary are considered. The first model includes the adsorption/desorption step and the electron transfer step,
whereas the second model also The finite-difference

incorporates

surface diffusion.
mass

approach

is used for

modelling

trans
are

port. The surface


considered
as

concentrations of adsorbed atomic oxygen

the time

dependent

state-variables within each ele-

*)

Submitted to

/. Electrochem. Soc.

General Framework, Modelling,

and

Structural Investigation

ment. The mass-balance

equations

are

obtained for the state-vari

ables. The reaction mechanisms


form and structural
is

are

formulated in state space

investigation

of the

resulting
is well

set of

equations
con some

performed

on

the

corresponding

transfer functions. The

cept of structural identifiability, which


domains of mathematical
sions

accepted

in

the

describing the frequency response


are

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


behaviour
are

derived. It is shown that

globally structurally identifiable under the given assumptions. It is emphasized that modelling and testing model structures for identifiability must be accomplished prior to exper imental work. In combination with Part II of this publication, a complete tool for the identification of heterogeneous reaction mechanisms is provided.
Keywords.
Electrochemical kinetics, state space

both models

modelling;

structural

investigation;

elec

trochemical

impedance;

oxygen reduction; solid oxide fuel cell.

2.1

Introduction
play
an

Metal electrodes devices such


as

important

role in

high temperature
or

electrochemical
Ni in anodes of
a

Pt in oxygen

sensors or

oxygen pumps,

solid oxide fuel cells. The reduction of electrode resistances has been

major

driving force for the investigation of these interfaces during the past 25 years. The design of electrodes with desired properties necessitates knowledge about the micro-kinetics of the overall electrode process. Although this field has been extensively examined and general agreement exists on the reaction pathway of oxygen at noble metal electrodes, there remains little knowledge and uncertainty about the relevant elementary processes and their kinetic
parameters [2,3]. But,
makes
tions
a

it is this information about the micro-kinetics that

prediction

of electrode

properties

under different

operating

condi

possible. The reason for this situation is probably due to the interdisci plinary of high temperature electrochemistry, where a number of problems must be solved in depth individually, in order to be able to identify a particu lar reaction mechanism. First, models taking into account the relevant elec trode processes are mathematically difficult. Second, the characterization of high temperature electrodes with electrochemical methods needs experience

20

2.1

Introduction

special equipment. Finally, sample preparation and characterization requires knowledge about ceramic materials and its processing. However, modelling is often considered as the most difficult step and is, therefore, put at the end of an investigation. It is one aim of this study to make clear that modelling, structural investigation of the associated set of equations, and digital simulation should be accomplished prior to any experimental work. A large number of authors have studied the behaviour of the Pt, 02(g) I solid
and

electrolyte system. Generally, analyses include an experimental investigation combined with a certain extent of modelling. The methods of modelling have been strongly related to the experimental methods employed for studying this electrode system and can be grouped into (i) steady-state current-voltage investigations [4-12] and (ii) electrochemical impedance spectroscopy (EIS) investigations [11,13-18]. In addition, there are reports of transient-signal (small and large) analyses [19-22]. In all cases, the starting points of a model formulation are the mass and charge balances describing the dynamic prop erties of a proposed reaction mechanism. These equations are obtained from ordinary chemical kinetics considerations. Steady-state models relate a con stant overpotential as the input quantity to a constant current as the output quantity (potentiostatic mode). The equations then may be independent of time and therefore facilitating the mathematical treatment of the equations.
As
soon as

the reaction mechanism is assumed to consist of

more

than

sin

gle reaction step, it becomes difficult to find analytical solutions to the emerg ing system of equations. To circumvent these difficulties, simplifying assumptions are introduced. The most popular, introduced by Bockris and Reddy [23], assumes quasi-equilibrium for all steps except the rate determin ing one. With this method, Butler-Volmer type relations are obtained relating the current J to the overpotential n
I
ir

'Ct,,F

ocF

'o

[exp^-nj-exp^-n]
current

(2.1)
the apparent

where

i0

is the

exchange
[23],
from

density,

cca and ac

are

transfer coefficients

A is the active electrode area, and the

charge remaining
can

symbols

have their usual


a

meaning.
Tafel

If A is known,

i0,

ac, and aa

be

uniquely estimated
sible to include
most

plane plot (log(J)


in the

versus

n).

It is further pos

mass

transport processes

models, although only the

boundary conditions can be treated [7, 8,9,24, 25]. In addition, the steady-state method offers the possibility of predicting the qualitative dependence of the exchange current density, iQ, or the limiting
simple

situations and

21

General Framework, Modelling,

and

Structural Investigation

partial pressure, tempera ture, or overpotential [8,10,14,15,25]. However, steady-state methods do not provide any information about the dynamic behaviour of electrode sys tems, and rarely give unique access to the kinetic constants of the elementary
current,

ij,

on

external parameters, such

as

oxygen

processes involved in the overall electrode reaction. For this purpose,

dynamic

methods

are

methods is limited to
i.e. where
one

indispensable. Furthermore, the use of steady-state investigation of relatively simple reaction mechanism,
step dominates the overall electrode behaviour.
reaction mechanisms at gas electrode of solids
a

reaction

Unfortunately, heterogeneous
state ionics devices involve

number of

dominating
Tafel

the overall characteristics.


an

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


estimates of the

teristics may exhibit

apparent Tafel behaviour, numerical


contain

parameters (P, and iQ) may


to

large

errors.

Interpreting

these data

might lead

wrong conclusions (see also

[1,12,26,27]).

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

02(g)

I YSZ

system with

second-order reaction mech


used to model
on a

[12,31].

This

approach

has been

increasingly

compli

cated reaction mechanisms

[32, 33].

The method is based

Tailor series

expansion of the charge balance equation, from which the current modula tion and finally an expression for the impedance is obtained [30]. Recently, Gabrielli and coworkers provided a general framework for dealing with elec trochemical reaction kinetics of heterogeneous aqueous systems [34-36]. The method allows for the treatment of multi-step reaction mechanisms. But the multi-step
mass

treatment of the electrode reaction must be

abandoned,

as soon as

transport processes become relevant (see e.g. [12] and references therein). Furthermore, the fact that both type of processes (mass transport

heterogeneous reactions) occur in parallel on the electrode surface, dras tically increases the complexity to solve the equation system. It is, therefore, often assumed that only mass transport being relevant within a characteristic length (often over the Nernst diffusion layer length 5, or a multiple of 8; see
and

22

2.1

Introduction

quasi-equilibrium approach is employed for the treatment of the boundary concentrations at distances larger than 8. However, these simplifications may give different solutions for the frequency-dependent
e.g.

[12,16,25]).

behaviour,

as

well

as

for the

limiting
an

behaviour

(see e.g. [37] p. 73, for the


which
occurs

problem

of surface diffusion of

atomic

species

in

parallel

with dissociative

adsorption). We propose to employ numerical simulation techniques in combination with an analytical treatment to overcome the mentioned problems. The general
system behaviour
tions
our

is obtained from

analytical expressions. Approximate solu space"


has not been used in the electro

can

be obtained from simulations of state space models. To the best of


the notion "state

knowledge,

chemical literature. We
In Part I of this

give a brief description in appendix 2-A.l. paper we provide a general framework for modelling electro
and

chemical reaction mechanisms in state space form, which makes structural

investigation, simulation,
tion
state

parameter estimation of heterogeneous reac mechanism possible. First, some general theoretical background about
space

modelling
a

is

given,

and the link between the theoretical concepts


is

and electrochemical cedure

quantities

accomplished. Second, we illustrate the pro


(YSZ).
the

using

fairly

well known reaction mechanism that describes the oxy

gen reduction at interfaces between Pt and Yttria-Stabilized Zirconia


We

particularly investigate steady-state and the small-signal


consider dissociative

the

influence

of

surface

diffusion

on

electrode behaviour. In the first model

(Ml)

we

adsorption

of oxygen molecules and reduction of


area.

adsorbed atomic oxygen within the active electrode

In

second model

(M2), surface diffusion of atomic oxygen


Part II ious
we

on

the Pt surface is included. In

report the computer implementation of the equations, we give var simulation results, and we discuss the results with respect to some of the

experimental results from literature [1]. We have found that it is extremely helpful for a better understanding of a particular reaction mechanism, if time
and

frequency dependent

behaviour

be mentioned that the method

by simulation. It should of state space modelling is widely used in con


can

be studied

theory as well as in chemical engineering (see e.g. [38] or [39]). Nevertheless, we briefly present the necessary theoretical tools and we focus on the peculiarities of electrochemical modelling.

trol and systems

23

General Framework, Modelling,

and

Structural Investigation

2.2
2.2.1

General Framework
The Process of
a

Modelling

basically determined by the purposes for which the micro-kinetic model is required. In kinetics three cate gories are generally distinguished for structure identification, parameter esti mation, and prediction purposes. Although there is general agreement about the reaction pathways at high temperature SOFC electrodes [2,3,40], we still have very little a priori knowledge of the actual electrode mechanism. Our interest has to be primarily focused on the identification of the overall proc ess structure; therefore we first need a of the over qualitative understanding all process and the corresponding elementary processes. Experimental results obtained from various electrochemical techniques provide such information. In addition, information is obtained from other physico-chemical investiga tions, in particular from surface science. From those, we develop a qualitative
picture
of the overall electrode reaction that considers the essential elemen
as

The form and detail of

mathematical model is

tary processes
ideas into
of
a

well

as

their interactions. Last,

we

translate the

qualitative

quantitative description of the model. Here three different types equations emerge: mass balance equations, physical relations, and equa
is obtained

describing the geometry. The final mathematical realization by casting the equations into a form suitable for further analysis
tions mentation in
a

and

imple

computer.
in the structure of the model and its

Often, uncertainties remain


Then simulation is

parameters.

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

At all levels within the

modelling

process, model validation should be


no

applied. Obviously

the model should contain

contradictions and the sim


to

ulation should be verified. In addition, simulations should


available data and the model should be

correspond consistent with accepted theories.

24

2.2

General Framework

2.2.2

General Considerations and

Hypotheses
general agreement

Electrode microstructure.
exists
on

For noble metal electrode

adsorption of oxygen molecules and surface diffu sion towards the triple-phase boundary (tpb) (cf. Fig. 2.1) [7,8,12]. The direct reaction of molecular oxygen from the gas phase with the electrolyte surface
the dissociative

(at least with YSZ)


trodes is

or

the solid state

tiansport of oxygen ions

in Pt

or

Au elec

generally ruled out [3, 41, 42]. For modelling purposes quantitative data for the tpb length l^ are needed. These values can vary over more than two orders of magnitude (0.1-10 urn/urn2), depending on the preparation procedure as well as on the operating conditions of the electrode. Although
estimates for

/^b

and the

mean

pore diameter

can

be obtained from micro

scopic data, modelling is complicated by the morphology of the porous elec trode and therefore simplified electrode geometries are employed (see

Fig.

2.1

Schematic view of the oxygen reduction process at interfaces between noble

ion-conducting electrolytes.The case of platinum is taken as an example. The oxygen molecules adsorb dissociatively (1) on the metal surface. Adsorbed atomic oxygen diffuses (2) towards the triple phase boundary (tpb). The electronation reaction (3) near the tpb may be considered as a single-step or a multi-step
metals and solid oxide
reaction. The concentrations of oxygen vacancies
e
,

as

well

as

the oxygen

partial

pressure pQ

V0, oxygen ions 00, facing the noble metal are

and elections considered to

be constant

over a

wide range of

operating

conditions.

25

General Framework, Modelling,

and

Structural Investigation

appendix 2-A.l). Fig. 2.2 shows a SEM of a Pt electrode on a YSZ single crys tal surface. It is readily seen that a description of the microstructure can be accomplished with a few simple quantities (see appendix 2-A.2). However,
an

uncertainty

remains and

large

errors

may be introduced into

model

description. Moreover,
how

there is still little information about the

question

of

spatial extension of the tpb is. It is easy to demonstrate that there must be a spatial extension of the electrochemical active area around the tpb to accommodate the high current densities experimentally found (see
large
the

e.g. [2,40,

43]).

We will

give

more

account

on

this

question

below.

Adsorption.
tation, oxygen

The

adsorption

of oxygen is the first process

taking place

on

the noble metal surface.

Depending on adsorption is generally

the noble metal and its surface orien


an

activated process which

proceeds

through
mentary

The ele sequence of precursor states (see e.g. for Pt(lll): [44, 45]). steps of the oxygen adsorption and desorption are rather well dis-

Fig.

2.2

Secondary
with Pt

Electron

Micrograph (SEM)
was

of porous Pt
with Pt

on a

(001)

YSZ

single

crys

tal surface.The YSZ surface

dc-sputtered
area

during

10 min,

additionally
Esti

painted
mates

paste,

and

subsequently
tpb

fired in air at 1223 K and the

(950C)
area

for 4 h. The SEM

shows the

boundary
length

between the

sputtered

painted

(lower right).

of the

of the

and the pore sizes may be obtained from

quantitative

image analysis.

26

2.2

General Framework

criminated for

Pt(lll) surfaces [4447]. However,

care

is necessary when

employing

these data in simulations because

they

were

almost

exclusively

obtained from

single crystal

studies under low

partial

pressures and at rela

tively low temperatures. Real noble metal electrodes are polycrystalline and are operated at high temperatures under ambient pressures. Furthermore, it is well accepted that low amounts of impurities may drastically influence the

adsorption

behaviour of oxygen

on

metals

[48].

We should also be

aware

of

experimental data show some scatter and some param eters, such as most frequency factors, are even not known. Nevertheless, information about the adsorption and desorption of oxygen on noble metal surfaces constitutes basically the only a priori knowledge we have for model
the fact that available

ling

the oxygen

exchange reaction at noble metal/YSZ


are

interfaces.

types of diffusion which may be relevant when modelling high temperature oxygen electrodes. First, binary gas phase diffusion of the oxygen through the pore network of the cathode. Second,
Diffusion.

There

two different

surface diffusion of adsorbed oxygen intermediates. The first type of diffu


sion
can

generally

be ruled out in these systems at

high

to moderate oxygen

atm) because of the very high diffusivities partial pressures (pQ > 10 through the large pores even at high temperatures [14]. For modelling pur poses, the partial pressure of oxygen is therefore assumed to be uniform over space and time. However, at oxygen partial pressures below ~10-3 atm, gas phase diffusion may become apparent at porous SOFC cathodes at high tem
peratures [49].
In contiast, diffusion of adsorbed oxygen intermediates due to
a

gradient

of

potential along the metal surface can generally not be consid ered to be either infinitely fast or absent. It is important to recognize that these limiting cases result in completely different dynamic behaviour of the
the chemical

electrodes. In the first case, concentration


can

gradients are absent and


where different

the system

be modelled

using

one

single compartment

species

are

distributed

homogeneously.

The concentration of adsorbed

species
of the

would

remain constant with time and would further be

independent

applied

overpotential (i.e. the resulting current). Therefore, the overall electrode reac tion would be entirely charge-transfer controlled. In the second case, diffu
sive transfer of adsorbed oxygen
over

the electrode surface is absent and

therefore

only

the reaction

zone

must be considered

[12]. The rate-controlling

mechanisms may either be the


ess,
or a

adsorption

process, the

charge
to

transfer proc

combination of both. Both

types of problems lead

systems of ordi-

27

General Framework, Modelling,

and

Structural Investigation

nary

first-order

differential

equations,

the

state

equations,

which

are

generally non-linear.
Electrochemical reactions. The rates of electron transfer processes
are

indi

rectly influenced by a change of the electrode stoichiometry or by a change of the electrochemical potential of the reacting species, whereas the rates are directly influenced by a change of the work function of the electrode mate rial. It is usually assumed that the rate constants of the election transfer reac tions depend exponentially on the applied potential [23,30,50].

2.2.3

Modelling Reaction Mechanisms


We consider the noble metal,

State space model. electrode form


as an

021

YSZ
can

high temperature

open time-invariant

system [38]

which

be described in the

(see also appendix 2-A.l)

x(t,p)

f[x(t,p),u(t),t;p]

(2.2)

subject

to the initial conditions

x(0,p)
In

x0(p).
state variables of the
e

(2.3)
model,

Eq. (2.2)
or

the vector x(t)

represents the

usually
variable

the concentrations of adsorbed

species; u(t)
the

is

some

external

input

that

can

be varied
or

during

experiment,

e.g. the

potential

difference the temperature

the pressure; p is the vector of the unknown the model consists of the observation

parameters.
In addition to the differential

Eqs. (2.2),

functions

y(t,p)
where

g[x(t,p);p],
is referred to

(2.4)
as

y(t)

Rp denotes the observed quantities and


or

the that

model output the

response function
are a

(most often the current). We


and that

assume

parameters

priori independent
or

and g

are

(generally

non-linear) real analytic functions for all possible


It is

sets of

parameters.

analytical solutions of this set of differential equations, that would describe the large-signal dynamic behaviour. Although non-linear studies are more general and yield more information, small signal methods are more often employed for they rely on a generally
difficult

impossible

to obtain

28

2.2

General Framework

linearisation of the model around

some

steady-state operating point

that is

associated with constant external variables. This mathematical treatment much easier.
Linearized state space model.
Linearisation of

procedures

makes further

Eqs. (2.2)

and

(2.4) yields (2.5) (2.6)

5x(t, p)

A(p)bx(t, p) C(p)Sx(t, p)
system

B(p)5u(t) D(p)bu(t) describing


the

Sy(t, p)
where A, B, C, and D,
ties
are

the
are

matrices

system proper

entirely.

The matrices

given as
R
nxn

A-*/
A"

dx

(2.7)

_d/
=

du

nxm

(2.8)

dx

pxn

(2.9)

du

pxn

(2.10)

particular operating point. The intrinsic dynamic behaviour of a system is given by the eigenvalues of matrix A. For intrinsi cally linear systems, 5x and 8w are replaced by x and u. However, in elec trochemistry we are dealing with intrinsically non-linear systems due to the exponential dependence of the electrochemical rate constants on the overpo tential [23]. In the following we will write x and u instead of dx and Sw, keep ing in mind that we only mean small deviations around an operating point.
(*) denotes
a

where the star

Transfer function ized state space

description. An equivalent representation of the linear description can be obtained by Laplacian transforms of
with

Eqs. (2.5)

and

(2.6)

x0

0:

Y(s,p)
where

G(s,p)U(s)

(2.11)

29

General Framework, Modelling,

and

Structural Investigation

G(s,p)
LZ(s) and Y(s,p)
nal y;
This
are

C(sI-A)_1B

D.

(2.12)

the

Laplace

transforms of the

G(s,p)

is the transfer function and I

description
is

is either called "transfer

input u and the output sig is the appropriate identity matrix. function description" or "Laplace

description". G(s,p) generally a three-dimensional matrix in case of a multi-input multi-output (MIMO) system. In case of single-input multi-output systems
(SIMO), G(s,p)
reduces to
a

transform

two-dimensional matrix, and in

case

of

sin

gle-input single-output (SISO) systems system, G(s,p) results in a fraction. In this case, G(s, p) can be easily obtained by means of Eq. (2.12) or by Laplace transforming, in the linear (or linearized) case, the input and output
Y(c n\
=

bts

Jfc

G(s,p)

^^=
U(S)

k
n

+bk
+ans

Jfc-2
,s x +
...

b-,s
-

bn

k~l

(k<n)

(2.13)

+...

+bls

a0
are

where

is the

Laplace

variable and

b{(p) and a{(p)

constant coefficients

of the transfer function.

systems and control


similar

Eqs. (2.12) and (2.13) are fundamental results from theory (see e.g. [38]). Gabrielli and Tribollet first used a

description

as

presented

above for the treatment of aqueous electro

chemical systems
The state space

[35].
is the most reliable linear

representation
use

time-independent

(LTI)

model to

for computer

analysis.

Stable computer

the eigenvalues, frequency response, time response, and other (A, B, C, D) quadruple are known [51]. Transfer function models are numeri cally more difficult to handle, and tend to be inherently ill-conditioned. Nev ertheless, this representation is often used for testing the identifiability of

algorithms properties of

for

low-order LTI systems

(see e.g. [52,53] and references therein).

2.2.4

Identifying G(s)

with Electrochemical
Classical

Quantities

deals electrochemistry with electrochemical systems as SISO systems. Specifically, in potentiostatic mode Ip(t,p) u(t), where ZF is the Faradaic current y(t,p) and r\(t) and the overpotential r\ E- E is defined as the deviation of the potential E from the equilibrium potential E We would like to point out that this approach is by no means limited to the treatment of SISO systems, but that it

Faradaic admittance and

impedance.
=

30

2.2

General Framework

is

applicable

to the treatment of SIMO

systems
as

in much the

same

way

(cf. [36,54]).
The linearized state space

description is
=

obtained

x(t)

Ax(0 Cx(t)

Bn(f)

(2.14) (2.15)

IF(f)
where D has become
a

Dr\(t)
In accordance with

scalar

quantity.

Eq. (2.11)

and

(2.12)

we

further obtain

h(s,p) YF(s)
which is
we
=

Y(s,p)T\(s)
+

(2.16) (2.17)

C(sI-A)_1B

obviously

the Faradaic admittance transfer function.

Accordingly,

find for the Faradaic

impedance

transfer function

ZF(s,
Frequency

^.
[30]

(2.18)

response.

imposes

impedance spectroscopy harmonically oscillating overpotential with frequency


at

Electrochemical

(EIS)
a)

and

amplitude fj

the

input

of the system

r|(0
It
can

f\cos((ot).
[38] that the output signal

(2.19)
in time

be shown for stable LTI systems

domain is

given by
y(t)
=

ycos(cof

(p)

(2.20)

where

|
The

|YF(;co)|

andcp

Zy-Zn

arg{YF(/co)}.

(2.21)

complex function YF(jco) is known as the frequency response, |YF(jco)| as the magnitude and arg{YF(jco)} as the phase of YF(jco), i.e. we have a relationship between the measurable frequency response and the model in a
state

space
use

or

transfer function

ral to

the admittance data

description. Note that it would be more natu than the impedance data because EIS is nor-

31

General Framework, Modelling,

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 small-signal excitation. If the non-linear physical system is excited with large input signals, the output might contain frequen cies other than the input frequency and the output magnitude might be dependent on the input magnitude. This can easily be checked with EIS by exciting a sample with increasing input amplitudes. The validity of linearity prevails as long as |YF(jo))| and arg{YF(jco)} do not depend on the input amplitude. Additionally, the system matrices should not be used to calculate any large-signal response since the non-linear model equations must be employed for these purposes. Let us identify some useful quantities that can be generally obtained from the state-space description of an electrochemical
system.

Charge

transfer resistance.

The

charge

transfer resistance

Rt

is defined

by

1/Rt
which becomes with

(2.22)

Eq. (2.15)

1/Rt
i.e.

lim
co-*

YF(jco),
on

(2.23)
the real axis at

Rt

is

scalar

quantity

which

can

be found
=

high

fre

complex plane plot of ZF(jco) 1/YF(jco) (cf. Fig. 2.3). Accordingly, 1/D is the most general description for Rt taking the non-reversibility of the elementary reactions into account. Note that only in the case where the concept of the rate determining step applies, we obtain
quencies
of the from

Eq. (2.1)

R"1
where

i0

[expj^n]- expj^n)]
at the

(2.24)
At
zero

f|

is the

overpotential

corresponding operating point.

overpotential we find

the well known result

Kt1

hd^rY, + c> o*f(.oaTv.c'-'o^r>


=

(2-25)

32

2.2

General Framework

ZgCjO))
ioo

316

L.

316/
N

3kZ

\#32

10k/*
i

100k/
*t

%
*c
i

-2
-

a)

10

15

20

Re(Zp/Q)

20

11 ii

11 r

20

CJ

-fc10
N
oo

10

1=^
*

'

ii

'

'

''

'

b)

10

101

102

103
-h
f/(2n*-1)

104

105

Fig.
()

2.3

General Faradaic

frequency
of

response

ZF(j(o)

of first-order electrochemical Bode

systems.(a) Complex plane plot


denotes

ZF(jco)
were

data and

(b)

plot

of the

same

data.

|ZF|

and

(- -) denotes the phase <p. The numbers


in Hz. The data

in the

complex plane plot

denote the

frequencies

obtained from

simulation of model M2

(fully
ance,

described in Part II of the present paper

[1]).
=

denotes the
-

polarization

resist

Rt

is the transfer resistance, and

resistance.

Ze(jco)

denotes the

R Rc Re Rt denotes the concentration frequency dependent part of the Faradaic impedance


=

ZF(jco).

33

General Framework, Modelling,

and

Structural Investigation

where

is the number of electrons which

were

transferred in the rate-deter

mining step,
is of

and

v as

is the stoichiometric number


it

(see [23], p. 1006). Eq. (2.25)

importance
can

gives

relation between the

iQ/

which

be obtained from
can

exchange-current density steady-state current-voltage measurements,


(see below).
output
to

and

Rt,

which

be obtained from EIS measurements


The dc

Polarization resistance.
its

gain
s

of

system
=

is the ratio of the

(constant) input after all

transients have
=

decayed.
0 in

To find the dc

gain of an

asymptotically stable system we put the polarization resistance R

jco

Eq. (2.17)

and obtain for

^-

YF(0)

D-CA_1B.

(2.26)

Obviously, Rp depends also on f\ at the operating point as well as on the experimental parameters (T,pQ). R is also a scalar quantity which can be found on the real axis at low frequencies of a complex plane plot of ZF(j(o) (see Fig. 2.3).
Concentration admittance.
write the Faradaic For
reasons

which will become clear later,

we

impedance ZF(s) as the sum of the charge transfer ance Rt and the concentration impedance Ze(s), an impedance due time dependence of the concentrations of the adsorbed species ZF(s)
=

resist
to the

Rt + Ze(jco)

(2.27)

From

Eq. (2.17)

we

obtain

yF(s)
and from

d^ ^si-a^b]
+

(2.28)

ZF(s)

-i,
=

YF (s)

we

further have

ZF(s)

D
=

D-(D
D

C(sI-A)

-l,

B)
B

-i, D + C(sl-A) B_

C(sl-A)

-l,

(2.29)

From

Eq. (2.29)

we

obtain

ZF(s)

C(sl-A)
D
+

C(sI-A)_1B.

(2.30)

34

2.2

General Framework

which is

equivalent

to

YF(s)-D

ZpW-V*.-^By comparing Eqs. (2.27)


and

<2-31>

(2.31)

we

finally

obtain

ZQ(s)
and

-Rt

-^H-r-

YF(s)-D
Yv(s)

(2.32)

by definition (cf. Fig. 2.3)


1/Rn-1/Rf

Ze(0)
Eqs. (2.23) quencies and by
From

Re

-Rt

^
that

'

Rp Rt
-

(2-33)

ZF(jo)) is limited by Rt at high fre R at low frequencies. The frequency response ZF(jco) in between these limits is described by the concentration impedance Zq(jco) (Eq. (2.32)). Note that the concentration resistance Re not simply depends linearly on the charge transfer resistance Rt, but that a rather complicated relationship exists. Thus, it is expected that the dependence of Re (or of R if R_ Rt) on temperature and on oxygen partial pressure shows a rather complicated behaviour.
and

(2.26)

we see

2.2.5
Bode

Working with Frequency Responses


plots.
If linear

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

35

General Framework, Modelling,

and

Structural Investigation

We will illustrate this


common

procedure later. The interested reader textbook about control theory (see e.g. [38,39]).
vs.

is referred to

Admittance

Faradaic admittance.

It is

emphasized

that

ZF

describes

yield the total impedance Z, i.e. ZF obscured by a double layer capacitance Cdl. A rig orous treatment of the electrode impedance must include coupling between Faradaic processes and the charging of the double layer. If, and only if, the origin of Cdl can be attributed to a space charge at the interface between the noble metal grains and the YSZ [12,50,55], can it be assumed that Cdl is associated in parallel with ZF and therefore:
dynamics.
In contrast, EIS measurements

the intrinsic electrode

Z(ja

' Zp(jco)
=
.

l+]CoCdlZF(]to)

(2.34)

un-compensated electrolyte resistance Re present. Therefore, the total electrode system can be represented by the "equivalent circuit" shown in Fig. 2.4.
is

In

addition, there

always

finite

C<11

*e *t
-

zeGco)

ZpXJG))

Fig.

2.4

"Equivalent circuit"
=

impedance Zp(s) function: Cdl(s) ZF(j(B) comprises a series combination of the transfer resistance Rt and the concentra tion impedance Ze(jco). Note that the (measurable) frequency response Z(jco) depends on ZF(j(o), Cdl, and Re and that the intrinsic dynamic behaviour of the electrochemical interface is exclusively described by its Faradaic frequency response ZF(joo) (not directly
is obscured

Faradaic metal/electrolyte system.The by an layer capacitance Cdj (transfer in parallel and an electrolyte resistance Re in series. l/(sCdl))
an

of

noble

electrical double

measurable).

36

2.2

General Framework

The various

possible frequency
as

cal reaction mechanism

responses depend on the actual electrochemi well as upon the values of Cdi and Re. We will
we

expand

this
is

point

in

part

II. However,
on our

would like to

ZF(j(o)

entirely dependent
with EIS

kinetic model and

point out here that that Re and Cdj are


can

(measurable!) external quantities. It

is well known that

Re

be determined

experimentally

[56]

or
can

with the current be almost

interruption technique [57].

equally well determined from EIS data, if the general "equivalent circuit" of Fig. 2.4 applies, even without mak ing any assumptions on the Faradaic impedance [58]. There are examples in literature where values for Cdl are reported from equivalent circuit analyses ([17,18,59] and references therein). Always, an a priori choice of an equiva lent circuit was made. Obviously, the values determined for Cdi from fitting impedance data to equivalent circuits largely depend on the choice of the cir
Cdl
cuit. We believe that the

But it is less known that

interpretation

of these data is doubtful.

2.2.6

Identifiability

of Linear Reaction Models

Testing model structures a well accepted practice


notion of

for

identifiability

and

distinguishability has become


systems [60, 61]. The

in identification of metabolic is most

identifiability

lems often encountered in

easily understood by considering the prob equivalent circuit fitting. There, identical simula
parameters for the
or

tion results may be either obtained with different sets of


same
same

equivalent
the
same

circuit

(problem

of structural

global identifiability),
same

the

simulation results may be obtained with different model structures


number and type of electrical

(with
tural

elements) but the

set

of

parameters (problem of structural model distinguishability). Note that

struc

global identifiability is a property of the model itself that is assessed. It has nothing to do with the accuracy of measurements and data. There are currently many methods available for analysing the identifiability of LTI sys
tems. In

contrast, efficient methods to

analyse

the

identifiability of non-linear
is

systems have only recently been introduced [62, 63]. The interested reader
referred to the cited literature and references therein.
It is

only recently that the concepts of model identifiability and model distin guishability have been introduced in the field of aqueous electrochemistry
[64, 65].
It is not
our

intention to present the

substantial, although mostly concerned


mechanical systems

theory, for the literature on it is with pharmaceutical kinetics [61] or

[62].

A reaction mechanism is said to be

globally
p
can

struc

turally

identifiable if, and

only if,

unique

set of

parameters

be deter-

37

General Framework, Modelling,

and

Structural Investigation

mined for

given input. The finite (and hopefully small)


a

mechanism is said to be number of

locally

identifiable if

parameter

sets is

estimated from

equivalent circuit fitting). Non-identifiable mechanisms give identical outputs for a given input for any set of parameters. We will encounter all three situation while investigating our proposed models of the Pt, 02(g) I YSZ system. experimental
data

(very

often encountered in

2.3
2.3.1
The

Reaction Models of the Pt,


Introduction
with the
use

02(g)

I YSZ

System

problem associated

of numerical methods may, in

our

opin

ion, best be elucidated using simple


idea

examples.

This section illustrates this

by considering a simple reaction mechanism of the Pt, 02(g) I YSZ sys tem, which is by far the most thoroughly studied electrode system in high temperature electrochemistry (see e.g. [5,11,13, 66]). Dissociative adsorption
of oxygen
on

Pt, surface diffusion of atomic oxygen, and electrochemical


a

reduction of adsorbed oxygen in


is considered In
our

two-electron transfer step

near

the

tpb

line

[25,66]. (Ml),
mass

first model

and

charge

balances

are

formulated and the


surface dif transfer of

complete model structure is developed. For illustration purposes, fusion is first neglected, i.e. we assume that any diffusive
adsorbed atomic oxygen is slow
~723 K

(which

is the

case

for temperatures below direct

(~450C) [11])

and therefore the oxygen is

only delivered by the

adsorption process near the tpb. The model Ml is tested for structural identi fiability in the steady-state as well as for electrochemical impedance spectros
copy.
In
our

second

model
is

(M2)

we

include

surface

diffusion.

The

finite-difference

approach

employed

for the treatment of surface diffusion.

Considering one-dimensional,
solution.
are

first-order

finite-difference method is the most

coupled differential equations, the straightforward method of numerical 021


YSZ

Computer implementation
part
II

and simulation results of both models

illustrated in

[1].

more

realistic model of the Pt,

system

(M3), accounting

for the

Pt surfaces, will be the

step-wise adsorption/desorption dynamics subject of a forthcoming publication [67].

of

02

on

38

2.3

Reaction Models

of the

Pt, 02(g) I YSZ System

2.3.2
Model

Basic

Equations

and

Assumptions
exchange
of oxygen at

equations.

We consider the electrochemical

the Pt/YSZ interface which is described

by
=

the overall reaction

^02
represents occupied
the electrons within the Pt.

V0 + 2e"

00

(2.35)

where, in Kroger-Vink notation, V0 represents the oxygen vacancies,


oxygen lattice sites in the

00

electrolyte,

and e~

represents

The overall reaction is considered to consist of several

elementary reactions [5,8J. Oxygen adsorbs dissociatively on the Pt surface, diffuses linearly in the direction perpendicular to the electrode surface, and is electionated and incorporated near the tbp in the active area of width w (cf. Fig. 2.1 and
Fig. 2.5):

2(g) + 2s 2ad
des

(2.36)

Tt

EMD
+

C237,

ad

Vb

2e

<00 +
1

(2.38)

where

kad and fcdes are the rates for adsorption and desorption of oxygen on polycrystalline Pt; c is the surface concentration of Oad; D(c) is the chemi cal diffusion coefficient of Oad on the Pt surface; kt and k- are the electro
chemical rate constants; and [s] is the concentration of vacant surface sites.

Assumptions.
(i)
The

We will base Ml

on

the

following assumptions: dissociatively


and

adsorption of oxygen Langmuir isotherm;


be

occurs

obeys

(ii)

The maximum number of surface sites per unit


can

area

which

occupied by Oad

is characterized

by N0;

39

General Framework, Modelling,

and

Structural Investigation

(iii) The

rate of

adsorption /cad
Vq

and
are

desorption kdes

are

independ

ent of surface

coverage and

known from the literature;


in the YSZ surface
are con

(iv) The

concentrations of

and

00

stant;

(v)

The electrochemical rate constants


ent
on

are

exponentially depend

the

potential
=

difference

*!
A-

klc(T)exp[-n$cFE/(RT)]

fcic(T) exp[npaF/(RD]

(239)

where

klc(T)

and k- (T)

are

potential independent
n

chemical

rate constants;

Pc

and

(3a

are

the cathodic and anodic transfer


is the number of
our case n
=

coefficients of the electrochemical reaction;


electrons transferred in the reaction step

(in

2);
n

T| where

eq

is the

equilibrium potential

and

is

the For M2
we

overpotential.
assumption:
on

make the additional

(i)

Surface diffusion

depends only

concentration

gradients.

No interaction of adsorbed

species

is

considered;

(ii)

The surface diffusion coefficient D is known from literature

data;

(iii)
Mass and

D is

independent of the

local surface concentration.


and

charge balances.
=

For Ml

mass

charge balance give


(2.40)

^[Oad] 2fcadp02[s]2

2fcdes[Oad]2
+

-MOadHVol

fcjtsHCk]
(2.41)
from the

IF
where

2EAa[fci[s][Oj] -fc1[Oad][Vol]
is the
area

Aa

tpb

x w

of the active

region extending

tpb

electrolyte grains, and/or along the electrolyte surface. For the moment we make no speculations as to the physical basis of this extension. From the modelling point of view, the active region is simply regarded as a

line under the

40

2.3

Reaction Models

of the

Pt, 02(g) I YSZ System

Fig.

2.5

Schematic view of the active electrode

area near

the

physical extension of the active area around the tpb ,w, from only the electron transfer rate in the active area Aa, and not the location of the reaction, determines the electrochemical properties of the interface. Accordingly, we can Aa con
sider to extend from the

tpb.Regardless of the a conceptual point of view

tpb

towards the Pt electrode.

strip extending from the tpb line along the noble metal surface towards the electrode (cf. Fig. 2.5). We assume for the moment that Aa is a priori known.
For M2
a

further term must be added to

Eq. (2.40) accounting for

the surface

diffusion.

Complete
malized

model structure.

The mathematical model should first be


its numerical

nor

or

scaled to

improve

plished by replacing the surface N0 coverage. By expressing [Oad]


=

conditioning. This concentration by its fraction

is

accom

of surface

and [s]

N0(l-6) Eqs. (2.40)

and

(2.41)

are

rewritten

/i=

dt

2*adPo N0 (i

e)2 ^desN0 e2
-

(2.42)

*i-[Vo]-e

*r[C&]-(l-6)

41

General Framework, Modelling,

and

Structural Investigation

gl:

IF

2N0FAax kv [00] (1 -0)-^ [V0]


(2.43)

which is

simply

representation

of

Eqs. (2.2)

and

(2.4)

with the state vector

x(t,p),

the

input

scalar u(t), and the

output scalar y(t):


=

Q(t,p)

x(t,p),n(t)

u(t), and I(t,p)


is

y(t,p).

(2.44)

The vector with the unknown

parameters

given by
(2.45)
reac

[fclc(T),Pc,fcIc(T),PJ.

Eqs. (2.42)
To

and

(2.43) generally describe the dynamic behaviour of the

tion mechanism Ml.

complete Ml, we have to consider all additional and independent alge braic equality or inequality constraints relating 9, n, and p or any combina tion of these, known a priori. The relationships are generally written as
/j[9(f,p),n(f),p]<0.
The

(2.46)

equation system of Eqs. (2.42) to (2.46) is defined as the constrained structure, which completely describes our model structure Ml. In our partic ular case we have the two following equality constraints (cf. e.g. [23]).

Pa
The number of

Pc"1

Oand/F(eq)

0.

(2.47)

independent parameters is therefore reduced by the number of equality constraints. Accordingly, the number of parameters to be deter mined in Eq. (2.45) is reduced to one rate constant and one transfer coeffi cient, e.g. p [klc(T), f5c]. In the following we will simply write P instead
=

ofp.

2.3.3
Let
us

Electrode
consider
are
a

Overpotential
type shown
in in
a

cell of the

ments

performed
same

three-terminal

Fig. 2.6. Electrochemical measure configuration where the working


counter electrode
aware

electiode

(WE), reference electrode (RE), and

(CE)
a

are

exposed
ence

to the

atmosphere.

We should be

of how

polarisation
refer

device interacts with the electrochemical cell. In

potentiostatic

mode

potential

difference between the WE and CE is set

by

the

experimenter.

42

2.3

Reaction Models

of the

Pt, 02(g) I YSZ System

Negative feedback of the actual potential difference ensures control of the ref erence potential. A polarisation is imposed on the CE side. As a consequence, the electrode reaction on the CE departs from its equilibrium point and the electrochemical potential of oxygen ions, ji 2-(P"), in the surface of the solid

electrolyte
fore,
a

is altered. This

causes a

current

through

the

electiolyte and,

there

net current

flows

through

the WE. If the electrode reaction is not infi

nitely fast, ji 2-(P') deviates from its equilibrium value, whereas jio2-(P) remains at its equilibrium value, ji 2.(P') is somehow related to the oxygen partial pressure and the current. The question which emerges is the follow ing: what is the physical significance of the potential difference between WE
and CE that
can

be measured?

We therefore consider the

following half-cell

reaction

02_(P)|02,Pt(a)
where

(2.48)
Pt

P denotes the solid electiolyte and where the electrode material


seems

(phase a)

not to be

involved in the electrochemical reaction. The poten

tial is determined

by

the

following reaction

k>2
i.e. the electrons
are

2e~>02~,

(2.49)
common

the

phase

and

p.

For the

only charge carrying species which are equilibrium of reaction Eq. (2.49) we have

in

WE
Pt

RE

'.

.'

YSZ
Pt"

P'
3"
,

CE

Fig.

2.6

Schematics of

three-electrode cell with identical porous Pt electrodes.The


are

notations used in subsection 2.3.3

indicated.

43

General Framework, Modelling,

and

Structural Investigation

^
jL(y)
=

2^(00

ji02-(P).
potential
of

(2.50)

With the definition of the electrochemical

species

i in

phase

y,

ziFcp(y), and the definition of the chemical potential, p..(y) + RTlnfl t(y) where flj(y) is the activity and m(y) is the stand p:.(y) ard chemical potential of species i, we can calculate the equilibrium potential difference (Galvani potential) between the metal and the solid electrolyte at
(i^y)
+
=

the reference electrode

as

follows

eq4

Acp

,a.

u(cx)-u(P)
=

RT

cp(a)-cp(p)

lnfle(p).

(2.51)

where

we

used
can

lyte, fle(P),
involved

1. The activity of the elections in the solid electio ae(a) be expressed in terms of the equilibrium in which they are
=

K(0\02

(2.52)

o(P)-WP)r
phase (g)
=

At the reference electiode, the gas

is in

equilibrium
=

with the solid

electrolyte

surface
=

(P), thus ApG


where

Mo^-lk^P)
conveniently
we

anc^

a0(P)

fl0(g)

JPo /*/p~

we

set

1 atm.

this result and

solving Eq. (2.52)

for

ae(P)

obtain for the

accordingly Using equilibrium

potential

difference

Acpeq
where
we

Acp
=

ln(^) ||ln[flo2.(P)]
-

(2.53)

used

Acp

Au

RT
+

ln[K(02IO )]

2-

for the concentration inde

pendent terms. The overpotential n

is defined

as

the deviation of the interfacial

potential dif
=

Acp- Acpeq. equilibrium potential difference A(peq, T| If a current flows through the interface between the electrode (a') and the solid electrolyte (P'), the equilibrium situation no longer prevails for polarizable electrodes. Analogous to the derivation of Acpeq we obtain for the non-equilibrium potential difference
ference Acp from the

Acp

A9

|ln[ao(P0]-f^m[ao2_(P')].
44

(2.54)

2.3

Reaction Models

of the

Pt, 02(g) I YSZ System

With the definition of the electrochemical

potential for

2-

we

obtain

gln[flo2.(P')] ^[ii02-(P')-lio2-(P')-lio2-0]+<P(P')
=

(2-55)

and jj,

similar
=

result
we

for

2-(P)

by

replacing

P'

with

p.

With

2-(P)

M^n2-(P')

obtain for the

overpotential

Acp-Acpeq

|[|io2_(P)
+

jio2_(P')]

[<P(P)

cp(P')]

(2-56)

RT,

MP')

2Tln

-fa-

Eq. (2.56)
the
the

overpotential is attributed to the ohmic drop due to ionic current in the solid electrolyte (first term: ohmic potential drop), to (ohmic) potential drop due to charge transfer (second term: charge-trans
shows that the
and to the deviation of

fer

overpotential),

fl0(P)

frm

me

equilibrium value
overpo

at the

electrode/solid electrolyte interface (third


can

term: concentration

tential). Accordingly, Eq. (2.56)

be used to validate simulation results.

2.3.4

Structural

Properties

of the Models

Model Identification. the structure of


a

Identification is concerned both with

determining

physical process
of
a

and with

estimating

the unknown parame

ters. The structure

mathematical model is reflected in its set of


The

(coupled)
question

differential of whether

equations. it is possible
on

question
a

of identification addresses the

to obtain

unique

solution for the unknown param


a

eters of interest

the basis of data collected in


as

question
If the

is often referred to

that of
can

particular experiment. This theoretical or structural identifiability.

theoretically identified uniquely, the parameters estimation problem is theoretically well posed and the actual experiment can be carried out to provide real data for parameter estimation. This assumes, however, that the experimental test data used for identification are noise-free and that the structure of the proposed model is not in error (question of practical identifiability). Indeed, the second assumption is often not fulfilled and therefore postulating a false of (partly) inappropriate model
parameters of
Ml and M2

be

structure constitutes

an

important

source

of

error.

45

General Framework, Modelling,

and

Structural Investigation

Equilibrium potential Eeq.

We first show that the unknown parameters p


can

of the model structures Ml and M2

be

overpotential measurements. We first describing the steady-state IF(n) behaviour. Starting from this result we prove in a second step the global structural identifiability of the mechanisms in the steady-state. Under steady state the condition dQ/dt 0 must apply. By solving 0/we obtain for the equilibrium potential Eq. (2.43) for IF(E )
=
=

uniquely obtained from currentrigorously develop the expression

eq

,Po>)

2/'

ta[*ic<T)'[o^'l-VT,p0z)J
in this way E

(2.57)

where

F/(RT). Note that


well
as

(T, pQ ) depends

on

the tem

perature

as

on

the oxygen

partial

equilibrium

surface concentration of

Oad

pQ ) denotes the which is obtained from the mass


pressure.

Q0(T,

action relation

(Eq. (2.36))

%(T, Pp2)

l-%(T,Po)
with the

K(T)

fc

(2.58)

equilibrium
in

constant

K(T)

Jkad(T)/kdes(T). By putting

Eq. (2.58)

Eq. (2.57)

we

obtain

,T

,
2

eq

2/

r^(T) [v] [k-lc(T) [0x^j


=

K(T)

^ln(p02)
=

(2.59)

and, accordingly,

eq(T, pQi)

eq(T) + eq(p02).
=

Eq. (2.59) is simply an expression of the Nernst form. We arbitrarily set the T and pQ equilibrium potential which evolves at T equal to p0 zero. In this way the electrode potential, and therefore also the electrochemi

cal rate constants,


For the

are

defined relative to this reference state.

temperatures

not too far

from T

we

make the

following

formulation for

temperature dependence of the chemical

rate constants:

klc(T)

*lc.exp[-El/(RT)]
k-lc-exp[-El/(RT)]
46

k-lc(T)

(2.60)

2.3

Reaction Models

of the

Pt, 02(g) I YSZ System

where

the_pre-exponential factors, klc and k- and the activation energies, a and a, are assumed to be temperature independent. Accordingly, we find in the reference state
,

V3

57-hl
fclc
we

fcic [V0]
*lc
=

[Oq]
and

+tf
kl(
=

hl<^5)

(2-61)

where, by definition,
With

fclc(T)

p020

1 atm

find

k-lc

at T

from.CEq. (2.61)

fcIc(T).
as

[V0]

[Oq]
The values for the forward and backward electrochemical rate constants at

equilibrium, kx(T,pQ ) and k-(T,p0), are finally obtained from Eq. (2.39) by use of Eqs. (2.59) to (2.62). In principle, we are free to choose the reference state. For obvious reasons, it is advantageous to take it at 1 atm. The reference temperature can be pQ taken anywhere, but once this temperature is fixed, the chemical rate con stants must be described by Eq. (2.60) and (2.62). For simulation purposes we need to assign the activation energies a and Ea some (reasonable) values. In principal, it is possible to determine these values experimentally. We will return to this point below. Finally, it is important to recognize that by defin ing the equilibrium potential in this way, a change in the oxygen partial pres sure influences both the forward and backward rate constant through the in change eq.

following we derive the expressions for the steady-state IpOl) behaviour and the exchange current density as a function of pQi at T. By substituting Eqs. (2.39), (2.60) and (2.62) in the expression for the Faradaic current (Eq. (2.43)) we obtain

Steady-state IpCn)

behaviour.

In the

Mm, T, p0)

2N0FAaklc[Vo]
x

(2.63)

K(T) (i -fi)
i.e. the

.e2<l-W<*i>_. f*f<****r
surface coverage of the

where 9

steady-state corresponding operating point. Eq. (2.63) is


=

8(n, pQ^, T),

Oad general description

at the

of the

47

General Framework, Modelling,

and

Structural Investigation

current-voltage behaviour of the proposed reaction mechanism (valid for Ml and M2). As long as 0 is independent of n, either because the adsorption flux or the surface diffusion flux is much larger compared to the electrochemical reaction step, we simply have to deal with a charge transfer-controlled reaction and 9 is obtained from Eq. (2.58) steady
state

K(T)- jpZ
6
=

%(T, Po) 2
exchange

2LEL.
l
+

K(T).Jp^2
are

(2.64)

The anodic and cathodic

currents densities

therefore

given

as

i0

i0a

2N0Fklc[Vo]K(T) (1 -90) i0c

e2(1_P)/eq

and

(2.65)

i0

2N0Ffclc[Vo] 90 <f 2P/eo.


(2.66)
for the

By taking the product of Eqs. (2.65) and (2.66) we obtain current density (note that we do not (!) assume that p 0.5)
=

exchange

i0

2N0Ffclc[Vo]-[90(l-90)]1/2-7K(7^j-e(1"2P)/e<'
and

(2.67)
with

By using Eq. (2.64) for expressing 90 1/(2/) ln(Jp^),we finally obtain

by replacing

(T,p0 )

i0(T, POi)
With

2N0F*lc[Vo]

*<^>
and Pq

Po2(1"P)/2

(2-68)

dependence of i0 is obtained at low and high oxygen partial pressures, respectively [8, 68]. This behaviour is generally explained with the Langmuir adsorption of oxygen (Eq. (2.58)). Our result is more general.
P
=

1/2, the well known pQ

The oxygen

partial

pressure where the maximum of

i0(T,po)

occurs

is

given by

Po2*(T)
The

Jjl2PPL
P2-[K(T)r

(2.69)

expression

for the

gen

partial

pressures

exchange current at arbitrary temperatures can be similarly calculated and is given by

and oxy

48

2.3

Reaction Models

of the

Pt, 02(g) I YSZ System

i0(T,Po2)

2N0Ffclc[Vo]
lVA + (AHad)/2 J+ lr R -2KfWX:
n|a
tj

(i
x

aH2

(2.70)

JK(T)K(T)
:=

1+K(T)-Jp^2
where
=

Po,

(i-P)/2

adsorption enthalpy, and where A a a. It is seen that the temperature dependence of i0 at a fixed oxy gen partial pressures shows a rather complicated behaviour and no straight line can be expected in an Arrhenius plot of i0. Let us finally note that Eq. (2.69) is generally valid for arbitrary temperatures and not only for
we
=

us_ed AHad

ad

des

for the

rp

By use of Eq. (2.70), Eq. (2.63) simplifies equation

to the well known Butler-Volmer

Un.T.PoJ-UT.fo,).A.-le^-M-e-**}
As
soon as

(2.71)
an

9 deviates from its

equilibrium value 9q (due

to

applied

over-

Ip(T|) will deviate from the ideal Butler-Volmer behaviour described by Eq. (2.71) and the reaction can not be considered as charge-transfer controlled. The actual behaviour depends on the relative magnitudes of the electrochemical rate constants to the rate constants of the
source

potential),

then

terms of

Oad (adsorption and


steady-state.

surface

diffusion).
use

Identifiability
give
an

in the

We

now

the result of

Eq. (2.71)

to

intelligible
are

and M2

said

identifiability. The mechanisms Ml to be globally structurally identifiable from steady-state /F(n)


n

prove of structural

measurements

when for all

hip)
It is

l-pip*),

if and

only

if p

p*
controlled
current

(2.72)
reactions
are

well-known

that
two

described

by only

purely charge-transfer parametersthe exchange


a

apparent transfer coefficient

(note that

we

density i0 and the deliberately use the symbol a

49

General Framework, Modelling,

and

Structural Investigation

instead of

p,

which

we use

for

elementary reactions)which
vs.

can

be

uniquely
in

determined
our

by

Tafel-analysis (log(ip)

n) (see

e.g.

[23], p. 888). Thus,

fclc and P can be uniquely determined if the reaction is entirely charge-transfer controlled. It is rather troublesome to show analytically that Ml is globally structurally identifiable in the general case, because the (non-linear) analytical expression for 9(T), p0 T) (which is obtained by solving d9/df 0) must be substituted in Eq. (2.63). For the case where Tafel behaviour should prevail (|r|| RT/(2F)) the problem reduces to show that the following must hold
case,
=
,

for all

Q(p)
It
can

Q(p*),

if and
of
a

only if

p*.

(2.73)
program such
as

be shown,
or

by

means

symbolic computer

Mathematica
is

MAPLE, that Eq. (2.73) holds and that therefore the

problem

uniquely identifiable in the steady-state, even if the reaction is not charge-transfer-controlled. (We do not give these results because they can be easily reproduced on the computer and it takes some space to present them.) Keep in mind that in this case the unknown parameters can not be estimated from a Tafel analysis, but can be obtained from a least-square fit of Eq. (2.63) to the experimental data. A Tafel-analysis of experimental data would give
incorrect values for the unknown

parameters.
M2. We
in

We
can

use

these results to infer the


that M2
is

expect

identifiability of reaction mechanism also globally structurally identifiable


are

the

steady-state,
Therefore,

because the model structures of Ml and M2

similar. In addi

tion, the surface diffusion coefficient of


we

Oad

on

Pt

was

assumed to be known.
into the

have not introduced any

new

parameter

problem.
is

Note that the

steady-state strongly influenced by the surface


as

concentration of

Oad

near

the

tpb line, 9,
to

diffusion of adsorbed

species.

We therefore

expect this
This
means

concentration to remain
in the
an case

approximately
is

constant up

much

higher overpotentials

where surface diffusion is absent much


more

(Ml).
a

that such

electrode

likely

to

exhibit

charge-transfer dominated behaviour, fromanfp(n) analysis.


Linearized state space
state space model from constants from

which allows for parameter estimation

description.

We

will

first

rewrite

the

non-linear
rate

Eqs. (2.42)
and

and

(2.43) using the definitions of the

Eqs. (2.39)

(2.60). With the abbreviations

50

2.3

Reaction Models

of the

Pt, 02(g) I YSZ System

keq
*

e_*/(RT) e"2P/eq

k-

.fE^RT\e2^-^fE^
(2.74)

we

obtain

fi-

^(t,p)

2fcadPo2No

[1

8(f,

p)f

2kdesNQ 9(f, p)2

(2.75)

[00].[l-9(f,p)].)cf-e2(1-pW)
[-

gl:

IF

2N0FAa

[VG] 9(f, p) fceq e~imt)

(2.76)

[oJ]-[i-eaP)].]fc?c'-e2(1-p)^)]

expressed through k^. The linearized state space description of Ml is obtained by linearisation of Eqs. (2.75) and (2.76), using for the rate constants, k\ the steady state values k^(E, T) and k-(E, T), and the surface coverage, 9 9(p, T, p0 ), at the correspond fcj
Note that

A^q

must be

ing operating point.

We obtain

5/i
=

39

a(p)

*kadpoN0 (1

9)

4kdesN0

(2.77)

[VG] h

[00] k-x

d/i
=

3t1

b(p)

[V0]-2B/fci-9
+

(2.78)

[00]-2(l-P)/fcr(l-9)

39

c(p)

-2N0FAa

[[00] k-x

[VQ] fci]

(2.79)

51

General Framework, Modelling,

and

Structural Investigation

dn

d(p)

2N0FAax[[Oo]-2(l-P)/-r(l-8) +
[VQ] 2P/ h 9]

(2.80)

which

finally

may be written

compactly
a(p)Q(t,p) c(p)Q(t,p)
+

9(f,p)

b(p)r\(t)

I(t,p)
where
we are
we

d(p)x](t),

(2.81)
to denote that

used lowercase letters for the

(A, B, C, D) quadruple

dealing with scalars (first-order SISO system) instead of matrices. Following the procedure described in subsection 2.2.4 we obtain the Faradaic impedance ZF(s, p) in transfer function representation (cf. Eq. (2.30)):

Z(s,p)

Rt

1s +

-([00]fcT

[V0]fci)
+

4kadN0po-(l-Q)

4kdesNQ-Q

(2.82)

l/d(p) by definition (cf. Eq. (2.23)). It can be shown that the Rt(p) result for Rt(p) and the expression for the exchange current density i0 (Eq. (2.68) or (2.70)), satisfy relation (2.25).
where
=

Identifiability with
structure is

electrochemical

impedance spectroscopy.
if the

This

model

globally identifiable at p* equivalence ZF(s, p) Z(s, p*) Vs determined by seeking solutions of


=

equations

in p that arise from the


=

have the the

p*. This is only solution p following system of equations for

any :

Rt

R*

[oD] fca

[vQ] h

[oG]

T*

[vG] i*

(2.83)

^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

k\c(r\, T,pQ), and that fcj should


is solved for illustiation purposes

expressed
=

in terms of
=

k\. The problem

T and pQ

constant and with

(by substituting the 0) for the second relation in Eq. (2.83)

backward rate

52

2.3

Reaction Models

of the

Pt, 02(g) I YSZ System

[K(T)
a

1]

(fclc)*[K(T)

l]

(2.84)
P
can now

which has

obviously

single

solution for

fclc.

The value for

be

uniquely obtained from the first relation. Accordingly, Ml is globally struc turally identifiable by impedance spectroscopy at least under equilibrium conditions, i.e. we could estimate a unique set of parameters from EIS data obtained at the reference condition and zero overpotential. Obviously, it becomes much more difficult to prove the structural identifiability of Ml
apart from
the reference state
or

for

n *

0 and

we

do not indent to do

so ana

lytically.
Let
us now

consider M2.

We

first-order process
constant

(Fig. 2.7) and (boundary condition).

approximate the surface diffusion by a 8 as keep the surface concentration at z


=

We obtain for the surface diffusion flux

(cf. Fig. 2.7)

%
1
CO
=

J\
-

h
-

e(t)
t=i

YSZ

tpb
investigation
of reaction mechanism
=

Fig. 2.7

Two-compartment

model for structural

M2.The electrochemical reaction takes

place

in the

tpb compartment (i

1). The

con

centration of adsorbed atomic oxygen is considered to be

partment.

At

distance

z >

8,

is considered to be

diffusion flux is

proportional

to the

homogeneous time-independent. concentration gradient.

within

a com

The surface

53

General Framework, Modelling,

and

Structural Investigation

/i(0

"e0-e(o"

"9

and/'^f)

(f)-90-

(2.85)

The

mass

balance for the

tpb compartment is
=

obtained from

('tpb8)-^(*)
which results in

(>Wi>-ztpb

(2.86)

24.Jr9(r)
where

90-9(f)

(2.87)

Td
(8

8 /(2D) is the time constant of the considered surface diffusion

process
tration

is often called the average diffusion

depth [7]).

We include this term in the The result is

length of Oad [25] or the pene mass balance of Eq. (2.75) and

re-evaluate

ZF(s,p).

given by

ZF(s,p)

Rt

1s +

-([Ool-fci
T+

tVolfci)
-

(2.88)
9

AKdN0Po7

(1

8)

4kdesN0
no

which

means

that the existence of surface diffusion has

negative

influence

identifiability of M2. Furthermore, we can expect to estimate Td from an impedance analysis under the experimental conditions where the simplifications are justified (at high cathodic overpotential and low oxygen partial pressure, i.e. under limiting current conditions). From these examples it might seem that the proof of unique identifiability is mathematically straightforward. But the mathematical effort necessary to test for identifiability increases with model complexity and the problem of Vs implies that p whether ZF(s, p) p* is generally a diffi ZF(s,p*) cult one. Berthier and coworkers [58, 64, 65] have proven the identifiability for a number of reaction mechanisms under different experimental condi tions. The reader interested in more elaborated examples is referred to their work and the references therein. Fortunately, computer implementations of efficient algorithms for testing structural identifiability are becoming increas ingly available [62], and the field is growing rapidly.
upon the
= =

54

2.3

Reaction Models

of the

Pt, 02(g) I YSZ System

Vagueness
upon the
width that
w

of wits consequences to
our

identifiability.
we

In the

following

we

will address

attention to the
or

question,

what consequences will it have

identifiability of Ml of the tpb is known,


no

M2, when

skip

our

assumption
w

that the

i.e. when

we assume

that

is unknown and
as men

we

would like it to estimate it from

experimental

data. Indeed,

plausible argument to assume that the width of the tpb can be considered as a known quantity. Let us first consider the simplest case of a charge-transfer controlled reaction under steady-state investigation. The IF(T|) behaviour is given by Eq. (2.71) where we put Aa lt b w. Thus, from a Tafel-analysis, P and the parameter product klc w are uniquely identifiable, but klc and w are not individu [P, k^0,w] is un-identifiable in the ally identifiable. Thus, Ml with p steady-state.
tioned before, there is
=

An

important point
n

to note is

that, for
+

classical EIS

experiment

on a

system

with
is

states, there are, at most, 2n

equations

in the

parameters. This fact

easily seen by looking at a complex plane plot where every loop provides two quantities: one time constant and one resistance. The number of states n determines, at most, the number of loops. The additional equation is given by the expression for the charge transfer resistance (cf. Eq. (2.83)). Thus, we could expect that EIS might be capable to give us unique estimates of P, kx
andu;.

Tafel-analysis, estimates for P and fcj0 w can be obtained. Obviously, fcj can still be uniquely determined from an impedance analysis. Accordingly, all parameters can be obtained uniquely from a combined analysis. Note that an impedance analysis alone can not solve the problem, because the last expression in Eq. (2.83) does not
We
answer our

conjecture

as

follows: From

Rt *q and R^k^, w, P), we are left with similar problems as in the steady-state. We see from this example that it is important to have as much as possible a priori knowledge of a system available at an early stage of experimental design. Let us close this section by touching on a problem which occurs in practical parameter estimation. A reliable quality measure of an obtained parameter
contain any unknown

parameter (at least

at

0).

Because

estimate is

sary

prerequisite for any reasonable use of the results. It is also neces for experimental design, in particular for determination of optimal input
a

signals.
that the

To obtain accurate

parameter estimates, it is
sensitive
as

necessary

requirement

object

function is

highly

on

the individual parameters. This

requirement
two
or more

is not

sufficient, however,

the

sensitivity

of

combination of
sensitivi-

parameters may be much smaller than the individual

55

General Framework, Modelling,

and

Structural Investigation

ties,

indicating point

high
part

correlation between the


II.

parameters [69].

We will illus

trate this

in

2.3.5

Qualitative Analysis of Frequency Response Behaviour


The
s

Nyquist plot properties.

expression

for

ZF(s,p)

(Eq. (2.82))

is

first-order rational fraction in

'

ZF(s,p)
which
be

Rt(p)
general
s +

1-

bp(P)
s +

a0(p) Eq. (2.13):

(2.89)

can

rearranged

to

the

form of

ZF(s)
where
on

Rt

(a0-b0j
s + a

(2.90)

we

actually

mean

that

Zp, Rt,

and the

polynomial

coefficients

depend

the set of parameters p. The

polarization resistance
b0 Rt-Rt =

is found to be

fUjco)
We also

lim
JO)

ZF(jco)

(flo"&o)

(2.91)

immediately see by comparing Eq. (2.32) Ze(s)


=

and

Eq. (2.89)

that

-Rt

'o
s + a,

(2.92)
o

which is the transfer function of


and
a

an

electrical circuit made up of


= =

resistance R

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

quency of the apex at go0 denominator in Eq. (2.82)


i.e. if the

ao

>

ana<

^p

^t

^e

can

furmer

see

that if the

(or Eq. (2.88))

is much

larger

than the numerator,


is much

adsorption

and

desorption

process

(or surface diffusion)

faster than the electrochemical reaction step, then this second term will
almost

disappear

and the overall reaction is

charge-transfer

controlled with

56

2.3

Reaction Models

of the

Pt, 02(g) I YSZ System

-0.2
0 0.2
0.4

0.6

0.8

1.2

Re(Zp//c)
Fig.
2.8

Qualitative frequency response of Ml shown


data
are

in the

complex plane
R )

.The The
num

impedance
witch

standardized with denote the

Rp(a0,b0).

We have

(Rt <

V(jco).

bers within the

figure

frequencies
Rt
are

in Hz. The simulations

were

obtained

increasing
so

values for the forward electrochemical rate constant. Note that

doing

the values of

b0

as

well

as

influenced. With

increasing

values for

by fcj, Rt

decreases and

|b0|

increases.

Rt (curve (1) in Fig. 2.8). In the limiting case the frequency Z(jco) would exhibit as a single point on the real axis at R Rt.
R
=

response

Bode

plot behaviour.
co2
=

x2

a0 in the

introducing expression of ZF(jco) we


t7

By

-l

xx

coj

a0-b0

and

obtain

jou-, +1

(2.93)

which is

well known transfer function in control

theory [39].

We have for

the

phase ZZp(jco)

ZRt-

Z(jcoT1
as

l)-Z(jct)x2 + l)

(2.94)

and the

magnitude can be

written

57

General Framework, Modelling,

and

Structural Investigation

log|ZF(JG))|
We
can

log

logClJcoT! +1|) log(|j(ox2 +1|).


-

(2.95)
of

identify

three kinds of terms, where the first term is

independent

the

frequency.
2.9.

The behaviour of the

frequency dependent ZZF( jcu)

terms is shown in

Fig. by

Note that the

frequency

where the maximum of

occurs

is not

given
is

the inverse relaxation time of the process, l/x*, but that this

frequency

inO
10

^^^^
--'"
,.-

N* 10-2
r

a)
in-4

/?t-T2/T, j(0X[ + 1 Qm2 + irl


' '

^_
-:
. .

'

10*

10J
0)/s

-l

1(T

103

100

'

'

-pit-'
"""*

"-r

*r

o
00

50-

~^^^"^ "Z^^^ ^^^


^^^

^^***"NW.
>w

^""""Sk. ^*s*sfc^

S
9I

0
""---....

-501-

"^-^

b)

-100

...

'

'

'

10J

10J
co/s

-l

10*

102

Fig.

2.9

Qualitative frequency response of Ml shown

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

Note that the overall

representation.(a) magnitude and over

all

phase

be

simply plot. The

obtained

electrode reaction.

58

2.3

Reaction Models

of the

Pt, 02(g) I YSZ System

//(27C-S-1)

b)
Fig.
2.10

-h

//(27C-S"1)

Frequency

responses of Ml in Bode

phases

of

ZF(jco)

data with different ratios of


-1 if

representation.(a) Magnitudes and (b) aQ/bQ. Note that the slope of ZF(j<o) only by
about
one

emerges

clearly

as

o>1 and co2

are

different

order of

magnitude.

given by
tance,

J^

u)2 (cf.

Fig. 2.9).

The

imaginary part

of the Faradaic admit

Im[Yp(jco)],

has its maximum at the relaxation

all process. This fact must be data.

kept

in mind when

frequency of the over discussing experimental

plots by considering the high frequency behaviours of the terms in Eq. (2.95). The magnitudes of these terms approach an asymptote at frequencies (axi 1. The slope of these terms in a Bode plot is either +1 or -1, i.e. it is possible to get information about the order of an electrochemical process by examining the slope of the magnitude in the Bode plot. But at the same time we draw attention to the fact that the polynomial coefficients a0 and b0 have to be different by at least one order of magnitude (in our particular example). Otherwise, both curves will overlap and the slope of the total curve will always be flatter than minus
can see a

We

further

important property

of Bode

59

General Framework, Modelling,

and

Structural Investigation

one.

Note that the ratio of the relaxation is

frequencies
These facts

as are

introduced in
in

Eq. (2.93), Fig.

given by tOj/o^
same

l-bQ/aQ.
Fig.
2.8
are

2.10 where the

data

as

in

given

in

envisaged Bode plot.

2.4

Conclusions

study, comprising of this and a second part, was undertaken to provide a tool to treat heterogeneous reaction mechanisms within a uniform framework. The concepts were presented by investigating the reaction mech anism of the rather well understood Pt, 02(g) I YSZ system. We showed that the electrochemical kinetics can be conveniently represented in (non-linear) state space models. In the cases where the reaction mechanisms are simple, analytical solutions for the steady-state and frequency response behaviours
The present
can

be obtained. Otherwise, numerical solutions which


we

can

be found for any II of this

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

present

in

part

discomfort at the present time.

However, it is obvious that these problems


ments are

must be

tackled before

experi

carried out to make certain that the

most

possible information.
(and use)
as

experimental work gives the We have also shown that it is extiemely important
priori knowledge of a
reaction mechanism
as

to have

much

pos

sible to be able to estimate unknown kinetic parameters from measurements.

Despite

these difficulties, the power of the


can

proposed

method is the fact that

state space models

be treated

on

the computer

efficiently

and in

straightforward way.

Acknowledgments.
portation,
thank
sions. In

The financial

support from the Swiss Department of Energy, Trans

and Telecommunication is

gratefully acknowledged.
on

The authors wish to

present colleagues

in the Chair of Nonmetallic Materials for many useful discus

particular,

we are

indebted to Prof. Dr. D. Bonnell,


our

sabbatical from

Pennsyl

vania the

University,

and Dr. M. Godickemeier from

laboratory,

for

carefully reading

manuscript and giving valuable comments.

60

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In

Sys

65

General Framework, Modelling,

and

Structural Investigation

Appendix
2-A.l
State

Space Description of an
space"

Electrical Circuit

by means of a simple example. Consider the electrical circuit shown in Fig. 2-Al.l. The circuit should be familiar to electiochemists. Let us derive the state space model for this partic ular circuit. In the appendix of Part II of this publication, a more complicated
system
The
is treated.

The notion "state

is best introduced

dynamic properties of this system are entirely described for times t > tQ, if the voltage U (t0) and the current I(t0), as well as the input voltage Uu(t) for t > tQ is known. From this information, I(t) and Uc(t) can be determined for t >t0. However, 7(f) and L7c(f) characterize the "state" of the electrical circuit and are therefore called state variables. From a node analysis for node 1
we

find

[Uu(t)

Ux(t)]

C
0

^[Uy(t)

Ux(t)}

(2-Al.l)

^[UyW-U^t)]
and

Kt)

^-[Llu(0-lli(0]-

(2-A1.2)

/(0
o o2

Rl

-O

R2

ua(t)

Uy(t)
-o

o-

Fig.

2-Al.l

RC electrical circuit.The notations

are

given

within the text.

66

Appendix

We

put

L7y(f)

(ground).

We solve

Eq. (2-Al.l)

for

L7a(f)

and sort the dif

ferent terms to obtain

^i(')
and

4-(h^]-"i(^
C

Ul

R2

CRl

U(0

(2-A1.3)

similarly for Eq. (2-A1.2)


7(f)

=--.Ul(t)
Rl

Rl

rUu(t).

(2-A1.4)

Eq. (2-A1.3) is called state equation and Eq. (2-A1.4) is called output equation. Form Eq. (2-A1.4) it is clearly seen that 7(f) depends on the input 17U(0 and the present value of L71(t). Because the circuit is a linear and time independ ent system, we can easily write Eqs. (2-A1.3) and (2-A1.4) in matrix form as
x
=

Ax

Bu

(2-A1.5) (2-A1.6)

y
where

Cx

Du

we

used

(A, B,C,D)

are

7(f), u Lf1(f),y Uu(t), and the state space matrices obtained by comparing the coefficients of Eqs. (2-A1.3) to
=

(2-A1.6)

LCRlJ
(2-A1.7)

State-space systems are easily treated numerically (see Part II of this publica tion). The dynamic properties of a system are entirely described by the (A, B, C, D) quadruple and the starting conditions.

67

General Framework, Modelling,

and

Structural Investigation

2-A.2

Calculation of

tpb length

from microstructural data


terms

We intend to describe the electrode

measurable microstructural data. coverage of the


can

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


as

of

the total

electrolyte surface, Acov,


image analysis.

well

as

the average pore size, d

be obtained from
as a

We will express the

length

of the

tpb,
can

I tib, We

function of these two

parameters.

assume

that the electrode microstructure metal

facing

the solid

electrolyte

be

regarded as a mesh of /char, is introduced, which


A2.1. Let
us

strips (Fig. 2-A2.1).

A characteristic
as

length,
Fig.
2-

reflects the size of the unit cell


as

defined in

consider
Then

/char
we

constant for the moment and let

dp

be the

only

free

parameter.

obtain for the

length

of the

triple phase boundary

'tpb

4rfP T^
char

C-A2-1)

char
-4
-

Pt

tpb

Simplified morphology of noble metal/electrolyte interface.A mesh of noble metal strips is arranged in a regular lattice. The unit cell size is characterized by it characteristic length /char and d is the pore size. The length of the triple phase bound
ary is

Fig.

2-A2.1

parametrized

in terms of the surface coverage

Acov

of the solid

electrolyte

and the

characteristic
from SEM

length Zchar

Both

quantities

can

be estimated with

satisfactory

accuracy

image analysis.

68

Appendix

where

A,,,

is the

apparent

electrode

area.

With the definition of the surface


we

coverage

Acov

(/char

)/lchaT

which

solve for

dp we find
(^A2-2)

'tPb

4/-^VriA7,char

Typical values for noble metal electiodes are in the range of 2-10 pm for l^j. and in the range of 0.4-0.85 for the coverage A^ (cf. Fig. 2.2 and e.g. [7,10,17,
20]).

69

General Framework, Modelling,

and

Structural Investigation

70

Chapter

Computer Implementation,

Simulation,
Abstract
In

and

Validation

part

I of this paper

nonlinear state-space model of the


was

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


structure of the

proposed
In this

and the
one

equations

was

investigated.

part

representation of the model is given. The computer implementation of the heterogeneous chemical and
electrochemical kinetics and the surface
mass

dimensional finite-element

transport

is devel

oped.

The

origin

of the double

upon the electrochemical


sion of the

layer capacitance and its influence impedance (EIS) is discussed. The prob
and numerical

lems of the space discretization of the electrode surface, the exten

triple phase boundary (tpb),

aspects

are

considered. The simulation method is described in detail. The

steady-state current-voltage
ance

behaviour and the Faradaic


K

imped

is simulated for

temperatures from 773


1
are

(900C), and oxygen partial pressures from


different
reaction
,

(500C) Pa to 105

to 1173 K

Pa. Three 1123 K

regimes

discriminated.

Above

overpotentials the reaction kinetics is essentially determined by the charge-transfer step. With increasing cathodic overpotentials, and/or decreasing pQ surface diffusion is in competition with charge-transfer. At tem-

(850C), high pQ

and low cathodic

*)

Submitted to

/. Electrochem. Soc.

Implementation, Simulation,

and

Validation

peratures between
dominated

773 K and 1073 K the reaction is

essentially

supply of atomic oxygen (Oad) via surface dif fusion and dissociative adsorption of 02(g) near the tpb. The charge-transfer coefficient, the electrochemical rate constants, and the activation enthalpy of the charge-transfer reaction can be uniquely estimated from EIS data. The activation enthalpy of the

by

the

dissociative oxygen

adsorption on Pt can be
on

estimated. With elec

trodes of well known geometry the surface diffusion coefficient of

chemisorbed atomic oxygen


ence can

Pt and its concentration

depend
a

be obtained. It is demonstrated that the simulation of


a

micro-kinetic models is

powerful technique

in order to obtain

deeper understanding
Keywords.
double

of reaction mechanism.

Reaction mechanism, electrochemical

impedance (EIS), state-space model,

layer capacitance, digital simulation, Matlab/Simulink.

3.1
In

Introduction
I of the

part

present paper

we

have

presented

general

framework for

modelling reaction mechanisms at noble metal electiodes in solid state elec trochemistry [1]. We illustrated the process of modelling and structural inves tigation by means of a well known reaction mechanism describing the Pt, 02(g) I Yttria-Stabilized Zirconia (YSZ) interface. In a first model (Ml), we considered the dissociative adsorption of oxygen on the Pt surface and the reduction of atomic oxygen near the triple phase boundary (tpb) line. In a sec
ond model included. Is

(M2), surface diffusion of


was

atomic oxygen

on

the Pt surface

was

only one electrochemical rate constant and one charge-transfer coefficient are unknown, whereas the remaining model parameters, such as activation energies or the rate of adsorption and desorp tion, were assumed to be a priori known. We investigated the structure of the
models in detail, showed the condition for their
a

assumed that

identifiability,

steady-state transfer controlled reaction. Expressions describing the behaviour as well as the small-signal frequency response behaviour were also given. However, we have not yet described how the theoretical results
rigorous
case

treatment of the

behaviour in the

presented a charge steady-state I(r\)


of

and

insight into the reaction kinetics of the Pt, 02(g) I YSZ system. In addition, the implementation and simulation procepart
I
can more

from

be used to obtain

72

3.2

Model Implementation

dure has not unknown


It is
one

yet been described and


can

it has not been demonstrated how the

parameters

be estimated from electrochemical measurements.

of the aims of this part to

present the computer implementation of


can

the model

equations

and to show how simulations

be obtained. We

use

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

3.2
3.2.1

Model

Implementation
Tools and General Procedure

Computer

We have chosen Matlab and Simulink


mentation and simulation of models

as

primary software
an

tools for the

imple

[2], instead using


an

ordinary

program

ming language,
with numerical

such

as

or

Fortran. Matlab is

efficient tool for

dealing
sci

analysis,

matrix
a

zation. Matlab has become


ence

computation, signal processing, widely used computer tool in engineering

and visuali

and is available
are

There

two
an

large number of computer hardware platforms. basically different approaches to implement the set of equa
on a
use

tions into

executable Matlab code. The first method makes

of the

graphical programming extension Simulink in Matlab [3], where the dynamic system is represented as a block diagram. Single Simulink models can be con verted to subsystems which can itself be further built to larger systems; a
property which
for
is

particularly
mass

useful when

treating

finite-difference models
Simulink

dealing

with

transport processes. From

function, the

73

Implementation, Simulation,

and

Validation

dynamic

behaviour of

system

can

be

investigated
models
can

in time and

frequency

domain. Linear time invariant

(LTI)

be converted between

state-space and transfer function representations.

commonly used in ordinary programming languages, uses the system of equations directly. Explicit state-space descrip tions are obtained by linearization of the state equations as described in part I. Each methods offers specific advantages; in fact both approaches are useful and are best employed in conjunction. When dealing with small mod els (i.e. if the number of state variables is below -50), model implementation in Simulink is considerably faster and more intuitive. In addition, the loss in performance during simulation is negligible. We mainly use the graphical
The second

approach,

which is

programming

environment.
a

The overall strategy to solve

problem

can

be summarized

as

follows:

(i)

by building a block diagram Simulink or by writing ordinary (C like) Matlab functions. Implement
Make the
lab

the model either

in

(ii)

physical and kinetic constants available to the Mat workspace. Estimate some reasonable values for the

unknown parameters.

(iii)

Determine the

steady-state
=

values for the state variables from

the condition

dx(t)/dt

(initial conditions).
in

(iv)

Run

large-signal

simulations

the time domain of the

non-linear model

(Simulink

or

Matlab

function),

or

(v)

generate
nal time

(linearized) state-space model of the non-linear

model and compute the

frequency

response

or

the

small-sig

dependent

behaviour.

3.2.2

Heterogeneous

Chemical and Electrochemical Kinetics

The

primary objective
balance
concern care

of these

procedures

is to

implement

the

mass

and
is

charge
no

equations

into the

computer suitable for simulation. There

need to

about the time discretization of the

equations

for Matlab
the

takes

entirely

of that. It is, therefore, not necessary to know

precisely

74

3.2

Model Implementation

nature

of the numerical

may be

helpful

in

integration techniques, although choosing the appropriate algorithms


can
or

basic

knowledge

for simulations in

time domain. Basic details

be found within the handbooks of the pro

gramming

environment

in textbooks about numerical mathematics

[3-5].

As it is the first time where electrochemical

systems

are

treated with this pro

gramming environment we put some emphasis on the actual implementation the model. Implemen process in order to facilitate the re-implementation of tation details specific for Matlab and Simulink will be given in the appendices
3-A.3 and 3-A.4.

We

use

the non-linear state-space model Ml


the

developed

in

part

I of this

cation

as

starting point
obtained
as

for the

implementation [1].

The

mass

and

publi charge

balances

were

h-

^eC>P)

2kadpoN0-[l-Q(t,p)]2-2kdesN0-Q(t,p)2

(3.1)

-[Vol-^t.p).^.^^
+

[00]-[i-e(t,p)] fc!qe2(1-p)/n(0

gl:

IF

2N0FAax [- [V0] 9(f, p)

k? e~2mn

(3.2)

[00]-[l-e(i,p)].^-e2(1-p)/,1(f)]
unknown

with

the

vector

of

the

parameters

[klc, (3],

and

fclc exp[-Ea/RT] exp[-2(3/E symbols was explained in part I or can


=

fc^q

]; the definition of the remaining


be found in Table 3.1 of
u

A.l. Let

us

rewrite
=

Eq. (3.1)

with

Q(t, p) (state variable),

appendix 3i\(t) (input

quantity), kt
*
=

[Vq]

k\q, and kb
(1"
"

[00] ke-q

as

2kadPo2M0

*)2 2*:desN0 x2
+

(3.3)
-

-krx- exp[-2p/u]

kb (1 -x) exp[2(l

p)/w]

The first two terms

adsorption and desorption of oxygen on the platinum surface. These reactions takes place on the entire cathode surface and are not restricted to the tpb area as the electron transfer reaction is (terms three and four of Eq. (3.3)). The model Ml is completed by adding the equation for the charge balance. Using y lF(t,p) and the same abbrevia tions as in Eq. (3.3) we write
are

related with the

75

Implementation, Simulation,

and

Validation

2N0FAa[-k(
(3.4)
can

<f2P/M + kh

(1 -x)

2(1-P)/m

(3.4)

implemented into a Matlab function or into a Simulink block diagram. Appendix 3-A.3 gives more detailed information about the Simulink implementation of model Ml and most of the Matlab commands used for simulation. The following gives an overview of the capa
Eqs. (3.3)
and be bilities of the method. The initial condition for the state variable,
x
=

x0, is obtained

by solving

only the first two terms must be taken into account and the well known analytical solution of the Langmuir equation is obtained (cf. 3-A.3). The time dependent behaviour of the system from any starting point towards the steady-state point can be followed by choosing an appropriate simulation algorithm and appropriate step sizes. Simulation results can either be followed directly within the Simulink envi ronment or by writing the simulation results into the Matlab workspace. Lin earized state-space descriptions of the models can be obtained by following either of two routes. First, analytical expressions for the state-space matrices A, B, C, and D can be obtained by linearization of Eqs. (3.3) and (3.4) as described in parti. This can be done for both Ml and M2, although it becomes tedious doing so for multi-compartment models. From linearized state-space models (SSM) the frequency response and the small-signal time dependent behaviour can be obtained at the corresponding operating point. Note that the linearized SSM can not be used to simulated the large-signal time dependent behaviour, such as potential-step responses or cyclic voltammetry. The second approach circumvents these limitations. The function "linEq. (3.3) numerically
x
=

for

0. If

0,

mod" from Simulink is used to extract numerical estimates of the state-space


matrices

from the

non-linear Simulink block

approach has the advantage that both small-signal behaviour of the model can be
and without the need to obtain

diagram (cf. 3-A.3). This the large-signal behaviour and analysed with one representation

(lengthy) analytical expressions for the state-space matrices. However, during the early implementation stage it is often useful to follow both routes simultaneously in order to validate the model implementation. In addition, Simulink offers the function "trim" which enables to determine steady-state equilibrium points from (non-linear) sys tems in block diagram representation (cf. 3-A.3). This is especially useful when the steady-state values for the state variables are needed under the con dition where an overpotential is applied, i.e. when a current flows. Under

76

3.2

Model Implementation

these conditions it is

generally
as

not

possible

to solve
=

equations

or

systems of

equations

of the type such

Simulink block

diagram of Ml

0 analytically. Eq. (3.3) for x is given in appendix 3-A.3.

The

complete

3.2.3

Surface Mass

Transport
different methods to deal with

There

are

basically

two

partial

differential

equation (PDE) systems numerically.


The second method, which finite-difference
we use

The first is the collocation method

[6].
it

in this paper, is the method of the

approach [7].

Whereas the first

technique

is

more

elegant,

generally requires more mathematical treatment. We employ the simplified model of the electrode morphology developed in part I. The height of the Pt stiips is assumed to be equal to the thickness of the electrode layer (Fig. 3.1 a). The z axis is divided into compartments of increas ing size directed away from the tpb line (Fig. 3.1b). However, there is no need to discretizise the electrode surface over its entire thickness, but only to a cer tain extent which is in the order of the Nernst diffusion layer (see below). The concentration of Oad is considered to be homogeneous within the compart
ments.

For

digital simulation it is convenient to rewrite sion along the z -coordinate in the form [8]

Fick's second law for diffu

I ^35
In

D>S a-lH!i)2
"

D>8dz'

(3'5)

part

we

assumed that D does not

depend

on

the concentration. Accord


term.
treat
cen

ingly,

the first term in

However, it is
tral differences
and out of
a

Eq. (3.5) vanishes and we are left with the second obvious that Eq. (3.5) is the starting point for a refined
are

ment of surface diffusion. The space derivatives

approximated

with

(see e.g. [7]). The diffusional flow/ (mol/(ms)) of Oad


is obtained from

into

compartment

/i

1, i

DicrNA

N0

xi -1
Az;

xi

i-l

Az,
2 )

and/'i,i

DaT
v

xi
AZ:

xi +
AZ;

1
+

(3.6)
1

V 2

77

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 one-dimensional finite element model. (a) 3-dimensional view of porous Pt on solid electrolyte according to the 2-dimensional

developed in the appendix of part I. d is the pore diameter and Zchar is the char acteristic length. Gas mass transport is considered to be infinitely fast in the Pt pores, (b) The plane (ABCD) is discretizised in compartments of increasing size starting with the tpb compartment of width w (= Az{). Mass balances are formulated for every compart ment. In addition, for the tpb compartment the charge balance is formulated.

model

78

3.2

Model Implementation

where Xj is the surface coverage of

of surface sites

on

Pt

Oad in compartment i, N0 is the number (atoms/m2), NA is the Avogadro constant (mol-1), and
mass

Azj

is the width of

compartment i (m). The


as

balance

(mol/s)

for

com

partment

i is obtained

Ai7n

dc-.
~

ldt

*'

Oi-l,l-/i,i l)
+

(3.7)

where

A{
is

Azf
xi

is the

area

of

compartment i,
of
mass

t is the width of the pore,

and

Cj

the

surface concentration
we

Oad

in

compartment

i. i

With

ci

N0/NA
dxi

finally

find for the

balance of

compartment

a Az-

D
=

dt

Az./2

(3.8)

x
Az;

*i-l"
+

i-l

Az
V

AZ:

i-l

AZ;

xi
+

1
/

Az

AZ:

AZ:

AZ;

or

in short form

Az;

dc-

1
~

dX:
rp

1
"

~2D~'Tt
where

rTt

i-l.i^i-l 'fli,ij:i

ai,i + la:i + l

(3.9)

T{

Az{ /(2D)

is the time constant of the diffusion process in

com

partment /, and the ai are numerical factors which and the boundary conditions.
The

depend on the geometry

state-space model is realized by writing the mass and charge balance equation for every compartment using the following initial and boundary
conditions:

(i)

Initial conditions: the surface concentration of

Oad

is homo

geneous before

establishing an external disturbance.

79

Implementation, Simulation,

and

Validation

(ii)

Boundary

conditions at

an

infinite distance
a

co

from the elec

sufficiently large distance from the interface the concentration of Oad is equal to the equilibrium surface concentration x0 determined by the an<^ adsorption/desorption equilibrium (c(o i xo 0). AZco i trode/electrolyte
interface: at
=

(iii) Boundary conditions

in the

tpb compartment:

the interface is

blocking for surface diffusion; the Faradaic current is equal to the charge balance; the electron transfer reaction can only take 0 and Azt b x oo. place in this compartment; i.e. ct b x
= =
_ _

boundary compartments can be conveniently obtained from the following argument: if the boundary is blocking we put either Azj _j or Az{ , depending on which boundary is blocking. +1 If the concentration of a neighbouring compartment is taken to be constant with time, we put Az{ 0. Starting from the tpb compartment we increase +1 the size of every successive compartment by a factor of q. Accordingly, we obtain an approximate state-space description of M2:
=
=

Note that the a{

of the

dx-.

2kadpoN0 (1
-krx1
dx{
Tt
+

xx)2

2kdesN0 x2

(3.10)

kh.(l-xl)

^-Tl-qx1 T]-qx2)
+

l:

2*adPo2No

(1

*i)2
+

2kdesN0 x2 +

(3.11)

TJ^Tq^-1
dx
co:
(0

~Xi

T7~qXi
-

l)
'

~di

2fcadPo2^0
1

(1

*o)2
+

2fcdes^0
+

(3-12)

q
+

TuKl
where denotes

q**-1

2q
_

l+qXa>

X> +

1)

co
=

the

outmost

compartment

facing

the

region

with

* +

xo-

80

3.3

Simulation Procedures

The

by putting Eqs. (3.10) to (3.12) into a Simulink block diagram (see appendix 3-A.4). The implementation of the tpb compartment almost corresponds to the implementation of Ml with the dif ference that the terms for surface diffusion are included. The charge balance complete
model M2 is obtained
is still

The
and

xx. given by Eq. (3.4) where Aa must be replace with Azx t and x remaining compartments account for the adsorption/desorption process the surface mass transport. More details concerning the implementation

of

mass

transport

in Simulink

are

given

in

appendix 3-A.4.

3.3
3.3.1

Simulation Procedures
Model Initialization and

Sensitivity
the numerical values of all constants

The models and

are

initialized

by making

parameters available to the Matlab workspace. The values for the parameters which are (assumed to be) a priori known are given in Table 3.1

(appendix 3-A.l).

These values

are

used for the simulations if not otherwise

stated. It should be mentioned that there is much information available in the literature about the faces

adsorption

and

desorption dynamics

of

02(g)

on

Pt

sur

(see model

M3 in

[33]). The

kinetic rate constants

were

chosen while
in

taking

into account most of this available information

(see references cited

Appendix 3-A.l). Note that the activation enthalpy of the electro chemical reaction is also reasonably known [9,10].
Table 3.1 of
In order to be able to
run

simulations,
=

some

values must also be chosen for

[klc, (3]. Often one can obtain reasonable esti mates of unknown parameters by considering the static properties of the sys tem. This is exemplified in the following. Assume that we would like to 1 atm. Assume that Rt has obtain an estimate for k*{q at T 1000 K and pQ been determined experimentally as Rt 10 Qcm2 for an electrode of 1 cm2 of find From the relation we RT/(2F) l/iQ apparent area. Rt [ VQ] fcf x Using i'0 4.3 mA/cm2. This value should be close to 2N0FA the parameters given in Table 3.1 and with Aa w /^b, where w is the width of the tpb compartment and l^b is the length of the tiiple phase boundary, a numerical estimate of k\q is obtained if x is calculated for the
the unknown parameters p
= = =

temperature and pQ considered. Other


similar way.

reaction rates

can

be estimated in

81

Implementation, Simulation,

and

Validation

Once the
estimates

priori

known

parameter values and the approximate parameter

are

made available to the Matlab

workspace,

simulations

can

be

goal of a study is to determine accurate estimates of unknown model parameters, it is generally not sufficient to test for (theoretical) identi fiability of the model (cf. [1]). Obviously, a further necessary condition for accurate parameter estimates is that the model frequency response shows a
obtained. If the

high sensitivity
sensitivity

with

respect

to the

parameters [11]. The relative parameter


to

magnitude obtained numerically [11]

of the

of

ZF(jco)

each

parameter p{

is

easily

S1(0)

.to(^|ZF(i.)|-Kg55|).
parameters

(3.13,

In addition, the correlation between the

must be low in the inves

tigated frequency

range.

3.3.2

Penetration

Depth

and

tpb

Width

Consider

porous Pt electrode of thickness L

(cf. Fig. 3.1a). So far


be

we

have

only

stated that the finite difference

approach will
But
we

employed
we

for the treat

ment of the diffusion

equation [12-14].

have neither fixed the distance


nor

up to which

we

intend to discretizise the surface

have

fixed the width


We have also

of the surface
not

compartments (especially the tpb compartment).


we

yet decided how many compartments

should

use

for this purpose.

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

mathematical sense, concentration


an

perturbations

at the

interface, i.e. due

to

applied overpotential, have an effect up to an infinite distance from the interface. In practice, however, there is a limit beyond which changes can be JUx and x is the neglected. This value is generally set to 68 where 8 experimental time interval [14,16]. This approach works fine for time-domain simulations but may it also help for simulations in the fre quency-domain, i.e. for electrochemical impedance simulations?
=

82

3.3

Simulation Procedures

77C 900
800

700

600

500

l(f

T=973K

\ \
\
10 20

30

10i

ReCZp/Q-crrT)

S-H

102

com

/(rad-s-1)

exp[21.11

117.6103 K/ffiT)]

10J
pn
=

U2

10D Pa
j i i
i_

0.8

0.9

1.1

1.2

1.3

103K/7;

Fig.
and

3.2

Temperature dependence

of C0max. The definition of comax

can as a

be

seen

in the

inset of the

figure.

The maximum of

-Im[ZF(jco)]

was

determined

function of T

p02.

The

quantitative

relation between comax and T is


were

parameters given
in the
ence

in Table 3.1

used. The inset shows


=

complex plane

obtained at T

973 K and pQ

figure. The typical impedance 105 Pa. A perfect pQ/2 depend


given
within the Faradaic
a

is found for comax at constant

temperatures from

773 K

(500"C)

to 1073 K

(800C)

(not shown).

83

Implementation, Simulation,

and

Validation

Analytical
sional

solutions for the Faradaic

impedance

are

available if one-dimen
is

surface

diffusion

(semi-infinite medium; without adsorption)

Warburg impedance is obtained at high frequencies and a perfect semi-circle is found at low frequencies in the complex plane (see inset of Fig. 3.2). The frequency of the maximum value of the imaginary 8 J(Omax/(2D) component, comax, is related to 8 by the expression 2/ Jk [15]. We have obtained simulations for ZF(jco) with the parameters given in
present [15].
A classical
=

Table 3.1 from T for


a

773 K
w
=

(500C)
10
nm.

to 1173 K

fixed value of

105 Pa to 1 (900C) and p0i The temperature dependence of comax


=

Pa is

shown in

Fig.

3.2. A pQ

dependence
was

of comax is found

the temperature range, which


Thus

found

by

others
we

by simulation over experimentally [15, 17].


limit the space discreti

having

found
as

an

expression

for comax and 8,

zation to 68

described above.
we are

Once 8 is determined,

left with the

question

about the number of

com

partments and the


ments

size of the

tpb compartment.

The number of space ele

required for a successful simulation can be reduced drastically by using a space grid with small space elements in the region near the elec trode/electrolyte interface. Joslin and Pletcher [14] and Feldberg [18] have
discussed
some

suitable transformation functions for the space variable with

regards to computing time. The function of Feldberg is an exponentially expanding sequence of box widths. We use increasing compartment sizes which expand according to a geometric series with a constant factor q. With 1.5 < q < 2 this transformation is close to the proposed transformations from Feldberg and loslin and Pletcher, but without making the implementation more difficult. Thus, as soon as we fix the value for the tpb compartment, the number of compartments can be determined from the length 68 and the con
dition for q.

There has been much debate about the extension of the

tpb

of

Sr-doped

LaMn03
trode

cathodes

on

YSZ

(see e.g. [19,20]). There


electrodes is low

is

agreement that the elec

conductivity of these length of the tpb at zero or


of mixed

approximately proportional to the overpotentials. For higher cathodic overpo


to increase due to the
occurrence a

tentials, the extension of the tpb is believed

conductivity of the

cathode at the interface

[21]. Similarly,

propor

tionality

between the electrode

conductivity
can

ae and the
on

length

of the

tpb

has

been determined for porous Pt electrodes mixed conduction in noble metals


the extension of the

YSZ

[22,23].

It is clear that

be ruled out. However, the ideas about electiodes

tpb

of

electronically conducting
metals)
are

(LaMn03

at

equilibrium potential

and noble

sparse.

Wang

and Nowick

[24]

84

3.3

Simulation Procedures

proposed a model where oxygen is supplied by surface diffusion towards the tpb and subsequently diffuses laterally in the two-phase region between the electrode and electrolyte. But, from the rather low solubility and diffusion coefficient of oxygen in bulk Pt [25], we expect this contribution to be negligi ble at bonded (i.e. sintered) interfaces between Pt particles and YSZ. In addi tion, this model is rejected by others [15,26]. Thus, we are left with the picture that adsorbed oxygen is reduced and incorporated near the tpb.
modelling point of view it can be assumed that the election transfer reaction takes place in the tpb compartment of width w. It is thereby not rele vant whether the real process takes place on the Pt surface, between the Pt
From the

grain
these

and the YSZ surface,

on

the YSZ surface,

or

whether

combination of

possibilities
area

takes

place.

The model accounts for the reaction

irrespec
to the

tive of its location. However, the Faradaic current active

IF

is

proportional

lt b w and to the electrochemical rate constants. We feel intuitively that doubling w should doubling the current, and therefore halve the polarization resistance Rp. But what happens, if we keep the product w klc constant and change, for example, the value for w in a certain range? If the Faradaic impedance ZF(jco) was independent of the choice of w (at least for a certain range and when the constraint is applied), we would be released from the task to assign a value to w. In this case we would state that there exists a strong correlation between w and klc. Let us first consider ZF(jco, p) of model Ml [1]
Aa
=

ZF()(o,p)

Rt

1+

*f + *b
jco + 4/cadNoPo

(1

x)

4fcdesN0

(3.14)

where

R-1
It is
w

M0F-zvltpb-[(l-P)f-kh-(l-x)

W-krx]

(3.15)

immediately seen that Rt is insensitive to changes of w, if the product klc is kept constant (note that kb is expressed in terms of k( and remem

fcf). However, the fraction within Eq. (3.14) is strongly sensitive to changes of w if w klc It is not a priori clear how the const behaviour of model M2 will be. Certainly, Rt will exhibit the same properties as in Ml. The sensitivity of Ze(jco) with respect to w should be investigated numerically.
=
.

ber the definition of

85

Implementation, Simulation,

and

Validation

In absence of detailed information


assume w

we

set

10

nm

for the moment. We

to be

independent
area

of

temperature and oxygen partial pressure.


the active
seems area

With

/^b

in the order of 1

pm/pm2,

will be in the order of 1%


a

of the

apparent electrode
examined

which

to be in

reasonable range. The

problem will be

numerically below.

3.3.3

The Double

Layer Capacitance
capacitive behaviour,
little

While it is clear that electiodes in SOFC do exhibit


attention has been

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

(assuming
The

boundary

between the metal and the


is

electrolyte) [27-30].
[28]

sharp inner layer


a

capacitance

generally

estimated from

Af, Aov e0e/r

(3-16)

where A, is the apparent electrode area, with electrode material, e0 is the

Acov

is the

electrolyte
e

coverage

permittivity
r

of vacuum,

is

an

effective die

lectric constant

(of order (1

1),

and

is the distance between the metal electrode

and the centres of the oxygen ions therefore be between


to

(a few tenth of
It is

nanometer). Q should

10) uF/cm2.

slowly varying function,


perature
ent
on

of interfacial

expected to be independent, or a potential. Since the concentration of

oxygen vacancies in YSZ is fixed


is to increase the ionic

by the content of yttrium, the effect of tem mobility. However, e and r could be depend

the

potential and/or

the

temperature.

86

3.3

Simulation Procedures

completely blocking electrodes without specific adsorption (of the diffuse double layer oxygen ions at the metal-solid electrolyte interface), is described by (z+ z_) [31]
For the
case

of

c<-A-4-<*{-m)
where
=
=

(3-17)

0) measured relative to 4> at <J>0 is the potential at the interface (x x oo, LD is the Debye length (i.e. the extension of the perturbation in con centration into the electrolyte due to the electric field), and the other symbols have their usual meaning. The Debye length is given by

^d

( ee0RT
=

V/2

(3.18)

2z F cxJ

where cx

is the concentration of mobile ions. However, the

theory

of diffuse

layers assumes mobile point charges and relatively low concentra tions of ionic species. Robertson and Michaels [32] have discussed the possi bility of a diffuse double layer in YSZ in terms of Eqs. (3.17) and (3.18). They
double estimated values for
828 K

LD

between 2.85

nm

at 968 K

(695C)

and 15.4
were

nm

at

(555C). The authors


with this

stated that their


In

experimental

results

in disa

greement
in YSZ is

theory.

addition, since the concentration of oxygen ions

high, it is unlikely that any diffuse layer effects will contribute to Cdl. Using a typical oxygen vacancy concentration of 4.6103 mol/m3 we obtain a Debye length of -0.015 nm at T 1000 K. Thus it is assumed that Cdl is essentially determined by the inner layer capacitance. This implies that the value of Cdi should be basically independent of temperature, oxygen partial pressure, and applied overpotential. Cdl should, however, be dependent on the coverage of the electrolyte surface with the noble metal. In addition, there may be some specific adsorption of oxygen ions at the metal/solid electrolyte
=

interface be present.

There

are

few reports

on

the

investigation

of double

layer capacitances

of

porous metal electrodes

on

YSZ solid

electrolytes.
can

Robertson and Michaels

[32] have given

summary of the values which


are

be found for Pt electrodes

in the literature. The values

in the range of 30
to 1073 K

uF/cm2

to 350

uF/cm2

at

temperatures between
obtained

673 K

(400C)

(800C). These values


EIS data.

were

by fitting equivalent

circuits to

experimental

Obviously,

87

Implementation, Simulation,

and

Validation

these values

are

too

high to

account for pure inner

layer capacitances.

In

con

reported rather low values between 0.3 pF/cm2 and 1.3 pF/cm2 from potential step chronoamperometry [32]. They fitted experimental current-decay curves to the equivalent circuit
trast, Robertson and Michaels itself have
shown in

Fig.

3.3a. The authors have claimed that the initial current after
=

potential step should decay exponentially with a time constant of x CdlRe is much larger than the when the polarization resistance of the electrode, Rp, resistance Re. From an evaluation of the eigenval uncompensated electiolyte ues of the equivalent circuit shown in Fig. 3.3a and Fig. 3.3d we see that the proposed relation between x and Cdl is approximately met if Rt > 2Re (cf. 3A.2). The condition Rp Re is a necessary one. Unfortunately, the first con dition is rarely fulfilled experimentally even at relatively low temperatures [33]. We believe that the estimated Cdi values from Robertson and Michaels
are a

factor of 2 to 10 too low electrode

(see 3-A.2).

Higher
termed

capacitances (between -0.1 mF/cm2 to lm F/cm2, usually "pseudo-capacitances" [19]) are usually obtained by fitting experi

mental data to Tab. 1 in

equivalent

circuits of the

type shown

in

Fig.

3.3 b

(see also
to the

[32],
a

and

[19, 34]). These high values have been attributed

layer between the metal surface and an adsorbed layer of oxygen atoms or ions. Assuming a complete coverage of the metal surface with atomic Oad species of radius -0.06 nm, we obtain (Eq. (3.16)) a capaci tance of -18 pF/cm2. Smaller coverages imply smaller values. Note that for this capacitance contribution the Pt surface area is of relevance. Typical val
presence of
ues

double

for porous Pt electrodes


et al.

are

in the range of few


an

cm2 (thickness

<

50

pm).

Vayenas

have

proposed

that

"effective electrochemical double


of oxygen ions from the

is established due to

backspillover
in the

spread over pensating (screening) charge


subject
to
a

These ions

the metal surface and

Oad are accompanied by their com metal, thus forming surface dipoles [36].
Pt

layer" tpb [35].

With XPS the authors found two

types of chemisorbed oxygen on

surfaces,

prolonged anodic current treatment. If these surface ions contrib ute to the double layer capacitance, experimentally determined values for Cdi should be dependent on the surface area of the porous electrode (i.e. its thick ness and microstructure), on the applied overpotential, and on the tempera ture, because the equilibrium concentration of adsorbed atomic oxygen on Pt strongly decreases with increasing temperature. However, values below 100 uF/cm2 are expected for typical porous Pt electrodes. There is considerable experimental and theoretical evidence that capacitance values above 100 pF/cm2 are almost exclusively caused by Faradaic proc-

88

3.3

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 semi-circle or one broad semi-circle is observed. Numerical fit leads to capacitances in the order of (0.1 to 1) mF. (c) "Equivalent circuit" proposed to determine Cdl, Re, and Rt. No assumptions are necessary for the concentration imped ance Ze(jco). (d) Simplified version of circuit shown in (c). The circuit may account for depressed semi-circles or broad semi-circles in the complex plane.
Fig.
3.3

Electrical

circuit to account for the

89

Implementation, Simulation,

and

Validation

esses

[37, 38]. The

occurrence

of this behaviour

can

be

easily

understood in

electiolyte systems, as we have shown in part I [1]. These Faradaic processes take place on the metal surface and near the tpb, i.e. they occur in parallel to the double layer charging. This justifies the proposed general equivalent circuit shown in Fig. 3.3c. A blocking interface would simply consist of the electrolyte resist ance in series with the double layer capacitance. The splitting of ZF(jco) into a series combination of the charge-transfer resistance Rt and the concentra tion impedance Ze(jco) has been justified in part I. In model Ml we deter
mined
a

terms of the

dynamic properties

of these cathode/solid

capacitance
C

(4

kadNQp0i

(1

0)

4fcdesN0e)

(3.19)

obviously depends on the rates of adsorption and desorption, as well as on the steady-state concentration of adsorbed atomic oxygen, 8. We imme diately see that C increases with decreasing oxygen partial pressure which is in contradiction to the idea of "pseudo-capacitances" (decreasing p0 lead to lower surface coverages). Note that the occurrence of this capacitive behav iour is entirely caused by the dynamics of the oxygen reduction at the inter face. However, if experimental data are fitted with an equivalent circuit of the type shown in Fig. 3.3b it is expected that high values for Cdl will be esti mated. But, as we stated in part I, parameter estimation requires that the pro posed model may reasonably well describe the behaviour of the real system. Fitting inappropriate model structures to experimental data will give errone ous parameters or even parameters without any physical relevance, even if the "fit quality" is excellent! The use of equivalent circuits of the type shown in Fig. 3.3b is discouraged. We have put some emphasis on this point for two important reasons.
(i)

which

dynamic properties of the electiode/electrolyte interface are reflected by the Faradaic impedance ZF(jco). The experimentally determined imped ance Z(jco) is always obscured by the double layer capaci
aware

We must be

of the fact the

tance,

as

we

have shown above. For

discussion of the

properties

of the interface it is therefore

required

to obtain

Z(jco). Fitting experimental data to an equiva lent circuit may give completely wrong estimates for Cdl and

Zf(jco)

from

90

3.3

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

mentioned that Berthier et al.

[39] have proposed

method which allows for the determination of

Cdl

without

assuming
(ii)

an

equivalent circuit.
is to

The second

important point Cdl


is

recognize

that

an

accurate
accu

estimation of
rate

is

mandatory prerequisite

to obtain

values for the

estimate of
estimation

Rt
on

charge-transfer resistance Rt. An accurate required if one aims to carry out a parameter
experimental
are

the

data. For Ml and M2

we

have

shown that these models


if

not

globally

identifiable with EIS

Rt

is not known

[1]. This

statement

follows: if

Rt can not be determined losing one (important) equation in the parameters. This fact generally drastically decreases the global identifiability of a system. We will illustrate these points in the following sec
tion.

generalized as independently, we are


can

be

3.3.4

Digital

Simulation and Numerical

Aspects
ver

The simulations

were

obtained

by nmning

version 4.2 c of Matlab and

sion 1.3 c of Simulink

on a

Sun SPARCstation 20

running
can

the Solaris 2.4 oper

ating system.
ble

The Matlab

Optimization

and Control

System
be

Toolboxes with

were

used in addition. However, most of the simulations

run

reasona

mid-range personal computer using the student editions of Matlab and Simulink. It is beyond the scope of this paper to discuss in depth the details of Matlab and Simulink. However, with a basic familiarity of the programs and together with the information given in the appendices 3-A.3 and 3-A.4 it should be possible to re-implement the models and to run simu lations. We believe that this is a good starting point to write own programs. The following information is addressed to the reader familiar with the pro
on a

speed

gramming environment.

91

Implementation, Simulation,

and

Validation

stability problems during simulation of the time dependent behaviour when using an inappropriate integration (e.g. Runge-Kutta or Euler method) algorithm due to the stiffness of the mass balance equation. By using the "gear" method with appropriate step sizes we were able to circum vent these problems. Steady-state values for the state variables were reliably determined with the Simulink function "trim" for any physically reasonable values of the overpotential 11. Appropriate starting values for x and y were
We encountered

given

while

u was

fixed. The state-space vector determined with "trim"

was

used for the extraction of linearized state-space models with the Simulink function "linmod" at the bation level of

corresponding operating point.


The

The default

pertur
for the

10"5

was

used. Different levels could be set to

probe
was

validity

of the linear

regime.

conditioning

of the system

achieved

through the scaling of the state variables with the maximum number of adsorption sites, N0. The values for the input and output quantities were in the range of unity for the chosen geometry, thus no further scaling of these
values
was

necessary. The condition number of matrix A obtained with the


was

Matlab function "cond"

generally

below

104, indicating

that the

prob

lem

was

well conditioned

obtained with the Matlab


mates for the inverse

([40], p. 1-66). Frequency response data were functions "bode" or "nyquist". Numerical esti
resistance R~
were

polarization

conveniently obtained

with the Control Toolbox function

"dcgain".

3.4
3.4.1

Simulation Results

Charge-Transfer Controlled
current

Kinetics
results obtained
K

Exchange
Pt,

density i0.

Experimental

on

the system

02(g)
to

zero

high temperatures (above -1123 moderate cathodic overpotentials indicate


I YSZ at

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


occurs
can near

that the oxygen reduction

under these conditions is

charge

transfer controlled

expect such
the

behaviour if the concentration of adsorbed atomic oxygen of the current

tpb

is

independent
to

through

the interface. This

if the

rate of surface

diffusion and/or the rate of dissociative


near

adsorption
assume

is fast

compared

the electron transfer rate

the

tpb.

We

for the broad

moment that the electrode kinetics is

charge-transfer

controlled

over a

range of temperatures.

92

3.4

Simulation Results

If, and only if, the electrode reaction is dominated by the


process at the

charge-transfer
=

tpb,

then the

following holds (with


RT
=

2 and

[1]) (3-2)

'o

Sf

2F

,._nx

Rt(n=0)

Rt(r| 0) is the charge transfer resistance at equilibrium potential. If Eq. (3.20) applies, the electiode properties can either be described by Rt or iQ. A quantitative expression relating the exchange current density i0 with the T as well as at arbitrary temperatures is oxygen partial pressure at T
where
=

given in part

I of this paper

[1].

At T

T the

expressions

reads

as

f0(r,pO2)
Fig.

2N0Fklc[Vo]

f^} l+K(T)Jp02
of

Po2l~W1

(3-21)

partial pressure experimentally by a temperature. 1/4 number of authors [9, 43, 44]. They found approximately a p0 dependence of i0 at low oxygen partial pressures and a p0 dependence at high oxygen 1/2. partial pressures. This follows immediately from Eq. (3.21) with P
3.4 shows the calculated
on

dependence

iQ

on

oxygen

and

A similar behaviour

was

obtained

one-quarter dependence of i0 on p0 was first analytically obtained by 1/2 and they consid Wang and Nowick [9]. However, they assumed P
The
=

ered the

Langmuir equation 9/(1-8)


->

K(T)Jp^

under the

limiting condi
on

tions of 9

0 and 9 1
on

(see [9] for details). From the available data

oxygen
are

adsorption

Pt it is

questionable

whether these

limiting

conditions

experimental situations considered [33]. However, the one-quarter dependence is also obtained without the simplifications of the Langmuir equation, as we have shown in part I. Note that the p0 depend ence is also a function of the charge-transfer coefficient P. This property has
reached under the
not

yet been stated

in the literature. A measurement of

i0(po )

may reveal the

value of

p accurately and uniquely.

The oxygen

partial

pressure where the maximum of


It is

decreases with

decreasing temperature (Fig. 3.5).


1-2P
+

i0 occurs, given by [1]

p0 *,

P2

^K(T)

1-P PK(T)

(3.22)

93

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

range considered. It is also

seen

that the value of p0

is rather sensitive

irmTTf

10

-1

1200

slope (1

p)/2

1100
-2
--

10

1000

CM

'-

6
o

10"3

-_

900

..^-^
10

rA

820

-.

slope ~p/2
10

-5

750
i.hi

"'

'"'

jJ

'

10

101

102

103

104

105

PoJ**
Fig.
3.4

Relation between the

exchange
given

current

density i0

and the oxygen

partial

pres
con

sure.The
stants

temperatures (K)
in Table 3.1

are

within the
were

figure.

The

parameters

and rate

given

(appendix 3-A.l)

used for the simulation. Note that

0.62.

94

3.4

Simulation Results

r=900K
_-/

p
7

0.65

./*

//I
(l

>>

0.5

0.5/#

/ /
/

0.2

/
p
=

"0:=

-P)2 p2*2

0.35

0.1

'

'

10L

101

102

103

104

10J

PO** )2y
Fig.
gen
3.5

Dependence of i0
=

on

the

charge
same

transfer coefficient
as

p.The
3.4. p0
*

simulation

was

obtained for T

900 K with the

parameters

in

Fig.

denotes the oxy

partial

pressure where the maximum value of z0

occurs.

to the value of

p0*
p0
*

P (cf. Fig. 3.5). Eq. (3.22) simplifies K(T)~2 with p 1/2 [44].
=

to the well known result of

In the

literature, the experimentally obtained temperature dependence of


=

was

AHad
on

employed for the ad Edes [44, 45].


-

determination of the heat of oxygen


Note that

ad

and

Edes

are

adsorption strongly dependent


From the

the surface coverage of Pt with atomic oxygen of

(see e.g. [46]).

Langmuir equation it is easily seen that the surface coverage


mum

where the maxi

i0

occurs

is

given by

9*

._ =

*<T>-^ l+W)JPo2
the

(3.23)

which

gives by

use

of

Eq. (3.22)

simple
1-p.

result of

9*

(3.24)

95

Implementation, Simulation,

and

Validation

Only

in

case

where

1/2

we

have 9*

0.5

[47]. However, if 9>0.2,

AHad
good

becomes almost

independent of surface

coverage

[48]

and

we can con
*

sider the activation energy obtained from


estimate of the oxygen
=

plot of p0 as a adsorption enthalpy AHad at high Pt surface


an

Arrhenius

coverages, i.e. at 9
mined for

9*. We would like to mention that the values deter

AHad by

Okamoto et al.

[44] and Mizusaki

et al.

[45] differ by
an

about 50

kj/mol.

It is

important
with

to note that

Eq. (3.22)

was

derived from

expression relating iQ
al. determined

experimental quantities (Eq. (3.21)).


=

Mizusaki et
,

AHad

from the electiode conductivities ae

R~

whereas

analysis on measured exchange current densities. We will show below that i0* is generally not located at the same pQ as ae*, therefore an Arrhenius plot of pQ (ae*) will not yield AHad. investigated. Fig. 3.6 shows iso baric Arrhenius plots of iQ. With decreasing temperature, the isobars show breaks to steeper slopes, which occur at a higher temperature the higher the p0 Note that only i0(po *) shows a straight line and that the corresponding activation enthalpy for charge transfer is given by
is
.

Okamoto et al. based their

Finally,

the

temperature dependence of i0

AHct*
where

(1-P)a + P-Ea
energies
The

(3.25)

Ea

and

Ea

are

the activation

for the forward and backward


result
in

electrochemical

reaction,

respectively.

Eq. (3.25)

is

easily

obtained from the

p0 with the

general expression i0(T, p0 ) given in part I by replacing expression given in Eq. (3.22). For arbitrary pQ we find a limit
with

ing apparent activation enthalpy at low pQ larly at high pQ wi\hK(T)Jp0 1. In the

K(T)Jp~Q

1, and simi-

first

case we

obtain

AH^t
whereas in the second
case

AHct*-<l^.AHad

(3.26)

AH!!1?!1 rhij

[<t,ct

=
-

AH..*

""ct

T2

'

AH^.

""ad

(3.27)

limiting pQ regimes, as well as the limiting behaviour of i0(po ) is clearly seen in Fig. 3.6. With P 1/2 we obtain the same results as developed by Wang et al. and by Velle et al. [9,10]. A behav=

The transition between the

96

3.4

Simulation Results

iour of
was

const) with temperature similar to the one shown in Fig. 3.6 i0(po found experimentally [9, 49]. With the parameters given in Table 3.1 we
=

obtain

AHJJ^th
AH^

AHct*
=

131

kl/mol,
et al.

AH^,Z

"
=

kJ/mo1'
96

and

183

kl/mol. Wang

[9] found

AHj,
et

kl/mol from the [10] determined

temperature dependence of
=

i0(po

), and Velle

al.

kl/mol from the temperature dependence of Rt(Pcy "H (equivalent circuit fitting of EIS data was used). Both authors used a rela 294 kl/mol. How tively high value for the adsorption enthalpy, AHad
199
=

ever,

relatively large discrepancy


170

exists between the

reported

values for

AHC* (Ref. [9]:


large

kl/mol; Ref. [10]: 126 kj/mol) which

is attributed to the

value used for

AHad. Using

a more

probable

value for the

adsorption
diminishes

enthalpy AHad and AHct* is obtained


In summary,

in the range of -180

kj/mol [48],

this

discrepancy

in the order of 140

kj/mol.

experimentally. The charge-transfer coef ficient P can be obtained from i0(po ) data at high temperatures (cf. Fig. 3.4). Unfortunately, Eq. (3.25) is now not sufficient to estimate uniquely the activa tion energies of the charge-transfer reaction, Ea and Ea It is expected, how AHct*
can

be obtained

ever, that both values

are

not too far

apart.

Estimates of

AHad

are

available
it is

through Eqs. (3.26) and (3.27). For reasons which will become clear below suggested that Rt data are employed rather than i0 estimates.
Electrode

polarization

and

experimental

determination of i 0

So

far
a

we

have assumed that the reaction is

range of temperatures. In this case,

charge-transfer controlled over the exchange current density i0

broad

and the

charge-transfer coefficient P determine the overall electrode characteristics. In solid state electrochemistry it has been common practice to obtain both values from a Tafel-plot analysis of Ip(T|) data. However, the parameters obtained from this analysis are only meaningful, if one charge-transfer (or one chemical) step is actually rate determining the overall electrode reaction
[1,50,51].
But how
can we

test whether this

requirement is fulfilled under

the

experimental

problem will be examined below and we will propose a method in the following subsection which may uniquely clarify whether an electiode reaction is controlled by a charge-trans
fer step
or

conditions considered? The

not. We
=

use

fications:

klc

2-105 m3/(mol-s)

the parameters of Table 3.1 with two and

important

modi

Ed

110

kj/mol.

97

Implementation, Simulation,

and

Validation

77C

900
t

800
i

700
i

600
i

500
r

io-1

10"2

I IO"3

10"5

0.8

0.9

1.1

1.2

1.3

1.4

103K/r

Fig.
cal

3.6

Isobaric Arrhenius for

expressions

apparent

activation

plot of i0 at different oxygen partial pressures.Analyti the charge transfer activation enthalpy at pQ *, AHct*, and the enthalpies at low and high pQ AH^t and AH^t are given in
, ,

the text. The

parameters of Table3.1

were

used. Note that pQ

*(1100 K)

10

Pa.

Compare

with the simulations of

Fig.

3.4.

98

3.4

Simulation Results

First, remember the

general

definition of the

charge

transfer resistance

^-?)*.
where x{ denotes the

(328)

steady-state surface concentrations at the correspond ing operating point (defined by T|, T, and pQ ). It is seen that Rt can be obtained at arbitrary operating points, whereas i0 (Eq. (3.20)) gives only a description of an equilibrium situation (i.e. where r| 0 and therefore 0). By considering Eq. (3.28) it seems that Rt could be obtained experi 7F
= =

mentally from a small-signal dc analysis

around E

or

around

overpotential, as it was done in the literature [44]. This is not case, as Eq. (3.28) requires that the surface concentrations xi remain constant. which is only Such an analysis will reveal the polarization resistance R equal to Rt if the reaction is charge transfer controlled. Similarly, we can strictly speak of a pure Tafel behaviour only if the concentration of surface species (in our case only Oad) remains constant over the overpotential range where the analysis is conducted. However, surface concentrations can not be measured directly and therefore it is difficult to draw conclusions about the reaction mechanism from fF(T|) curves alone. In addition, it has been shown that an apparent Tafel behaviour may be caused by a competition between surface mass transport and charge transfer, if some requirements are satisfied
[38].

steady-state generally the

fF(n) curves of M2 at 1123 K (850C). It is seen that the IF(r|) behaviour at high pQ follows an ideal Tafel behaviour up to relatively low cathodic overpotentials of approximately -0.15 V. Strong devi ations from the purely charge-transfer controlled behaviour occur at larger overpotentials. The deviation from Tafel behaviour is shifted to lower
Fig.
cathodic
curves

3.7 shows the simulated

overpotentials
an

with

decreasing

pQ

It is further

seen

that the

follow

apparent Tafel behaviour at low cathodic


process and
a

ip(T|) overpotential
a

(with apparently lower P than used for the simulation), indicating


tion between the

competi

charge-transfer

further reaction.

easily found in the deviation of the surface concentration x from its equilibrium x0 value near the tpb. Fig. 3.8 shows the high p0 curve from Fig. 3.7 in a linear plot. Although the deviation from the
reason

The

for the deviation is

Tafel behaviour is obvious, it would be difficult to

recognize
seen

this without the


con

given

curve.

The inset of

Fig.

3.8 shows the behaviour of three surface

centrations at different distances from the

tpb.

It is

that the concentration

99

Implementation, Simulation,

and

Validation

of

Oad

near

the

tpb strongly
a

decreases with

increasing
Note that
to

cathodic

overpoten
a

tial. This is the the


occurrence

reason

for the deviation from the ideal Tafel behaviour and for

of

concentration

polarization.
very

we

used
this

very

high

value

for

the

surface

diffusion

coefficient

obtain

behaviour

layer of -10 pm. Real values for D are expected to be one to two orders of magnitude below this value at T 1123 K [52]. In contrast to the simulations shown in Fig. 3.7, the real porous electrode/electrolyte system does not exhibit a limiting If(t\)
(D
=

3.5510"9 m2/s).
=

This also

causes a

large

diffusion

10

>

\
\

\
\.
\

'

7= 1123 K

\
\

*\

\
^

\
V

y^

N\-\
\
v

io-1
.

X
\

*-*
^

i\
\

\.

'a

*\
\

\
*

,s

^io-2 5-

\
\

A
i

\
A

\
\
\

1(T3
-

Po2=15pa
2
a

1
:

104Pa

103Pa

i
>

'

in-4

<

-0.5

-0.4

-0.3

-0.2

-0.1

n/Vvs.eq(r=1123K)
Fig.
3.7

Steady-state 7f(n)

behaviour of Model M2 at T

1123 K.The

filled

circles

represent the simulated JF(T)) behaviour. The lines give the IF(r\) behaviour under the

assumption
The
T
=

that the surface concentration remains constant is defined relative to the

(i.e. pure

Tafel

behaviour).

overpotential
1123 K.
as

Parameters:

110

kj/mol;

Equilibrium potential develops at 2 105 m3/(smol); remaining Jtlc


=

which

parameters

given

in Table 3.1

100

3.4

Simulation Results

behaviour under the considered conditions. This is due to the fact that model M2 does not account for the

stiong coverage dependence of the adsorption

desorption rate. The sticking coefficient of Oz(g) on Pt may vary many orders of magnitude with surface coverage [46]. Accordingly, the adsorption rate should strongly increase with cathodic overpotential [33].
and
Let us,
as

it is often done in
curves
seen

practice, perform

Tafel

analysis
an

on

the simu of the

lated

IF(n)

from

=-0.15 V to -0.35 V

Fig.

3.9 shows

some

results. It is

that the simulated

IF(r\)
1

curves

follow

apparent Tafel

7"= 1123 K p

j>^*

"

=io5pa

,y^
/ /

-0.2

/
/

#
#

/ /
04

<

-0.4

/
/

/
/
1

0.3
/
s

/
/

1
1

-0.6

/
/

^02

50nm
-

J
0.1

3.75 nm 5
nm

-0.8

/
-1
III
1

-0.4
-0.2 0

-0.4 ri/Vvs.E
eq

-0.2

(r=1123K)

Fig.

3.8

Deviation of

JF(n)
=

from theoretical Tafel behaviour.Linear


10

plot

of the data

shown in

Fig.

3.7 at pQ

Pa. The filled circles show the simulated behaviour of

M2 and the solid line denotes the ideal Tafel behaviour. The inset shows the

ing

surface concentrations
n
.

as a

function of the distance from the

tpb

and the

correspond applied

overpotential

Note that the surface concentration

gradient extends

over

~10 pm.

101

Implementation, Simulation,

and

Validation

line

over

the range of

overpotentials
=

considered. However, the estimated

value for the


below the

charge-transfer actual value of P


ones

coefficient
0.62.

decrease with p0

and

are

all

Fig.

3.10 compares the theoretical results

analysis. It is seen, although the values are rather close to each other, that the pQ dependence of i0 estimated from the Tafel analysis is completely different to the expected (theoretical) p0 dependence. It can be further seen that a relative large number of meas urements (or simulations) are necessary to reveal the p0 dependence. It
10l

for

i0

with the

estimated from the Tafel

VI

X
,-1
10
7

'VV (0-49,6.5)
x

^s*\
X

;
^K ^^.
.

*S ">

*^~-^-

V
-

(0.19, 10.5)xs^^^~^^
x

N^-Q^^
'Y

*>.

^V Nw

"^s.
^v\
*V\ ^L
\
*

"""""*>^

10
C4

,-2

^^-~~-^ %^

\.

s-

s
<

^^

\
v
\

*^

\ \

>

-.

'.

~*

(0.08,2.5)

^T~X

*v
'

\
I

\
\ ^
1

L
_

10"

T 1 k
1

*-

*.

*
i

1
'

* *
.

i
:

t
i

10

,-4
pn
2
-

!
c

< >

W Pa

3.16103Pa

* i

i
.

102Pa
10

,-5

-0.5

-0.4

-0.3

-0.2

-0.1

i\/V

\s.

E(T= 1123 K)

Fig.

3.9

Simulated

Ip(T\)

behaviour and Tafel

analysis.The
The value for

Tafel

analysis

was
are was

obtained from the simulated

/F(t|)

data from T| =-0.15V to -0.35 V. The results

given

as

(P, f0/mA-cm"~2) pairs


same

within the

figure.

in the simulation

0.62. The

parameters

as

for the simulations in

Fig.

3.7

were

used.

102

3.4

Simulation Results

should be mentioned that the estimated values of the number of simulated data

iQ

are

rather sensitive to

points used

for the Tafel

analysis.
an

We end this subsection with the

following
does not

conclusions: first,

apparent

Tafel behaviour of the

JF(T|)

curve

assure

that the reaction kinetics is

charge-transfer controlled. Second, Tafel parameters (P and iQ) obtained from values and an a Tafel analysis of IF(t|) data may be far apart from the real interpretation of these parameters will be questionable. Third, measurements of the jf(t|) behaviour impose a large perturbation to the electrode/electro lyte system which may cause irreversible changes to the microstructure and/or the interfacial structure. Finally, Jf(t|) measurements reveal the least possible amount of information about an electrode/electrolyte system, which
nevertheless, might be needed in combination with further electrochemical

10

's
<

s
1

slope(l-$)/2

0.5

from Tafel

analysis

L, theoretical value

0.2

101

itf

10"

PoJ**
Fig.
3.10

Comparison i0

of theoretical and estimated j0 values at T

1123 K.The open

circles represent the estimated


Note that the
can not

be

i0 values from the Tafel analysis as described in Fig. 3.9. compared with the data in Fig. 3.4 because the electrochemi
factor of 10. The
same

cal rate constants differ

by

parameters

as

for the simulations in

Fig.

3.7

were

used.

103

Implementation, Simulation,

and

Validation

methods, such

as

electrochemical

impedance spectroscopy (cf. part I

of this

publication [1]).
Electrode

impedancesdetermination of Rt

and

Cdl.

As

mentioned

above, electrochemical impedance


Faradaic

measurements do not

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

directly reveal the concealed by a double layer

cuit and

interpret

the values obtained for the resistances and the


work well in this
cases.

capaci
fail in

tances. This
more

might complicated

simple

case, but it will

certainly
as

We therefore propose to continue

described

below.

Fig. 3.12 shows two series of spectia, each points of M2 but with different values for
The

series taken at different

the double

operating layer capacitance Cdl.

spectra show the Faradaic impedances ZF(jo)) (thick lines) of a purely charge-transfer controlled reaction kinetics (figures on the left), a kinetics
where

charge-transfer
and
a

is in

competition

with surface diffusion

centre),

kinetics where surface diffusion is rate


seen

(figures in limiting (figures on


come

the the

right).

It is

readily

that it is almost

impossible

to

to these conclu-

104

3.4

Simulation Results

r=1123K,/70 =103Pa
n=0V

S
C!

s
l-H

a)
0

3.1

3.2

3.3

3.4

10

12

Re(Z/Qcm2)
1.5

ZF(jw)
Z(ja))

7
0

32k 100k <

ri

-0.30 V

-0.50 V

b)
0

0.5

1.5

2.5

Re(Z/Qcmz)

complex plane.The spectra were sim overpotentials given within the figure. The results can be directly compared with the JF(r|) simulations given in Fig. 3.8. The num bers within the figure denote the frequency in Hz. The same parameters as for the simu lation of the JF(r|) curve in Fig. 3.7 were used. A double layer capacitance of Cdl 20 pF/cm2 was assumed. Note that the Faradaic impedances ZF(jo)) at low cathodic overpotentials are almost invisible because Rt ^p (see inset f upper figure).
Fig.
3.11

Simulated
=

Z(j0))

of M2 shown in the
=

ulated at T

1123 K and pQ

10

Pa at the

105

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
1-1

01

o>

J*

5
05
V V
01

9
M)
01

o
u

JS S 'I
.m

01
cy

>

ja
-

3
o
to

S
CO CO

2
01

5
O

3 -3 5

1 J!
CO
<^

>

CL.H
co

X
-M

QJ 01

-a

^
ft;
V

N
o>

*
"-1
j_

3
N

x CO

<0

g
CU
01
~

of

01

c
I-l

6
W)

S
'
,>

.2
N

CO Oi

c
'

&, T3 SX c
co

'C

jCl,
O)
~

C
O

esp
*-

~&*
^rL
^

0 1V
05
tl

/'*8 O
0

-"*<

ance cor
CO

X,
o

of

0 0

ooe

=*O
<1

(
\

/
n

Su
fti

"j
c
co

c
>

o.,
U

> O

fsi

-"a
co co

01

<"">

CO

^">

01

tj
C
-

a
O
(J
M

o>

>
in

Oi

II

II

O, CL, 3

ik/
d

J
O

10k/
z-

^
^\_m
^-_. -

3
o

o
o
a,

X, *

<u

.z-

c
M

-g

^ 8.
"

39
3

o.S
1
to
.

2J
o

^
01

N
o>

13

^ .2
^1
CO

CO

(T1 +3

106

3.4

Simulation Results

,_

300
. #

100

Ik

4
CN

.*

30

Cdl
10

20jiF
^ #

d
S3
0
.

(iF
.

20k

X5HF 4
*

\
x

lUF J?

.o\xx

V
1

-4

0
i i
i

2
1 1

4
1

6
1

8
1

10

12

16

20

Re(Z/a-cm2)
impedance data.The parameters as given in Table3.1 were used at T 1000K with Cdl 28 pF/cm2 and Re 1.3 Qcm2. Weighted (1/|Z|) random noise of a maximum amplitude of 1% was added to the data. The inset shows the high frequency part of the spectra for decreasing values of Cdl.
Fig.
3.13

Complex plane plot

of simulated

impedance Z(jco) spectra (thin lines). We further see that the actual value of Cdl strongly influences the appearance of Z(ja)) and that the appearance of a single semicircle in the complex plane is by far not a suffi

sions from the

governed by a single step (see [51]). We feel that it is necessary to determine the Faradaic impedance ZF(jco) rather than just the impedance Z(jco), i.e. we need to know Cdl. We demon strate a promising procedure in the following.
Fig.
3.13 shows
a

cient condition that the reaction kinetics is

simulated

impedance

of M2 in the

complex plane.
an

ran

dom noise is added to the spectra. The

impedance

from the

given
3.13

data without

problem fitting the

is to extract the Faradaic

data to

clearly shows the influence of a itance on the ZF(jco). Rt is expected to be in the order of 7 Qcm2 and Re is -1.3 Qcm2. We apply the method proposed by Berthier et al. [39] on the impedance data. Fig. 3.14 shows the final result. The Faradaic impedance is obtained by subtracting Cdl and Re from the impedance data. Once Cdl is

cuit. The inset of

Fig.

equivalent cir double layer capac

107

Implementation, Simulation,

and

Validation

12

'cdl

II
zg<d)
II

-I *. f-

1
1

i
, ,

ZF0co)

L-r-\RT\- Z9(jco)
1

^Zptjo))

B
C!

o o o o

S3
ii

o o o

o o

oo

\
Rp
1

10

15

20

Re(Z/Qcm2)
Fig.
3.14

Determination of

ZF(j(0)
[39].

from simulated

noisy Z(jO))

data.The

method

from Berthier et al. is used


With
=

The

electrolyte
=

resistance is subtracted from the data.

1.3 Q-cm2 a value of Cdl 28 pF/cm2 is estimated. The inset shows the Re circuit" which describes Z(ja>). Note that Ze(joa) can not be represented by "equivalent

an

electric circuit.

estimated, R

and
in

Rt

can

be

accurately
an

estimated from the function S'

(equation (26)
ance

[39]). S' for the data

set considered is shown in

However, the method requires

accurate estimate of the

Fig. 3.15a. electrolyte resist

Re, as was also mentioned by Berthier et al. [39]. In practice Re is often not accurately known and it is estimated by extrapolating the high frequency impedance data towards the real axis. This may cause large errors in Cdl and, therefore, in Rt as shown in Fig. 3.15b. If Re is only approximately known one can run the algorithm for a series of electrolyte resistances around the expected
mental
value

(Fig. 3.15b).
always
we

We have done
we

so

for

large
Fig.

number of

experi
of the

[54]

and simulated data and

have found that the shown in

shape

Cdl(Ke)

function

looks like the

one

3.15b. Furthermore,

Re is always located near to the maximum of the curve towards higher electrolyte resist ances. This procedure helps to obtain a starting guess for Re. Further refine ment is achieved through an iterative search of the "optimal" (CdI, Re) pair

from simulations

have found that the "true" value for

108

3.4

Simulation Results

by optical inspection of the resulting spectra. In the following we will always give both the Faradaic impedance ZF(jo>) and the impedance Z(ju)).
give only meaningful parameters if the reaction kinetics is dominated by a single reaction step. Interpreting P and, especially, i0 is doubtful. EIS spectra alone do not generally help to clarify the
In conclusion,
a

Tafel

analysis

may

layer capacitance Cdl must be determined and extracted from the EIS raw data. Re and, more importantly, Rt are obtained with reasonable accuracy, where Rt is related through (RT)/(2F) R^1 with the exchange current density iQ (at arbitrary oper i0 question
of

single-step

control. The double

ating points).

A discussion of

iQ

data obtained in this way

seems

reasonable.
as

Much information is contained within the Faradaic illustrated in the

impedance,

further

following

section.

3.4.2

Competition

Between Surface Diffusion and


At

Adsorption
to -773 K

Electrode conductivities.

temperatures below -1073

(800C)

(500C) and
electrode

at

oxygen
on

partial

pressures above ~100 Pa, surface diffusion of

atomic oxygen

the Pt surface is believed to be rate

kinetics

[10,15,45,47,55,56].

Various

determining the overall analytical expressions

IF(T|) characteristics, and the elec trochemical impedance have been presented in the literature. However, it has been always assumed that no adsorption takes place in parallel to the surface 1/2 diffusion process. Under this assumption, a pQ dependence has been jR~ at low pQ In the following derived for the electrode conductivity ce describing
the electrode

conductivity,

the

we

will obtain simulations for

compare the results with


The relation between

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


and R~
as a

and T and

R^

function of pQ

is shown in

Fig.

3.16

for temperatures from 773 K

(500C)

to 1073 K

(800C). By use of Eq. (3.20) the

exchange

current densities

spond

to those

given

in

i0 can be obtained from Rt. The iQ values corre Fig. 3.4. The simulations give a picture which is in

reasonable

qualitative

Mizusaki et al.

quantitative agreement with the measurements of (see Fig. 7 in [45]). The maxima of the log(fv~ ) versus
and shift to lower pQ
of R~ with

log(p0 )
there

curves

decreasing temperature. However,

are some

differences that attain further attention.

First, the pQ

dependence
.

region

than in the

considerably stronger in the low pQ high pQ region. Fig. 3.17 shows the pQ dependencies of
is
a

Rp

and

R^

Note that not

clear pQ

is found for the

conductivities, but

109

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/(Q-cm2)

Fig.

3.15

Determination of
two maxima for

showing [39] (Eq. (26)). (b) Dependence lyte resistance Re.

Rp and Rt after subtraction of Cdi-(a) Rt and Rp. The definition of the function
of

Cost function

S'

S'

can

be found in electro

Cdl

on

the initial value of the

uncompensated

110

3.4

Simulation Results

dependence varies continuously over It is clearly seen that a pQ dependence of R~


that the

more

than

one

decade of

is found at low oxygen

pQ^. partial

pressures. The
gen
in

reason

for this

can

be found in the fact that dissociative oxy

adsorption

occur

parallel,

of oxygen molecules and surface diffusion of atomic oxygen the pQ even near the tpb. Analytical solutions describing

10-5

L_

,_

10

101

102

103

104

105

Pon*

Fig.

3.16

Electrode conductivities

as

function of

temperature and oxygen partial

pressure.The temperatures (K) where the simulations were obtained are given within the figure. The data for Rt and R were obtained from the linearized state-space model M2 ((A, B, C, D) quadruple) at the corresponding operating point. The parameters
given in Table 3.1 were used.

Ill

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

dependence of ZF(jco), and larly at high oxygen partial


of
R~

therefore also of R

can

be found in

[57]. Simi

,-i

pressures
seen

is

obtained,
R

as can

be

in

one-quarter pQ dependence Fig. 3.17. It is further found (but not


minus

independent of the charge transfer coefficient P, where in contrast, R^ (pQ ) strongly depends on P (cf. Fig. 3.5). Taking a closer look at the experimental cre(p0 ) data from Mizusaki et al. reveals that the p0 dependence tends to be stronger than 1/2, especially at high temper atures (cf. Fig. 7 in [45]). Similar observations can be made on the early results from Fabry and Kleitz [58]. We again see that a relatively large number of measurements is necessary to reveal the pQ dependence of the
shown) that

(pQ)

is almost

electrode conductivities, otherwise the information

might get

lost in the

experimental errors.
A Pq

dependence
(10
to

of R~

has been

reported

for oxygen

below

100)

Pa

by

number of authors

[59-61]. This

partial pressures is generally attrib-

112

3.4

Simulation Results

uted to gas model M2

phase

diffusion of oxygen in the porous electrode network. Our

can

not account for

this.

It has been claimed

by

Mizusaki et al. that the activation energy for


an

Oad

dif

fusion

on

Pt

can

be obtained from

Arrhenius

plot

of Rl
.

(pQ +),

if surface

diffusion of

Oad
R~

argued that dependence


R"

determining (pQ +) is where


is

the electrode kinetics


6
=

The authors have

1/2

and therefore the

temperature
we

of the concentration term should be excluded. However,

have shown above that

R^ (pQ
higher

*) results
than

at 9*

P and

we

see

that

(p0 t)

is located at

pQ

shown in

Fig.
P

3.16 it is

seen

that the

R^ (p0*). From the simulations log(pQ ) difference between the two


Because R~
is

maxima is almost

independent of temperature.
*

virtually inde Fig. 3.5),


find
we

pendent

of

and Pq

for

R^
at

is

given by Eq. (3.22) (see

also

find that this distance decreases with


simulation that

decreasing

values for

P (we

by
as

pQ

pQ

1/4 for M2 and the other

parameters

given in Table

3.1.

Fig.

3.18 shows the

723 K
seen

(450C)

to

temperature dependence of l/Rp at different pQ from 1073 K (800C). Note that pQ1 > 105 Pa for T > 1000 K. It is
of the

that the

slope
of

log

R~

(pQ +)

versus

1/T

plot

is

approximately
We find
an

independent

temperature

and the value of

P (not shown).

apparent activation energy of -152 kj/mol at high temperatures and a value of -167 kj/mol at lower temperatures. Mizusaki et al. determined a value of
-171

kj/mol
155

experimentally
it is
seen

(see

Fig.

10

in

[45]).

We

assumed

Ed

kj/mol and

that the activation

enthalpy

of R~

(pQ t)

does not
becomes

correspond to the activation energy even more pronounced if a larger value


apparent activation
-873 K
as

of surface diffusion. This for


in the simulation

is used. It shows that the

AHad enthalpy of

R~

(pQ t)

comes

close to

AH^

at

temperatures below Pa)


is obtained

energy of R~ (10
surface coverage
tures. At low

(600C). The apparent activation -200 kj/mol at lower temperatures (high


to -140

regime)
and

and it T

changes

kj/mol

p0

high
can

(low

surface coverage

higher tempera regime) we find a very


at

low apparent activation energy of -45 These simulation results


ture

kj/mol.

dependence

of the

easily explained by considering the tempera concentration impedance Ze(jco) as introduced in

be

*)

pQl

is the oxygen

partial

pressure where the maximum of ae is obtained;


*

we use

this notation in order to avoid confusions with pQ obtained. Note that Mizusaki et al.
use

where the maximum of

R^"1

is

the notation

ae*

for

expressing

pQ *.

113

Implementation, Simulation,

and

Validation

parti.

From the

two-compartment ZF(jco) transfer function of

M2

we

find

the concentration resistance

[1]
kf
+

Rc

Zeo

0)

Rt 1
f
d
+

kb
u.

(3.29)

4/cadN0Po,

(!"*)

4fcdesN0

'

Remember

the

definitions

of

Td
and

S2/(2D),
=

vadexp[(-Ead)/(RT)], fcdes in terms of k( (see part I) it is seen that the temperature by expressing kb dependence of the product Rt (kt + kb) cancels and we are left with a simple expression for the temperature dependence of Rc. We consider two limiting
=

Kd

D0exp[(-Ed)/(RT)], Vdesexp[(-Edes)/(RT)] Again'


=

cases:

(i)

low T and

high pQ (high
remaining
=

coverage: (1

x)

>

0): surface dif

fusion vanishes (1. term of the denominator in

Eq. (3.29)).

We

expand
result:

the

fraction of

Eq. (3.29)

with

l/kdes

and

obtain with K(T)

Jkad/kdes

and (1 -x) 0 the

following

AHj
and with
=

Edes
given
in

(3.30)
Table 3.1

the

AHj
(ii)

parameters

200

kj/mol.

high

T and low pQ
x >

(low coverage:
0
we

0): proceeding

as

above and with

obtain:

des-d
=

(3-3D

and, accordingly, Ai-L


The simulation results

45

kj/mol. agreement with Eqs. (3.30) and (3.31).

are

in excellent

Obviously, the apparent activation energy may vary in between these two limiting values, as seen in Fig. 3.18 for the simulations of R~ (10 Pa). t Let us finally consider the temperature dependence of (cf. Fig. 3.19). An p0 average apparent activation enthalpy of -150 kj/mol is obtained over the temperature range considered. The value is slightly higher at lower tempera-

114

3.4

Simulation Results

800

700

600

500

77 C

0.9

1.1

1.2

1.3

1.4

103
Fig.
3.18

K/T

Isobaric Arrhenius
were

plots

of electrode

conductivity

R ".The
were

parameters
obtained from

given

in Table 3.1

used for the simulation. The values for R~

the linearized SSM at the

enthalpies AH^

are

corresponding operating point. within the figure. given

The apparent activation

tures

(158kJ/mol)

and

decreases

with
Pt is

(-140 kj/mol). The surface coverage of


constant in the

increasing temperatures relatively high and remains not


et al.

temperature range considered. Mizusaki


activation

[45] deter

mined

an

value of
between

enthalpy of ~220kJ/mol for the maximum the electrode conductivity. Accordingly, a large discrepancy exists our simulations and these experimental results. However, the
apparent
result
was

reported

obtained from

number of different measurements

115

Implementation, Simulation,

and

Validation

which itself exhibited

rather

large

mean

variation

(see Fig.
to

9 in

[45]).

It is

questionable whether this large value can be attributed by the authors.


We would like to

AHad,

as was

done

point out two important

differences between

our

model M2

investigated by Mizusaki et al. [45, 47]. First, Mizusaki et al. assumed that the charge-transfer reaction was infinitely fast. However, we show below that this influence is significant in the temperature range considand the model

106

105

CN

104

103

102
j
i i L

0.9

1.0

1.1

1.2

1.3

1.4

103K/r
Fig.
R~
3.19

Simulated

temperature dependence of the oxygen partial pressure where the

maximum of the electrode


,

conductivity occurs.The data were obtained from by determining the maximum value for R~ The inset shows (pQ the corresponding equilibrium surface concentrations of adsorbed atomic oxygen.
T) simulations
.

116

3.4

Simulation Results

ered and at

high
-

oxygen

partial

following

formulation

al. made the pressures. Second, Mizusaki et coefficient: diffusion surface for the

D09(l 9). By use of this formulation we obtain simulation results which are in qualitative agreement with the results obtained before with the difference that the pQ dependence of R~ vanishes at low temperatures (T < as experimentally observed by Mizusaki et al. 773 K (500C)) and high pQ
D0(9)
=
,

[45]. However, there


concentration

can

be

no

data found in the literature

concerning
of

the
Pt.

dependence of the surface diffusion coefficient Accordingly, the proposed formulation seems rather arbitrary.
Electrode

Oad

on

polarization. Fig. 3.20 shows simulation results for the IF(T|) behaviour at 973 K (700C) at low cathodic and anodic polarizations. The
results
can

be

directly compared
(see Fig.
our

with the simulations and the


8 in

experimental
There is

results of Mizusaki et al.

[47]

and

Fig.

11 in

[45]).

reported results. We find cathodic currents in the simulations at relatively high pQ of 10 Pa to 10 Pa. The reason for this can be found in the strong pQ dependence of the
agreement
between

simulations and

good limiting

Oad in the model M2. To improve the model, the rate constants for the adsorption and desorption should be taken as a function of the surface coverage. It is known from adsorption studies that the initial sticking coefficient of 02(g) on Pt surfaces may vary many orders of magnitude, depending on the Pt surface coverage (see e.g. [46,48]). The inset of Fig. 3.20 shows the JF(T|) relation at small overpotentials and compares with the behaviour we would obtain if the reaction was charge
equilibrium
concentration of

transfer controlled. A
these low low

large

difference between these the

curves

is

seen even

at

overpotentials. Evaluating

slope
.

of small

overpotentials will therefore reveal the electrode not the inverse charge-transfer resistance R~ Only if the reaction kinetics is charge transfer controlled, i.e. Rt R small signal dc analyses reveal Rt. The difference between the two curves is attributed to a concentration polariza tion which can be clearly seen in the Faradaic impedance which is shown
=

signal dc curves at conductivity R~ and

below.
More information about the rate

limiting process is obtained from the pQ dependence of the limiting-current I,. For the system Pt, 02(g) I YSZ at high cathodic overpotentials, pQ and pQ dependencies of I{ have bee found [9,
is

59,61]. The stronger dependence

generally attributed to gas mass transport limitation whereas the weaker dependence is attributed to a surface diffusion limitation. However, clear relationships become apparent only at oxygen par-

117

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.

3.21 shows the simulated

l_i

it

-0.1

-0.05

0.05

0.1

r|/V

Fig.

3.20

Simulated

JpOl) relationships
is

under different oxygen within the


.

partial

pressure condi
Pa

tions at 973 K

(700C).The pQ
at

given
Pa

figure.

The solid line shows the the


=

oretical Tafel behaviour at pQ

=10

The inset shows the results for pQ of 10 mV,


as

10

(real and Tafel behaviour) and


in EIS. From
a
=

dc

analysis

of the
R_
=

obtained:

Rt

10.5

Q-cm2,

usually employed small-signal data in the inset the following results are 29.9 Q-cm2. Compare these results with the impedance
overpotentials

small

spectra

in

Fig.

3.22 at the

same

conditions.

118

3.4

Simulation Results

explained

charge transfer resistance Rt decreases to very low values and the entire electrode polariza tion is caused by the surface diffusion of Oad and the adsorption of 02(g)Because the later two processes occur in parallel, a pQ dependence of
as

follows: at

high

cathodic

overpotentials,

the

Il(p0 )

is found. This is consistent with the simulation results for the R


as

(p0J

behaviour

shown above

is dominated
ence

by

the

Rt, (Fig. 3.16). Rp concentration polarization and

If

then the electrode reaction therefore


a

pQ

depend

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

porous electrodes. We would


electrodes where the Pt

expect

the described behaviour at Pt


in the order of

pattern

strip width is

(10.. .100)

pm, i.e. consid

erably larger than the Nernst diffusion layer width 8.


One

might expect that further information is obtained from the temperature dependence of the limiting current. The temperature dependence of I\(Pq ) is directly obtained from the data shown in Fig. 3.21. For the limiting behav
iour
at
=

low
64

Pq

we

find
a

an

average

apparent kj/mol
at

activation

energy

of

AH,.
of

kj/mol,

where

value of -76

is found at low

tempera

tures and the value decreases to -54


our

knowledge,

no

high temperatures. To the best corresponding experimental data are reported in the
kj/mol
must be from

literature
wise gas

(note that the results

non-porous electrodes, other

limiting process). By consideration of Eq. (3.29), and with kb > 0 it is seen that a rather complicated temperature dependence of I\(Pq ) results, where the activation energies of surface diffu sion, adsorption, and desorption have an influence, although an analytical
diffusion could be the
can not

expression
Electrode

be derived for

limiting case.

experimentally found that the impedance Z(ju)) in the complex plane exhibits as a single (depressed or Warburg-like) semi-circle at intermediate temperatures and at high pQ [15, 42,45,55,56, 61,62]. With decreasing pQ a second semi-circle generally appears [15,41]. There can no study be found where EIS spectra were recorded under a cathodic or anodic polarization of the cell. The interpreta tion of the spectia has been generally difficult and is further complicated by the presence of the double layer capacitance Cdl. As we have shown in the previous section, it is necessary to consider the Faradaic impedance ZF(jco) which can be obtained from the measured impedance Z(jco) by subtracting the double layer capacitance and the electrolyte resistance. In the following we will give both the Faradaic impedance and the impedance, assuming that
Impedances.
It has been often

119

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.

limiting-current behaviour of M2.The temperatures (K) are given within the figure. The same parameters as in Fig. 3.20 were used. The iF(T|) behaviour was simulated to -0.6 V and the corresponding current was taken as Zj. the inset shows the concentration gradient (surface coverage 9) of Oad near the tpb
3.21
=

Simulated cathodic

at T

973 K,

-0.6 V, and

pQi

10

Pa.

constant double

ture

layer capacitance Cdl dependent electrolyte resistance Re


a

of 20

pF/cm2,

as

well

as a

tempera

in series is

present.
we

To obtain

simulate

complete picture of the electrode behaviour at 973 K (700C) the frequency response at different overpotentials and compare ZF(r|)
behaviour.

the

Fig. 3.22 shows simulated EIS spectra for two different pQ at low cathodic overpotentials in the complex plane. It is readily seen that an interpretation of the impedance alone is difficult. In con
tiast, the information is contained within the Faradaic

results with the

impedance.

From the

120

3.4

Simulation Results

25
8/
^-

vN,806m

ZQ(o)

ZpOco)

20

n*

n=-o.5v3m^
Ik 2k

C!

15

3k

10

a)

Re(Z/2-cm2)

120
9m

Z(jW)

/28m/^

^^
Tl
=

Zp(jco)
A

-g80
a

/
0.5M

-0.5 V

_()

IM

8
*

Tl=-35mV

7 40

_^~

"--.

N^2
\

b)

0 0 50

V
1

-10 mV

\ 806m \

100

150

Re(Z/Q-cm2)

Fig.
The

3.22
same

Simulated

impedances
as
=

at T

973 K

(700C)

at

parameters

for the simulation of the

employed. Spectra at (a) pQ tials as given in the figure.

105

overpotentials n. JF(r|) curves in Fig. 3.20 were

different

Pa and

(b) pQ

103

Pa for different

overpoten

121

Implementation, Simulation,

and

Validation

knowledge of Rt can immediately

with respect to R

and the

shape

of the

impedance
,

arc,

we

infer the reaction mechanism. At


we

Rc

Rt)

and

find

Rt~ Rc (where that a competition exists between the charge trans high
pQ

fer process and the chemical processes. From the conclude that the surface diffusion process the
and

shape

of the

causes

ZF(jco)

understood

JF(r|) data at high pQ (Fig. 3.22 why the /F(r|) behaviour resembles a

Rc. From a and Fig. 3.20)

ZF(ju)) arc we comparison of


it
can

be well
over

Tafel behaviour. The

all kinetics is still influenced

by

the

relatively large charge

transfer resistance

Rt.

If the p0

is

lowered, the reaction kinetics is almost completely domi

by the surface diffusion process (Rt Rp). In both cases, the concen tration polarization increases with increasing cathodic overpotential, which can be readily explained with the decrease of Rt with cathodic overpotential (as long as Oad near the tpb is not too far from the equilibrium concentra
nated

tion).

Note that the values for

Rt

and R

obtained at

high

pQ

and

zero over-

potential (Fig. 3.22 a) are in full agreement with small-signal dc analysis in Fig. 3.20.
It
was

the values obtained from the

parallel process of 02(g) adsorption and Oad sur face diffusion was responsible for the limiting-current behaviour. This can be seen from the ZF(jco) at high cathodic overpotentials (see inset in Fig. 3.22). However, more information is obtained from a Bode plot of the ZF(jco) data and the slope of the log|ZF| versus log(u)) curve (Fig. 3.23). We have dis cussed some properties of frequency response data in Bode plot representa tion in more detail in part I of this publication [1]. With increasing cathodic overpotential the influence of the adsorption process can be seen in the high frequency part of the spectra: the w dependence of |ZF| changes from -1/2 to -1. This behaviour becomes more pronounced with decreasing temperatures. However, we believe that this behaviour is particular to the modelling of the

said above that the

adsorption process and that real electrodes should not show a first-order dependence of |ZF| at such high frequencies. Remember that the adsorption of 02(g) was assumed to occur directly from the gas phase on the Pt surface. Relatively high rate constants for the adsorption and desorption were chosen.
This the
causes

short relaxation times for this process which


It is well known that the

can

be observed in

spectra.
act

chemisorption

of oxygen

proceeds

via

one or more sors


as a

physisorbed
reservoir. A

precursor states
more

[63, 64]. Accordingly, these precur

refined model should include this

dynamic

behaviour

[33].

122

3.4

Simulation Results

a)

co/(2tc-s_1)

b)

co/(2rc-s

l)
and different cathodic overpo

Fig.

3.23

Simulated
=

impedances
Pa.

at T

973 K

(700C)

impedance ZF(jw) and the impedance Z(jto). (b) Phase angle of the corresponding data. Note the change of slope in the log[|ZF|] versus log(o)) plot from -1/2 towards -1 at high frequencies with increasing cathodic overpotential.

tentials.p02

10

(a) Magnitude of

the Faradaic

123

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 charge-transfer coefficient, P, and the forward electrochemical rate constant, k^q, are unknown. The remaining parameters were assumed to be known with high accuracy. Fig. 3.24 shows the sensitivity of |ZF| with respect to P and k^q. S(P) is relatively low compared to S(k\q). We may infer that the higher the frequency the better. However, at high frequencies the influence of the electrical double layer becomes dominant and ZF(jco) must be first obtained from Z(jco) raw data. This procedure generally introduces rela tively large errors in the high frequency part of the ZF(jco) data. Therefore, P can not be estimated accurately from EIS measurements. However, as shown above, P can be obtained from the dependence of the charge-transfer resistp, should be

30

26
^

(S

a
-

??,

to

0.4

C!
**^

u.
-

18

14

oV(27t-s_1)

Fig.

3.24
were

Sensitivity

of

IZpl
=

with respect to the unknown

parameters.The

simula

tions

obtained for T
is

973 K in oxygen

(cf.

simulations in used
to

Fig. 3.22a).
the

The

magni

tude

of

sensitivities

ZF(jco) S(P)

also shown.

Eq. (3.13)

was

calculate

individual

and

S(kl).

124

3.4

Simulation Results

ance,

Rt, on the oxygen partial pressure, pQ (cf. Fig. 3.4). k\q is accurately obtained from EIS measurements.
assumed
so

Once

is known,

This method works well for the considered system if, and

only if,

the remain
in real

ing parameters are well known (as we have


porous

far). However,

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

solid

electrolytes

must be

employed
a

instead of porous

seeks for the electrochemical rate constants. This allows to


to
a

/^b experimentally

certain value within

small range,

as

long

as

the

30

26

6
03

22

a
N

18

14

10l

101

w1

10J

10<

103

co/(2jc-s_1)

Fig.
w
=

3.25

Sensitivity

of

IZFI

with

respect
as

to the

length

of the

tpb

and the width of the 3.24


were

active area.The 10
nm.

same

parameters

for the simulations in

Fig.

used with

125

Implementation, Simulation,

and

Validation

microstructure remains stable at

high temperatures.

We are, therefore, left


area w.

with the

question

of how to obtain the width of the active

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

While

model. However, due to the low


w

sensitivity
nm

of

|ZF|

with

respect

to

(if

klc

const)

we a

can

obtain rather accurate estimates of

klc

from EIS

measurements if
area w.

value of

(1...10)

is assumed for the width of the active


we

This is close agreement with what

would

expect intuitively for


we

w.

Practical cal

identifiability.
we

In

part I of this publication

proved

the theoreti

identifiability

of the model parameters of model Ml and M2 with EIS.

However,

have shown above that the feature of

sensitivity

must

be also
are

considered.

Unfortunately, theoretical identifiability and high sensitivities


requirements
for
an

only

necessary

accurate
a

parameter

estimation. If

a corre can

lation between parameters exists, become

numerical parameter estimation

impossible as we show now. 105 Pa, and with the remain Let us produce ZF(jto) data at T 973 K, pQ ing parameters given in the appendix (Table 3.1). It is now the objective to estimate the unknown parameters from the generated data and the model M2, while different values for p [P, klc] should be used as starting guesses
= =

problem is well known from numerical optimization methods. We consider the weighted sum of squared terms (see appendix 3-A.4 for more mathematical and computer implemen
generation
were

than for the

of

ZF(jco)

used. This

tation

details)

126

3.4

Simulation Results

7 = 973 K

pO2=105Pa

^5ft^

4
^"N

lur

"X

\
'

\\
-

0
'

/
w
=

If

2
'

'

2 S

nm nm
nm
-

-A
1

/ / / / / // 1 / /
/

10

///

-8

1//
1

20

nm

0
12
i

a)
10
15

14
i

16

20

25

30

35

Re(Z/Qcmz)
-"-"T

^\IZFI
0.12
\ \ \

/
/ / /
-

30

26 E

20

nm

0.08
CO

^/ xv
\ \
'

22
-

CI
N

10 nm^^/

\ \

0.04

H
\ \

18

nm

__^~^*^

w
n nn

nm

's^
102
103
10< 103

14

10l

10'

0)/(27l-S_1)

Fig. 3.26 Sensitivity of IZFI with respect to w with under the (a) Zp shown in the complex plane for different values of w
text in at

condition from 2

w-klc
to 20

const.

the

figure).

The inset shows the


w.

different levels of

(- -) corresponds

high frequency part to IZpl at w 10 nm.


of
=

nm nm (see (b) Sensitivity of IZpl ZP

127

Implementation, Simulation,

and

Validation

Fig.

3.27

Correlation between

and

fclc.The parameters given

in

Table 3.1

were

used to

calculate/(p) (Eq. (3.32)).

The bold line denotes the minima of the function f(p).

fW
*

ih X<Zf(P> 0
*

rF|

zf(/>>

0)2

(3.32)

,-

ZF(i) denotes the generated data. Fig. 3.27 shows the function f(p) for this particular problem. There are a few things worth to note. First, the sensitivity of f(p) with respect to klc is considerably larger as to a (as already mentioned above). Second, there exists a strong correlation between a and klc which is reflected in the fact that the cost function f(p) exhibits a shallow minimum. Although the absolute minimum can be found numeri cally at P PN and A:lc fclcN for these noise free data, this is generally not the case for experimental (and therefore noisy) data. It becomes clear that the numerical estimates of a from EIS data may be completely wrong. Accord ingly, a must be obtained from different measurements than EIS measure ments, even if S(P) was high (but which is not the case as shown in Fig. 3.24). Once P is determined, fclc can be obtained accurately. We have shown that the electrode reaction of the Pt, 02(g) I YSZ system is dominated by surface diffusion of atomic oxygen species over a large range
where
= =

128

3.5

Summary

and

Conclusions

aV(2K-s-')

Fig.
sion

3.28

Sensitivity of IZpl with respect of Oad.See explanations in the text.

to the activation

energy of the surface diffu

of

operating

conditions.

Accordingly,

we

can

expect that the sensitivity of

|ZF|

with respect to the surface diffusion coefficient of


can

Oad, D,

is

high and,
can

therefore, its value


more,

be estimated

easily

from EIS measurements. Further

the

dependence
a

of D

on

the surface coverage of Pt with

Oad

be

obtained from shows the


It is
seen

series of measurements and of


is

parameter

estimations.

Fig.

3.28

sensitivity S(Ediii)

|ZF|

with respect to the activation energy of D,


at low

Ediff.

that

extremely high, in particular

frequencies.

3.5

Summary

and Conclusions

It has been the purpose of this paper to demonstrate the tation of


a

computer implemen

describing the oxygen reduction at interfaces between Pt and YSZ. The simulated steady-state and small-signal behaviour have been compared with reported data. A procedure for the identification of the rate constants of the considered model has been attempted.

kinetic model

129

Implementation, Simulation,

and

Validation

Although

the considered Pt,

Oz(g)

I YSZ

seems

to be

quite

well understood

electrode/solid electiolyte system, the actual


of the reaction mechanism is the theoretical

by far not a

procedure for the identification straightforward and easy task. From


unique
identifi
to be

analysis we

determined the conditions for the

ability of the unknown parameters which proved ness for the practical identifiability.
We suggest the
ters

only of limited useful


the model parame

following procedure for the estimation of of model M2 describing the Pt, 02(g) I YSZ system:
(i)
Determine the
versus

charge

transfer coefficient The

P from log(R^ )
values should
measurements

log(pQ ) plots

at -1000 K.

be obtained from electrochemical

Rt(pQ ) impedance

by subtracting
(ii)

the double

layer capacitance.
of the

charge transfer reac tion, AHci*, from an ln[f0(po *)] versus 1/T plot. Note that i0(po *) is accurately obtained from Rt data which can be enthalpy
obtained
as
-

Determine the activation

described

in

(i).

The

relation

i0

(RT)/(2F)

Rj"

can

be used to obtain

z'0.

(iii)

adsorption enthalpy AHad for high surface coverages from a ln(pG *) versus 1/T plot either at high Pq and low T (high surface coverage), or at low pG and high T (low surface coverage). Note that a large amount
of data is available in the literature for

Determine the oxygen

Ead

and

Edes,

as

well

asfcadand/cdes.
(iv)
From electrode with well known

geometry (e.g. strip elec

length of tpb, no porosity, and known Pt surface area), obtain impedance spectra. Use the parameter
estimates obtained in

trodes with well known

(i)

to

(iii) and

estimate

klc

with the

numerical method described.

(v)

Estimate

D(Oad)

and

Ed

from EIS measurements of elec

tiodes described in

(iv).
data and model

It is clear that

validation of

should be carried out

experimental continuously.

parameters

130

References

Model M2 accounts for the

adsorption

and

desorption

of oxygen
a

on

the Pt

surface, the surface diffusion of atomic oxygen, and for


fer reaction
near

two-electron trans

the

tpb. However,

much information is available about the be included in of


a

interaction between

refined model.

02(g) and Pt surfaces which could First, the adsorption/desorption dynamics


more

02(g)

on

the Pt

surface should be modelled in several orders of

detail,

as

the kinetic constants may vary

magnitude over

the pQ

range considered. To
diffusion

fully describe
diffusion and

the behaviour of porous electrodes, gas Knudsen

mass

(binary
can

diffusion) should be taken

into account. This

be

easily

accom

plished

with the numerical method

presented

in this paper.

centration

dependence

of the surface diffusion coefficient

Finally, the con of Oad could be

accounted for in the model.

Acknowledgments.

The financial

support from the Swiss Department of Energy, Trans

portation,
thank sions. In

and Telecommunication is

gratefully acknowledged.

The authors wish to

present colleagues

in the Chair of Nonmetallic Materials for many useful discus


to A.

particular we are indebted Matlab/Simulink code examples.

Bieberle and R. Stadler for

carefully testing the

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C. G.

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La2Zr207 formation
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the characteristics of the oxygen electrode reaction J. Electroanal. Chem. Interf. Chem., 57:165-177,1974.

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Giir, I. D. Raistrick, and R. A. Huggins. Steady-state D-C polarization char acteristics of the 02, Pt/stabilized zirconia interface. /. Electrochem. Soc, 127:26202628,1980.

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Braunshtein, D. S. Tannhauser, and I. Riess. Diffusion-limited charge transport platinum electrodes on doped Ce02. /. Electrochem. Soc, 128:82-89,1981.

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J. Olmer. Comparison of materials as oxygen catalytic electrodes zirconia electrolyte. /. Electrochem. Soc, 129:436-443,1982.
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Luntz, M. D. Williams, and D. S. Bethune. The sticking of 02 Phys., 89:4381^395,1988.

on a

Pt(ll 1)

sur

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G. F.

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135

Implementation, Simulation,

and

Validation

Appendix
3-A.l
Reaction Model Constants and Parameters

Table 3.1

Parameters and Constants used in Model Ml and M2

Quantities

Symbols
area

Values

Units

Ref.

Apparent

electrode

10-4
0.7

m2
1

Electrolyte

coverage

^cov 'char
L

[1] [1] [1]

Characteristic

length

pm pm
nm

Electrode thickness
Extension of

20 10

tpb

Azx D0

Surface diffusion constant


Activation energy of surface

4.65 155

10-*

m2/s
kj/mol

[15] [52]

diffusion Number of surface sites for


atomic oxygen

d
N0
v*d

1.6603

lO"5

mol/m2
s"1

[63]

Frequency factor of oxygen adsorption Frequency factor desorption


of oxygen

109 io12
No

[67]

vdes

m2/(mo-s)

[67]

Activation energy of oxygen

adsorption
Activation energy of oxygen

Ead
Edes

33

kj/mol

[48]

200

kj/mol

[48]

desorption
Concentration of oxygen vacancies in YSZ

[V0]

4.65

103 104

mol/m3 mol/m3
kj/mol [9,10]

Concentration of oxygen ions in YSZ


Activation energy of for

[Oc]

4.45

ward electrochemical
tion

reac

E\

125

136

Appendix

Table 3.1

Parameters and Constants used in Model Ml and M2

Quantities
Activation energy of back

Symbols

Values
135

Units

Ref.

ward electrochemical
tion

reac

El
*lc
p
T

kj/mol

[9,10]

Forward electrochemical
rate constant

2-106
0.62

m3/(smol)
1

Charge

transfer coefficient

Temperature

650... 1200 1 to

Oxygen partial

pressure

Po2

105

Pa

3-A.2

Determination of

Cdl by

Potential

Step Chronoamperometry

impedance of a Pt, 02(g) I YSZ system can be reasonably well described by the equivalent circuit shown in Fig. 3.3d. The only difference to the equivalent circuit of Fig. 3.3 c is that we assume that the Faradaic impedance ZF(jco) can be approximated by a conventional parallel circuit of a capacitance C and a concentration resistance Rc. From a node analysis (see, for example, any textbook about electrical engineering) of this circuit we obtain the following state-space description for the circuit in Fig. 3.3 d
Let
us assume

that the electrochemical

-1/Cdl(l/Re + 1/Rt)
l/(CRt)

l/(CdlRt)
-1/C(l/Rt + 1/Rc)

[l/(CdIRe) 0] [-1/Re o]
[1/RJ

(3-A2.1)

with

x(t)

Uix(t)

and where T denotes vector

m2(o]

"o

"(f), and y(0

l/Re(u(t)-ul(t)),
are

transposition.

Two relaxation times tx and x2

137

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 Q-cm2 and C is typically in the order of 1 mFcm"2. The values for Rt, Re, and Cdj are at least one order of magnitude lower. This makes a simplification to a certain extent of the expression for t^ possible. In addition, if Rt Re we can finally derive
obtained from the

eigenvalues

of the matrix A

(use

Cj]RRt

x'a^fLet
us now

(3"A2-2)

analyse the relative error we make in the estimation of Cdl when experimental potential step chronoamperometry data are evaluated with the expression t* ReCdl instead of the expression derived above (note that the exact value for x of the equivalent circuit shown in Fig. 3.3a is easily obtained from a node analysis as x (CdlReRt)/(Re + Rt) which corresponds to Eq. (3-A2.2)). The result is shown in Fig. 3-A2.1 for C 1 mF, Rc 100 Q, Cdi 1 pF, and Re 10 Q. It is seen that the expression x* ReCdl is only a good approximation for x if Rt > (5... 10) Re. If Rt < Re, the values for Cdl are estimated too low if the step response data are evaluated with the expression for x* instead of x. In addition, the expression derived above for Xj (Eq. (3A2.2)) is a very good approximation down to very low values of Rt. We conclude that the true values for Cdi of Pt/YSZ interfaces can be obtained from potential step chronoamperometry experiments if the current decay curves are evaluated with Eq. (3-A2.2) if Rt Re, which is generally ful filled at low temperatures. However, numerical estimates of Rt (and Re) are required. But, as we show in the main text, Rt is related with the exchange current density i0 which itself can be obtained from a Tafel analysis. Unfortu nately, a Tafel analysis only gives reasonable values for /0 if the reaction is charge-transfer controlled, which is certainly not the case for the Pt, 02(g) I YSZ system at temperatures below 1000 K. On the other hand, at high temperatures the reaction would be charge-transfer controlled which implies that Rt R (i.e. Rc 0), thus making a simplification of the equation describing the relaxation time impossible. We propose to employ the method of Berthier et al. [39] for estimating Cdl from impedance data, as demon
=

strated in the text.

138

Appendix

0i
-1

logctyjy
potential step responses of equivalent circuits.The ratio x/x* is shown (relative error). Only if Rt > Re, the error is below a factor of 2. The fol lowing parameters were taken (see equivalent circuit of Fig. 3.3d): Re 10 Q, Rt 10 Q, 0.1 ms and X 0.045 ms. The rela Rc 100 Q, Cdl 10 pF, C 1.5 mF. We obtain X*
Fig.
3-A2.1

Comparison

of

tive

error

is

a
a

factor of ~2 for these parameters (see


+10 mV

figure).

The inset shows the current

response to

potential step input.

3-A.3

Implementation
In this

and Simulations of Model Ml

General.

example

the

implementation and

simulations of model Ml

Only a basic familiarity with the pro grams is assumed which can be obtained by working through the introduc tory chapters of the handbooks [3, 4]. A very good introduction to block diagrams can be found in the textbook from Franklin [65]. The reader is encouraged to try the implementation for himself and to experiment with the model. All the examples shown below can be worked through with the stu
dent version of the software

in Simulink and in Matlab is shown.

(Matlab:
are

version 4.2; Simulink: version

1.3). The
3-A.l
concern

parameters used for simulations


and evaluated at T
=

taken from Table 3.1 in


=

appendix
need to

1000 K and pQ about the parameters for the moment.

1 atm. There is

no

139

Implementation, Simulation,

and

Validation

Fig.

3-A3.1

Simulink block

diagram

for the

adsorption/desorption dynamics.The
can

initial value of the

integrator

block is set to xO. The simulation


an

be followed within

the Simulink window


to

any connection

by connecting line (although it

Auto-Scale

will be most

Graph from the Sinks Block Library interesting to follow x (t)). Set the

parameters

in the Simulation-Parameters... sub-menu and start the simulation. This pos

sibility

is convenient in the

early stage

of model

testing and debugging.

Adsorption dynamics.

First, the

implemented
parameters

in

block
as

adsorption and desorption dynamics is diagram (Fig. 3-A3.1; filename: simadsl.m). The

are

defined

p02
NO kad
=

1;
1.6e-5;

in

units

of

(10^5

Pa)

1.8888e7;
=

kdes

4.3007e6;

The initial value of

is set to xO

0.65. The rk45

(Runge-Kutta

fifth

order) integration methods


tol
=

is used with

le-3;
=

minstep

le-6;

maxstep

le-3;

options
xO
=

[tol,

minstep,

maxstep];

0.65;
=

[t,x]

rk45('simadsl', plot(t,x),

1.5e-2,

xO,

options);
ylabel('x')

subplot(221),

xlabel('t/s'),

140

Appendix

0.68

200
^v
/
'

0.67

Is]
N

o5 100
CO

^^s.

0.66

'

n
0

0.65 0.01

4r\n

200

400

Real(Z,Zf)
x10" 10

110*
o
-

3"

o
o

g-10*
10"
-0.2

-0.1 etaA/

0.1

-0.2

0.2

voltage/V

Fig.
ters

3-A3.2

Simulation results for model Ml at reference conditions.The


were

parame
sub

from Table3.1

evaluated

at

1000

and p02
a

atm.

plot (221)

shows the time response of x(t)

for

small deviation from the

equilibrium
ance

value X0. subplot (222) shows the Faradaic


=

impedance and
V

the

imped

A (larger semicircle) double layer capacitance of Cdl 10e-6 wasassumed. subplot (223 ) showsthe charge transfer resistance Rt and the polarization resistance Rp as a function of the overpotential eta. subplot (224) shows the current-voltage behaviour of Ml.
at eta

and eta

-0.8

(smaller semicircle).

The

subplot(221)
Graph

of

Fig.

3-A3.2 shows the time


can can

dependence

of the surface
on

concentration. The simulation

also be followed within Simulink be found in the Sinks Block

the The

Auto-Scale

block which
can

Library.

integration parameters
submenu.

be set

directly

in the Simulation.Parameters...

The surface concentration attains its

equilibrium value

X0

K*sqrt(p02)/(1+K*sqrt(p02))

141

Implementation, Simulation,

and

Validation

where

sqrt(kad/kdes)
The relaxation time for small

(cf. part I).


tau
=

perturbations

is

given by [66]

l/(4*kdes*X0+kad).

Note that the result for the relaxation time is based the

on

the

assumption

that

perturbation

is small. If the

starting

value is far from the

equilibrium

value, the simulated values for the relaxation time will deviate from the

small-signal value.
Electrochemical reaction.
We
now

include the electrochemical reaction.


Simulink block

diagram (filename: simmodla.m). See the main text and Table 3.1 for a detailed description of kf, kb and the remaining parameters. Non-linearities are due to the exponential dependence of kf and kb on the overpotential. The Fen block in the Nonlin ear Block Library is best used for this purpose. Note that the eta (t) block corresponds to an inport block and that the IF(t) block corresponds to an outport block from the Connections Block Library. From this block diagram we can easily obtain the Faradaic admittance YF(jco) at equilibrium potential.
Fig.
3-A3.3

shows the

corresponding

We define the

following
A
=

constants

ac

0.62;

2.73e-7;

8.314;

1000;

96487;

f kf

F/(R*T);
=

2.7474e3;

kb

5.7577e3;

Note that the electrochemical rate constants

can

not be chosen

independently

(cf. part I).


is set to
a

It is

good

idea to check the time

different value than the

dependent behaviour now. If xO equilibrium one, the system will relax


a

towards the decrease to

equilibrium

state

within

short time. The current should


If

(or very low values) due to the constraint linearized state-space model (SSM) is obtained as follows:
zero

(Eeq)

0. The

XO

K*sqrt(p02)/(1+K*sqrt(p02))
=

[a,b,c,d]

linmod('simmodla',

XO,

0);

142

Appendix

eta(t)

Fig.

3-A3.3

Simulink block

diagram

of Ml in order to extract linearized state-space

models.The

integrator block

is set either to 0

(zero)

or

to XO.

where the
is

a,

b,
to

c, d

quadruple denotes
that XO is
was

the linearized state-space matrices. It


as an

important

recognize

given

argument

to

the function
zero

linmod. If

no

argument

given,
for
a

the function linmod would take


a

for

the surface concentration which would result in

wrong SSM. See also the

on-line

help (help linmod) impedance form,

description

of the purpose of the function

and its arguments. Note that than in

we

have the SSM in admittance form rather


a

because "simmodla" defines

model of the form

YF(s)-r)(s) where s is the Laplace variable, ri(s) is the Laplace transform of the input, IF(s) is the Laplace transform of the output, and YF(s) is the Laplace transform of the Faradaic admittance.
IF(s)
=

We continue with the transfer function to obtain the electrochemical


ance

(we

use

deliberately
as

"electrochemical

ance" because,

it should have become

imped impedance" and not just "imped clear, we could analyse different

143

Implementation, Simulation,

and

Validation

input/output relationships (e.g. current as output))


[numYf,denYf]
w
= =

the oxygen

partial

pressure

as

input

and the

ss2tf(a,b,c,d);

logspace(-l,5,100);
=

[reZf,imZf]
Zf
=

nyquist(denYf,numYf,w);

reZf

j*imZf;
Note that

where Zf denotes the Faradaic

impedance.

we

changed

the varia

bles for denYf and numYf in the

input of the nyquist function to obtain the result for the impedance (see help nyquist). A simple calculation reveals the electrochemical impedance Z including a double layer capacitance Cdl
an

and

electrolyte resistance Re
=

Cdl
w
=

10e-6;

Re

10;
the
Z

w';%

transpose
+

frequency
=

vector!

j*w*Cdl

l./Zf;

Re

l./Y;

Let

us

plot the results (Fig. 3-A3.2)


plot(real(Zf)
'-');
500 -100
+

subplot(222),
real(Z),
axis

Re,

-imag(Zf),

'',...

-imag(Z),
axis([0

equal;

300]),...

xlabel('Real(Z,Zf)'),

...

ylabel('-imag(Z,Zf)'),

grid;

The low
ance,

frequency intercept of Zf

and

correspond to the polarization resist

Rp

l/(d-c/a*b),

the

high frequency intercept

of zf

corresponds

to the

charge

transfer resist

ance,

Rt

1/d,

and the
ance,

high frequency intercept of z corresponds to the electrolyte resist Re (see part I of this publication for further details). It is seen that the

144

Appendix

reaction kinetics is almost

entirely

controlled

by

the

adsorption

of oxygen.

The

charge transfer resistance is low compared with the polarization resist ance. It is generally a good idea to validate the simulations with analytical results. In part I of this publications we give the linearized SSM in analytical
form

al= bl=
cl=

-4*kad*pO2*N0*(l-X0)
2*ac*f*kf*X0
+

4*kdes*N0*X0

kf-

kb;

2*(l-ac)*f*kb*(l-X0);

-2*N0*F*A*(kb+kf);

dl=

2*N0*F*A*(2*(l-ac)*f*kb*(l-X0)

2*ac*f*kf*X0);

which Let
us

are

equal to the a, b,

c, d

matrices obtained with the function linmod.


a

know obtain simulations at

cathodic

overpotential

of

eta

-0.08.

With

eta

-0.08;
=

[X,U,Y]

trim('simmodla',
=

XO,

eta,

[
X,

],
U)
;

],

[1],

]);

[a2,b2,c2,d2]

linmod('simmodla',

and with the

same

calculations
an

as

in the

equilibrium

case are

we

obtain the

impedances
procedure

zf and z at

overpotential

of -80 mV which
hold

also shown in

subplot(222) of
as

Fig.

3-A3.2

(use subplot (222),


are a

on, and the same

things which are noteworthy about these three lines of Matlab code. If an overpotential is imposed at the input, the system state will change to a new steady state. The value for the state variable x will be lower than the equilibrium value X0 (cathodic overpo tential). The corresponding current is given by Y. The output of trim is used as the input of the function 1 inmod which give the linearized SSM at the new operating point. Note that Rp decreases with increasing eta. However, increasing eta to much higher values will increase Rp drastically because the steady-state values for X decrease. We find that the reaction is limited by the rate of adsorption. If we wanted to obtain simulations at overpotentials with the analytical
in the first

case). There

few

model,
ble
x

we

had to substitute the state variable X0 with the actual state varia
on

analytical expressions of the state-space matrices. This requires either an analytical solution of the mass balance equa tion, or that we solve this equation numerically. This can be done with the
eta)
constr

(depending

in the

Simulink function

(or, if available, with the function

f solve

from

145

Implementation, Simulation,

and

Validation

the

Optimization Toolbox).

We

see

that it is much

more

convenient to find the

steady-state point with the function trim. The function constr may solve a number of different problems and it will be needed for parameter estimation (fitting). The function trim makes use of constr. It is worth to know the abilities and limitations of trim and constr in some depth.
Let
us

consider the behaviour of


run

Rt

and Rp

over a

range of

overpotentials

from 0.2 V to 0.1 V. We

the

following commands:

etaList
for
m
=

[-0.2:0.04:0.1];

1:length(etaList),
etaList(m);

eta

[X(m),U(m),Y(m)]=trim('simmodla',x0,eta,[],[],...
[1],[]); [a2(m),b2(m),c2(m),d2(m)]
X(m), Rt(m) U(m));
=
=

1inmod('simmodla',

...

l/d2(m); l/(d2(m)-c2(m)/a2(m)*b2(m));

Rp(m)
end

Occasionally,

the

following warning message may appear


of

Maximum number

iterations

exceeded

increase OPTIONS(14)

In this

case

trim has not found


more

solution after

default number of iterations


and the function

(options (14)). For

details about the


or

options vector

trim, refer to the manuals

the on-line
that any

help (help

foptions; help
should be taken
The results

trim). We would like

to

point out

warning message

seriously and the reason for it should are finally plotted in a semilogy plot
subplot(223),

be found

(and eliminated).

semilogy(etaList,
grid

Rp,

'o',

...

etaList,Rt,'*'),
xlabeK'eta/V),

ylabel('(Rp,Rt)/Ohm')

exponential dependence of Rt on eta is readily seen. Finally, we look at the steady-state current-voltage curve of model Ml. All blocks in the model simmodla are selected and grouped. A Repeating

where the

146

Appendix

m
eta(t )
Sut>systern

IF">

eta

Fig.

3-A3.4

Simulink block

diagram

of Ml for simulation of

current-voltage

behav

iour.The

port is

Subsystem contains the block diagram given in Fig. needed to plot the data in an I (U) diagram.

3-A3.3. The second out-

Sequence

block from the Sources Block

Library

is used

as

input

and

second

outport is used for the feed-through of the input (cf. Fig. 3-A3.4; filename: simmodlb.m). The vector [ 0 dt 2*dt 3*dt 4*dt] is used as time value
and

[0

-du

du

0] is used

as

output value
is almost

in the

Repeating Sequence
con

block. We

scan

with 6 mV/s

(which

zero

for the system under

sideration).

dt

100;

du
=

0.3;

TF

4*dt;
TF,

[T1,X1,Y1] [le-3,
If
=

gear('simmodlb',
TF/20]);
=

X0,

...

TF/1000,
V

Yl(:,l);

Yl(:,2);

subplot(224),

plot(V,If),

grid

The results

can

be found in subplot (224) of

ing
The

cathodic and anodic behaviour is found

Fig. 3-A3.4. Note that a limit at relatively low overpotentials.

step response
we

to

an

in 3-A.2. Because Cdl

potential step at the input can be simulated as shown and Re play a significant role in the time-dependent
I-V
curve

behaviour

must

include them in the model.

We learn from the EIS

spectra and the

that further processes, not


must

just

the dissociative oxygen

adsorption

near

the

tpb,

play

significant

role in the towards

supply of atomic oxygen. Surface diffusion of atomic oxygen the tpb must be taken into account when investigating the kinetics of
gas electrodes.

high temperature oxygen

147

Implementation, Simulation,

and

Validation

3-A.4

Implementation and Simulations


In this

of Model M2

appendix we present the implementation of model M2 in Matlab and Simulink. Special emphasis is given on the implementation of the mass transport phenomena in Simulink. Note that the full version of Simulink is required to perform the simulations (the student version is limited to 40
General. blocks per

model). The parameters used for the simulations

are

taken from
=

Table 3.1 of

appendix

3-A.l and evaluated at T


on a

973 K and

p0z

103

Pa.

Matlab version 5.1 and Simulink version 2.1

SPARCstation 5

operating

under Solaris 2.5.1

were

used for the simulations.

Programme
ters

initialization.

We first define the model constants and parame

(see also appendix 3-A.l).


=

Aelectrode
Acov

le-4;

% %

apparent

electrode

area

=0.7;
=

electrolyte

coverage

Lchar

2e-6;

characteristic
*

length
%

tpb
R
F
=

4*Aelectrode/Lchar
%
% % % % % %

sqrt(1-Acov);
constant constant
constant

Eq.

(2-A2.2)

8.314; 96487;
=

gas

Faraday Avogadro

Na T
=

6.023e23; 973;
=

temperature
in units
of

in

units

of

p02
Voo

le-2; 4.65e3;
4.45e4;

(10^5

Pa)

oxygen oxygen

vaccancy

concentration

Oox

ion

concentration

The

penetration depth
=

8 is obtained

as

described in subsection 3.3.2:

DO

4.65e-4;
=

surface

diffusion constant
energy

Ediff
D
=

155e3;

activation
surface

D0*exp(-Ediff/(R*T));%
=

diffusion

coefficient

wmax

exp(21.11-14150/T);
wmax*(p02)A(1/2);% cf.
=

Wmax

Fig.

3.2

delta

6*2/sqrt(pi)*1/(sqrt(Wmax/(2*D)));

Having determined the penetration depth we can divide 8 in compartments of increasing size according to a geometric series (note that we fix the width of the tpb compartment to 10 nm):

148

Appendix

dzl

10e-9; 2;

% % % % %

width

of

tpb compartment
guess

qO
n
=

starting
number
of

10;
=

compartments;

dzl
A
=

10e-9;

width active

of

tpb compartment
around

dzl*tpb;

area

tpb

fzero('compart',

qO,...
%

[],[],dzl,delta,n);
dz for

find

series
of

factor

=[];
k=l:n,
=

width

compartments

dz(k)
end

dzl*q"(k-l);

where

'compart'
f

is

small M-file called compart.m:

function f
=

compart(x,dxl,delta,n)
-

dzl/delta

(1-x)/(l-xAn);

The

midpoints

of the compartments

are

obtained from:

for

pp=l:length(dz),
=

Zaxis(pp)
end

sum(dz(1:pp-l))

dz(pp)/2;

and the time constants for surface diffusion

(Eq. (3.9))

are

obtained

as

Tdiff

dz.A2./(2*D);

We continue with the constants for the

adsorption and desorption:


of

NO

Iel9/Na;
=

%
%

number

adsorption sites
of

nadO ndesO
Ead
=

le9;
=

freq.

factor
factor

adsorption desorption
for for

2el2/N0;

% % % %

freq.

of

33e3;
=

activation activation
activation

energy

adsorption desorption

Edes
DH
=

200e3;

energy

l/2*(Edes-Ead);

enthalpy

We

now

determine the electrochemical

quantities:

149

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));

Note that the backward chemical rate constant k-

(klbchem)

must be

expressed in terms of the forward chemical rate constant klc (klf Chem). This must be accomplished via Eq. (2.62). The equlibrium potential is obtained as follows (cf. Eq. (2.59)):
EeqT
=

1/(2*ff)*log(klfChem/klbChem*...

exp(-(Elf-Elb)/(R*T))*Voo/Oox*K);
EeqP
=

l/(4*ff)*log(p02);
EeqT
+

Eeq

EeqP;

and

finally (cf. Eq. (2.74)):


=

klfEq
klbEq

klfChem*exp(-Elf/(R*T))*exp(-2*ac*ff*Eeq); klbChem*exp(-Elb/(R*T))*exp(2*(1-ac)*ff*Eeq);

We

finally

add

some

electrolyte
one

resistance

(thickness: 0.5

mm; area: 1

cm2)
to

and further

assume

that

half of the

electrolyte

thickness is

contributing

the

electrolyte
sigma
Re
= =

resistance

(three-terminal measurement):

1.63e2*exp((-0.78*1.602e-19*Na)/(R*T))*le2;
*

0.5

l/sigma*0.5e-3/le-4;

150

Appendix

At

zero

current the surface

coverage is

given by (cf. Eq. (2.58)):

xO
x
=

K*sqrt(p02)/(1+K*sqrt(p02));
ones(n,1)*x0;
%

surface

concentration vector

The last command generates

vector of

length equal

to the

number of

com

partments. Under zero current conditions there will be no concentration gra dient, therefore, all components of the vector x will be equal.
It is

generally useful
parameters
are

to

keep

all these parameters and constants within

dif

ferent parameter M-file, except the temperature and oxygen

partial

pressure.

The

loaded into the

workspace

from within the main program

where

appropriate.
diagram.
In

Simulink block

Eqs. (3.10)

to

(3.12) the

mass

balances

were

given
block

for the various

diagram

of Ml

compartments. We start our considerations with the (cf. Fig. 3-A3.3). The block diagram of the tpb compart

ment of M2 is obtained

in

Eq. (3.10)).
are

The

by adding the blocks for surface diffusion (last term resulting diagram is shown in Fig. 3-A4.1. Note how we
con

added the terms for surface diffusion and that the electrochemical rate
stants

defined
were

slightly

different than in

Fig.

3-A3.3. In Ml the results for

kf and kb

obtained from:

kf

klfEq*Voo;

kb

klbEq*0ox;

Using
as

1000

Kandp02

we

obtain the

same

results for kf and kb

appendix 3-A.3. Note also that the initial value of the integrator block must be set correctly, this is best accomplished by introducing a vector x of appropriate length (equal to number of compartments) and setting the initial
in

conditions of each individual

compartment

to

(i). The

same

time constants of the surface diffusion process

(compare

the

applies to the multiplication

block with 1 / Tdi f f

(1)).

Similarly we obtain the block diagrams for the other compartments. The complete block diagram for M2 is obtained by packing every compartment into a subsystem and by connecting these subsystems appropriately. Fig. 3A4.2 shows an example with four compartments and the notation introduced in Eqs. (3.10) to (3.12). The entire block diagram can be easily extended to
more

than four

compartments by copying and pasting


it with the

an

intermediate sub

system and connecting

remaining part.

Note that the initial condi-

151

Implementation, Simulation,

and

Validation

Oad(1)

Oad(2)ad(2)

l*^*"^

eta(t)

Fig.

3-A4.1

Simulink block from Ml with

diagram

for the

tpb compartment
is the

of M2.We

used

the

block

diagram

process
IF

(marked

(Fig. 3-A3.3 ) and added dropped shadows), eta(t)


is fed into this

the blocks for the surface diffusion

system input quantity and


atoms in Oad (1) is fed into com-

(t) is the

system output quantity. The concentration of adsorbed oxygen


two

compartment patment
two.

(Oad (2))

compartment and

Oad(3)

Oad(2)

%
oo

Oad(4)

Oad(1)

>
i=3

Oad(3)

>
i=2

Oad(2)

eta(t)

>
tpb

IF(t)

Fig.
tem

3-A4.2

Simulink block
to the block

corresponds

diagram of M2 with four compartments.The tpb subsys diagram shown in Fig. 3-A4.2.

152

Appendix

tions of the

integrator
for every

blocks and the 1/Tdiff (i)

blocks must be set

appropriately

subsystem. For clarity the block diagram of subsys tem 2 is given in Fig. 3-A4.3. Obviously, only the blocks representing the sur face diffusion process and the adsorption/desorption process are present.
The initial condition for the
stant for the surface

integrator

block is set to

(2) and the time


we

con

diffusion is set to Tdif f (2)

(note how

defined the

vector of Tdif f).

Simulations. Simulink block under the


can

In order to be able to

run

simulations of M2

we save

create

diagram
mode 12

with ten
.

(n

10) compartments. We

this file 3.22b

name

m.

We show in detail how the results from

Fig.

be obtained.

We

begin
T

with the Faradaic


=

impedance
0.01

at zero

overpotential (note

that

we

defined

973andp02

above):
0);

[a,b,c,d]=linmod('model2',
[numYf,denYf]
w
=

x,

ss2tf(a,b,c,d);
w
=

logspace(-l,5,100);
=

w'

[reZf,imZf]
Zf
Y
= =

nyquist(denYf,numYf,w);
Cdl
Z
=
=

reZf

j*imZf;
+

20e-6;
Re
+

j*w*Cdl

l./Zf;

l./Y;

Oad(2) Oad(1)

Oad(3)

Fig.

3-A4.3

Simulink block

main text for further

diagram explanations.

for

compartment

two of M2

(subsystem).See

153

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
=

which should value


Rp
=

give

the

curve

shown in
resistance

Fig.

0. Note that the

for

the

polarization
973andp02
=

(Rp

l/dcgain(a,b,c,d)

of
in

82.52 should also be in


=

agreement with the simulation results given


0.01.
a

Fig.
It is
eta

3.16forT
more

interesting
to the

to consider

situation where
we can

cathodic

overpotential

is

imposed

system.

Note that

not

simply repeat the calcula


x,

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


x

eta), because

does not contain the actual

the

steady-state steady-state equilibrium point:


=

values. We first have to determine

eta

-0.035;
=

as

in

Fig.

3.22

options(2)

le-6;

options(4)=le-8; options(10)
while
=

le3;

xtemp
>=

x;

options(10)

100,

options(14)=100;

[X,U,Y,DX,options]=trim('model2',...
xtemp,eta, [],[], [1],[],[],[],options); xtemp
end
=

X*(l+eta*randn(l));

Type

help

f options to

get

more

information about the options. We

use

the while within


tor
a

loop

because the function trim does not

always

find

solution
vec

reasonable number of iterations. The result of trim is the state

X, the

input u

and

the output

Y.

Check these results

by typing:

x
=

0.1151 0.1202 0.2165


0.2141

0.1278 0.1388

154

3.5

Summary

and

Conclusions

0.1536
0.1718 0.1907 0.2059

U
=

-0.035

Y
=

-3.2038e-04

input overpotential of -35 mV and that Y cor responds to an output current of -0.32 mA/cm2. The sort order of the X vector
Note that
u

corresponds

to the

seems

somewhat

strange,

but the necessary information


as

can

be obtained

from the variable info which is obtained

follows:

>>

[str,xo,info]
info
'

model2;

>>

model2/Subsysteml/Oad'

'mode12/Subsys tem2/Oad' 'model2/SubsystemlO/Oad' 'mode12/Subsystem9/Oad'

'model2/Subsystem3/Oad'
'model2/Subsystem4/Oad'

'model2/Subsystem5/Oad' 'model2/Subsystem6/Oad' 'mode12/Subsys tem7/Oad' 'mode12/Subsys tem8/Oad'

This order is

obviously

in

agreement with the order of

X.

The concentration

profile

of adsorbed oxygen is

easily

obtained with:

plot(Zaxis,

sort(X));

We

can now

obtain the linearized SSM

as

follows:

[al,bl,cl,dl]=linmod('model2',

X,

eta);

155

Implementation, Simulation,

and

Validation

Note that not the initial values within the

integrator
x

blocks

are

used

by

the

function linmod, but that the state vector


are

is evaluated. The initial values

contained within the vector

to

plot

the results.

procedure as above can be used Compare again with the curves shown in Fig. 3.22.
xo.

The

same

Similarly, current-voltage simulations can be obtained as described in appen dix 3-A.3. Limiting currents are determined with trim using high cathodic overpotentials (cf. Fig. 3.21).

156

Part

III

The Interface between

La0.85Sr0.15Mnt/3+5

and

Yttria-Stabilized Zirconia

158

Chapter

Lanthanum Zirconate

Formation

and

Oxygen

Reduction Kinetics

Abstract

growth of lanthanum zirconate (LZO) between (001) single crystals of 9.5 mol% Y203-stabiUzed Zr02 (YSZ) and 0.95... 1.10) perovskites were porous La085Sro.i5Mny03g (y investigated. The perovskites were screen-printed on the solid electrolyte and sintered in air at 1373 K for short periods. High
=

Nucleation and

resolution

transmission

electron

microscopy, electrochemical
force

impedance spectroscopy, and atomic employed for interface characterization.


tration in the

microscopy

were

The manganese

concen

perovskite

affect the onset of nucleation and the

growth
LZO

rate

of lanthanum zirconate. Excess lanthanum oxide

within the

perovskite reacts immediately with YSZ to form dense layers. Layer growth kinetics is controlled by bulk diffusion perovskite
leeds to the reductive forma

of cations. Stoichiometric

cathode/electrolyte interface after a few minutes of sintering. The A-site deficient perovskite is char acterized by the reductive dissolution of Mn into YSZ in the early

tion of cubic LZO islands at the

*)

Submitted to Solid State Ionics.

La2Zr207

Formation

and

02

Reduction Kinetics

sintering stage

and

by

pronounced

surface diffusion of cations.

perovskite is reached, reductive nucleation of LZO originates. Island growth is control led by surface diffusion of cations and the supply of lanthanum.
After the critical Mn concentration in the
The electrochemical

properties

of the cathode/YSZ interfaces


LZO at the

are

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


nated from electrochemical

triple phase
are

of adsorbed molecular discrimi

oxygen ions, and surface diffusion of atomic oxygen

impedance data.
strontium

Keywords.
(SOFC).

Lanthanum zirconate

(La2Zr207); lanthanum

manganite;

oxygen

reduction; electrochemical kinetics; electrochemical impedance; solid oxide fuel cell

4.1
4.1.1

Introduction
General
ion

conducting Yttria-Stabilized Zirconia (YSZ) and perovskite-type Sr-doped LaMn035 (LSM) have been widely used as electrolyte and cathode materials in Solid Oxide Fuel Cells (SOFC). The target operating tempera tures of SOFC have been markedly reduced from -1273 K (1000C) to Oxygen
-1173 K

(900C)

or even

less

over

the past ten years. A further reduction of

the

operating temperatures

seems
a

required
cause an

to circumvent the
or

use

of expen

sive interconnect

materials, such

lanthanum chromite

nickel base

alloys.

But lower

operating temperatures

increase of the electrode and elec

tiolyte resistances, thus, the overall power output of the cell decreases. These circumstances have heightened the need for a better understanding of the factors influencing the electrochemical properties of SOFC electrodes. Of par ticular interest is the interface between the cathode and the electrolyte, i.e. the triple phase boundary (tpb) region, where the reduction and incorporation of adsorbed oxygen species is supposed to take place [1]. Nowadays, it is gener ally accepted that the electrochemical properties of LSM cathodes depend to a larger extent on the nanostructure and the phase composition of the inter face, than on the microstructure of cathode layer. The formation of badly con ducting foreign phases during heat treatment and/or operation is believed to be the main factor for a degradation of the electrochemical properties of per-

160

4.1

Introduction

ovskite cathodes. Lanthanum zirconate zirconate

(La2Zr207,

abbr.

LZO) and strontium


with

(SrZr03,

abbr.

SZO)

are

well known to form under certain condi

tions. The successful

employment
activity for
extent

of Co and Fe

containing perovskites
at

high

electrochemical

SOFC
on

operation

intermediate tempera
or

depend to a large mation of foreign phases.

tures will

the

ability

to

control

inhibit the for

4.1.2
Lau and

Microstructure and

-Chemistry

Singhal [2] first reported pyrochlore-type La2Zr207 formation between diffusion couples of dense Lag 9Sr01MnO3 and (ZrO2)0.8(YOi .5)0.2 single crystals. La2Zr207 and perovskite-type SrZr03 have been found to form at interfaces between YSZ and (La,Sr,Ca)Mn03 at high temperatures in
air
or

[3-4]. The

amount of LZO has been found to decrease with

increasing

Sr

longer reaction periods or higher sintering temperatures, respectively. Formation of SrZr03 has been found to occur between heavily doped La1_xSrt.Mn03 (x>0.3) and YSZ [8,4,9,10]. A-site deficiency in (La,Sr)1_yMn03 has been shown to decrease or even prevent zirconate formation during high temperature treatment. Yamamoto et al. [11] found no reaction product by X-ray diffraction analysis for the mixture of La08MnO3 and (ZrO2)0.84(YO15)016 after sintering at
to increase with

Ca substitution for La

[5,6,7], and

1473 K
1573 K
ment.

(1200C) for

192 h;

however, when the temperature


zirconate
was

was

raised to

(1300C), lanthanum

detected after 50 h of heat treat


reactive than the sto

(La,Sr)0 9Mn03 was


[5].
was

found to be
In

considerably less
an

ichiometric material

addition,

induction

period

for zirconate

formation

observed when A-site deficient LSM

was

used [5,12]. The fol

lowing explanation [12] was given: Mn diffuses in larger quantities than La, therefore lanthanum manganite depletes in Mn which further leads to La203 precipitation, which itself immediately reacts with YSZ to form LZO. These experimental findings are in good agreement with the chemical equlibria

calculations

of

mixtures

of

(La1_x_ySrxCay)Mn03

and

(ZrO2)087(YO15)0.i3 by Yokokawa et al. [13,14]. The reaction of LaMn03 with Zr02 has been characterized as a combination of the LZO formation and a
reduction of the Mn ion [15]. The
valence state of

thermodynamic origin

of the

driving

force

of this reaction has been attributed to the destabilization of the unusual

Mn3+

in the

perovskite
case

in presence of zirconia.

Thermody
lanthanum

namic studies showed for the

of

LaMn03 that the relatively stable tetravrise


to

alent

manganese

ions

in

the

perovskite give

the

161

La2Zr207

Formation

and

02

Reduction Kinetics

nonstoichiometry.
between
oxidized in the
nese

It

was

pointed

out

[15-16]

that when

La2Zr207

is formed

LayMn035 and YSZ, a small number of the manganese ions may be


perovskite
structure. In to

contrary, the dissolution of manga


from the size of manganese ions:

is reductive. This

seems

originate

the ionic radius of the tetiavalent state is small, and this makes it easy to accommodate the La

nonstoichiometry

in the

relatively large

size of the divalent ions

perovskite phase, whereas the ensures the large solubility into YSZ

(see [16] and references therein).

Manganese, a major constituent of doped LaMn03, is known to be a mobile species at high temperatures and can easily dissolve from lanthanum manganites into YSZ, thereby changing the properties of the cathode and electio lyte surface [2,3,8,12,17,18]. Diffusion coefficients of Mn in (ZrO2)0^(YOj 5)0 2 single crystals were reported to be (10-13 to 10"12) cm2/s at
1673 K

(1400C) and

two

orders of

magnitude higher

[2].

This

large

difference has been attributed to fast

polycrystalline YSZ diffusion paths through


in
were

grain boundaries [3, 6,19].


lated from chemical shown that manganese
as can

Total solubilities of manganese oxides

calcu

equilibria

calculations

by

Yokokawa et al.

be dissolved up to 11.4%

(2.1%

as

[20]. It was Mn3+ and 9.3%

(Zr02)o.85(YOL5)o.i5 at 1573 K (1300C) in air. At 1273 K (1000C), calculated solubility is lowered to 5.1% (1.4% and 3.7% for Mn3+ and Mn2+, respectively). This contradicts the observations of Roosmalen and Cordfunke
in

Mn2+)

La^Sr^MnOs (x 0, 0.15, 0.3, 0.5) into YSZ from diffusion couple experiments. They observed a mass tiansport of lanthanum and strontium from the perovskite into YSZ. How ever, the previously mentioned studies were performed under different experimental conditions and employed different sample preparation and characterization methods, which may be the basis to discrepancies and disa greement concerning the reaction mechanism of YSZ with LaMn03 based cathode materials. This conjecture is supported by Yokokawa et al. [21] who pointed out that oxygen plays an important role in the reductive dissolution of manganese from the perovskite phase in YSZ:
no
=

[4] who found

diffusion of manganese from

MnOn(p)

MnO,(YSZ) + (n'

n)/2

02(g).

(4.1)

Oxygen removal may be hindered in dense diffusion couples, therefore retarding manganese dissolution. In contrast to Mn, diffusion and solubility of La from the perovskite phase in YSZ has generally found to be much

162

4.1

Introduction

smaller, whereas Sr diffusion and solubility in YSZ have been found


almost

to be

completely absent [2,8,11,12,18].


was

Also

migration

of Zr and Y into the

perovskite

observed

[6,8].

4.1.3

Influence
on

on

Electrochemical

Properties
type

The literature

the relation between electrode characteristics and the


is far less extensive in

and amount of

foreign phases
=

comparison
(1000C)

to thermo

dynamic studies. La!_xSrxM03 (M

Yamamoto et al.

[9] first showed the influence of annealing


at 1273 K
on

Cr, Mn, Fe)/YSZ interfaces

the

cur-

rent-overpotential behaviour at 1073 K (800C). The overpotential of these cathodes was not significantly affected with the annealing process. However, at annealing temperatures of 1373 K (1100C) the overpotential increased rap idly with annealing time. This was attributed to the formation of large
amounts of

SrZr03

which

was

detected with

X-ray

diffraction. On the other

r/-sputtered LaCo03 cathodes increased rapidly with annealing time, which the authors explained by the chemical reaction of YSZ and LaCo03 to form lanthanum zirconate. Similar results were found by Ivers-Tiffee et al. [22]. Kaneko et al. [12] followed the change of the electro chemical impedance during sintering at 1673 K (1400C) in air and investi gated the interfaces after sintering with EDX. Both the high frequency resistance and the low frequency resistance increased markedly with time
hand, the overpotential for
and
a

the presence of LZO

was

observed after

sintering.

The authors

explained this increase in electiode resistance with the formation of a LZO layer at the interface, but they did not attribute any relaxation frequency to a particular electiode process. They noted that the cathodes were almost dense after the experiment and the low frequency losses were in the range of (0.01 to 1) Hz. From this it seems unlikely that the increase in cathode resist ance was caused entirely by the LZO layer, rather gas phase diffusion through the almost dense cathode must have been mainly responsible for the low frequency losses. Electrochemical impedance spectroscopy (EIS) was also employed by Elangovan et al. [23] to study the La0 89Sr0 jMnO^ air I YSZ sys significant changes in the high frequency part of the spectrum during operation at 1273 K (1000C). Although they failed to prove the existence of foreign phases at the interface by means of SEM in this work, they concluded from diffusion couple studies [3] that lanthanum zirconate must have formed at the interface. Similar experiments were carried out by Kenjo et al. [24] who conducted polarization measurements at 1173 K (900C)
tem. The authors found

163

La2Zr207

Formation

and

02

Reduction Kinetics

on

YSZ-LaMn03
in air.

cathodes mixtures sintered at 1273 K

(1000C)

to 1573 K

(1300C)

They

detected traces of lanthanum zirconate at the cath

ode/electrolyte interface by means of XRD after removing the cathode. Although, a general correlation between the amount of LZO and polarization resistance Rp was found, no detailed explanations were given for the increase in Rp. It was argued that a layer of badly conducting LZO simply increases
the ohmic resistance of the cathode. We note that those studies
out at
ances were

carried

high operating temperatures of -1273 K (1000C) where cathode resist are generally low (< 1 Q-cm2) and where it is experimentally difficult to impedance
measurements up to

obtain accurate electrochemical

quencies. Using
more

lower

temperatures for cathode


on

high fre characterization would yield


[25,26].
of the oxygen reduction

information about the oxygen reduction reaction mechanism

We will

give

brief review

the present

knowledge

reaction mechanism in the discussion section.

Recently, transmission electron microscopy (TEM) studies were performed by Tricker and Stobbs [17] on porous La0.8sSr015Mn03/YSZ reaction couples which were sintered at 1573 K (1300C) and operated at 1273 K (1000C) in air. The authors were able to detect grains of lanthanum zirconate in an early stage of growth. Growth of LZO was predominantly epitaxial and directed away from the parent YSZ into the abutting LSM. Similarly, Clausen et al. [18,27] performed TEM studies on diffusion couples as well as on pressed
and sintered mixtures with different ratios of manganese
YSZ.
excess

LSM and

They

concluded from their measurements that nucleation of LZO

occurred at the interface between LSM and YSZ


rial from both the cathode and the

grains

with

supply

of mate

electrolyte. According to these authors, the diffusion of manganese into YSZ causes manganese depletion of the LSM and in the case of stoichiometric LSM chemically active La203 is formed at
the interface, whereas this process is
in the LSM.

impeded

or

delayed by

an excess

of Mn

They

further showed, that the extra manganese does not have to

be contained within the


increase the manganese
ions.

manganite

structure, but that it is sufficient to of

activity by

means

doping

the cathode with Mn

Although these TEM measurements gave a

rather detailed

picture of the

microstructure and

microchemistry
the

of the YSZ/YSZ/LZO interface, the of how the electrochemical proper

authors gave
interfaces.

no answer on are

question

ties of cathodes

influenced

Ostergard et al. 1273 K (1000C) on slurry coated and screen printed cathodes. Unfortunately they carried out TEM not on

by the presence of LZO at cathode/electrolyte [28] performed electrochemical measurements at


LSM-YSZ

these

composite samples but on

164

4.1

Introduction

dense

pellets

of mixtures between

LSMy and YSZ. Nevertheless, the polariza


i.e.

tion resistance
ues

Rp for the oxygen reduction at 1273 K showed decreasing val


by increasing composite cathode, and Rp decreased with parallel, samples with manganese excess
no

upon

increasing the length of the triple phase boundary,


excess.

the volume amount of YSZ in the

increasing manganese

In

and low amounts of YSZ

developed

lanthanum zirconate, whereas stoi

large amounts of YSZ showed the K. The performance presence of lanthanum zirconate after sintering at 1573 increase of the cathodes has been explained with the increase of the length of the tpb and an improved electrode adhesion. Mn dissolution was considered as the controlling factor for LZO formation; however, the authors did not quantify the different factors which influence Rp.
chiometric cathodes and cathodes with

4.1.4

Open Questions
the fact that
a

and Aims of the

Study

Despite
have
most

faces

large number of experimental and theoretical studies been performed, important questions are not yet answered. First and important, it is unclear how the oxygen reduction at LSM/YSZ inter is influenced by the presence of LZO and the microchemistry of the
seems

play an important role in the kinetics of the LZO formation. But, does A-site deficiency in LSMy lead to an incubation time in LZO formation and to a decrease in LZO growth, or were these con clusions drawn due to the detection limits of the experimental apparatus employed? And finally, can we circumvent the formation of detrimental for eign phases by lowering both the fabrication temperature and operating tem
interface. Second, Mn
to

perature, and/or by choosing appropriate cathode stoichiometiies?


The purpose of
our

work

was

to

investigate

the influence of the manganese

stoichiometry

in

La0.8sSr015Mny03 (LSMy)

upon the nucleation and the

growth of lanthanum zirconate at 1373 K (1100C) in air at electrode/electro lyte interfaces, and to simultaneously determine the electrochemical proper ties of these interfaces. The study was performed with porous screen-printed cathodes on (001) YSZ single crystals. After sintering, the cathode layers were
first removed before any further microstructural formed. Atomic force and

investigation

was

per

microscopy (AFM) X-ray photoelectron spectros copy (XPS) were used for analysing the YSZ surfaces. High resolution (HR) TEM was employed for structural analysis and phase analysis of the YSZ sur
faces after heat-treatment. Electrochemical
was

employed

to monitor the

impedance spectroscopy (EIS) frequency response of cathodes during the

165

La2Zr207

Formation

and

02

Reduction Kinetics

heat-treatment process. Distinct differences in nucleation and


were

growth

of LZO

depending on the stoichiometiy of LSMy. Surface diffusion of cations was predominant in case of near-stoichiometric and A-site deficient LSMy. LZO islands formed predominantly at the tpb which caused an increase of the cathode resistance. The charge-transfer reaction was found to be not rate determining at temperatures below 1173 K (900C). The electiode
found
resistance
was

attributed to the dissociation of adsorbed oxygen and the

sur

face diffusion of atomic oxygen.

4.2
4.2.1

Experimental

Procedures

Sample Preparation
couples
were

prepared from dense YSZ substrates and porous per ovskite layers. Single crystals of 9.5-mol% Y203-stabilized Zr02 (25x25x0.5 mm, (001) orientation, polished on both sides) (Zirmat Corp.,
Reaction
N. Billerica, MA,

USA)

were

obtained. The

impurity

content of the

raw

mate

single crystal fabrication is low, and the impurity concentration of the single crystals is expected to be even 1 to 2 orders of magnitude lower than of the raw materials due to the single crystal fabrication process (skull melting). The primary crystallite size of the perovskite powders (ball milled after calcining at 1223 K (950C) for 2 h) (SSC Inc., Woodinville, WA, USA) was -250 nm. The powders were strongly agglomerated. The powder com positions were verified with inductively coupled plasma (ICP) atomic absorption spectroscopy (AAS). Two powders with nominal stoichiometiies of La0.85Sr0.i5Mn{).95O3 (LSMo.95) and La085Sr015Mno.9803 (LSMa98) were
rials for used in this
Pastes of

study.
were

prepared by mixing appropriate amounts of pow der (71.9 wt%) with a solvent (24.5 wt%) (diethylene glycol monobuthyl ether acetate, Fluka AG, Buchs, CH), a binder (0.9 wt%) (Ethyl cellulose, Ethoxyl content 48%, Aldrich, Inc., Milwaukee, WIS, USA), and a dispersant perovskites
(2.7 wt%) (Furan-2-carboxylic acid, Fluka AG, Buchs, CH)
Screen
in
an

agate

mortar.

printing pastes with higher manganese contents (0.98<y<1.10) were prepared by adding Mn(N03)2-4-H20 (Fluka AG, Buchs, CH) (dissolved in ethanol) in appropriate amounts to the LSM0 98 powder before preparing the
paste. This procedure
ensures

that the additional manganese is and within the

homogene
Table 1

ously distributed on the powder surface

organic paste.

166

4.2

Experimental Procedures

Table 4.1
the cation

Characteristics of the
ratio

screen-printing pastes
to

used in this
cation

(column 3) refers
paste.

the

nominal

study. Note composition of


consist

that

the the

screen-printing

LSMy

(y

1-02)

screen-printing

pastes

of

Lao 85Sr0 jsMrio 9803 powder

with additions of manganese nitrate.

Sample
LSMa95

Description
SSC, Inc., calcined 1223 K for 2 h,
ball milled

Mn/(La
0.95

nSr)

LSM0.98

SSC, Inc., calcined 1223 K for 2 h,


ball milled

0.98

LSM102

LSMg 98

with additions of

1.02

Mn(N03)2-4H20

LSMy (y

>

1.02)

LSMq 98 with additions of Mn(N03)24H20

>1.02

summarizes the
were

screen-printing 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

before use, i.e. the additional manganese is sup

by means of a thermocouple which was located close to the samples. The samples were held at 1073 K (800C) before and after sintering in an supplementary furnace. The heating
was

GmbH, FRG). The temperature

controlled

rate

was

K/min from

room

temperature
a

to 873 K

(600C) with

dwell time

heating rate of 3K/min to 1073 K. The samples were taken from the supplementary furnace, put into the sinter ing furnace for the desired period, and subsequently put back into the fur nace held at 1073 K. The cooling rate from 1073 K to room temperature was 3 K/min. Home-made high purity alumina crucibles (CERALOX HPA0.5 Mg, Condea, Tucson, AR, USA) were employed as sintering supports. The pore size distributions and porosities of cathodes were obtained from mer cury-intrusion measurements (model 2000, Carlo Erba, Italy) on -0.12 g of sintered screen-printing paste. The cathode layer thickness was -20 pm after sintering. In order to examine the YSZ surface and the reaction products on the YSZ surface after sintering, the sintered porous perovskite layers were dissolved with concentrated hydrochloric acid in an ultrasonic bath at room

of 4 h at this

temperature followed by

167

La2Zr207

Formation

and

02

Reduction Kinetics

temperature. Finally, the samples


and lanthanum zirconate dissolves
are

were

cleaned with water and ethanol. YSZ

stable

against hydrochloric

acid whereas

LSMy

rapidly.

4.2.2

Investigation

of Surfaces and Interfaces

Topographic observations of YSZ single crystal surfaces were conducted with AFM (TMX 2010, TopoMetrix, Santa Clara, CA, USA). All the AFM experi
ments
were

conducted in air

using

constant force mode. A

square

pyrami

dal

Si3N4 tip

with radius of curvature of -100 nm,


nm

produced

lateral and

respectively. The base of the pyramid consisted of a square with sides -5 pm long. The aspect ration was about 1:1. A tripod scanner (70 pm scan range) was used for scanning large ranges. Higher resolution was obtained with a tubular scanner (7 pm scan range).
vertical resolutions of 2
and 0.5 nm,

analysed quantitatively, with each image consisting of 1024 lines with 1024 points. The quality of the silicon nitride tip was regularly checked with a sample of known surface structure. Numerical analysis of surface data was carried out with the AFM software package (version 3.08) on a windows compatible (486) personal computer. Raw data were first corrected for sample tilt before conducting numerical analysis. Quantitative estimates of the volume amount of surface phase, its average height, the YSZ surface coverage, and the length of the tpb between the YSZ
Five

images

from each

sample

were

surface and any surface


HRTEM

foreign phases

were

obtained.

analyses were conducted on YSZ surfaces. Electron transparent sam ples were prepared by dividing, polishing, and argon-ion-thinning. Follow ing standard procedure of mechanical pre-thinning of cross-sectional specimens, two slices from the sample were epoxy bonded in a metallic tube face to face. This composite was sliced, mechanically thinned, and polished
to
a

thickness of

(20.. .30)

pm. Plan-view

samples

were

cut into disks of 3

mm

dimpled from the substrate side to a final thickness of 20 pm. In both instances, final thinning to electron transparency was done by argon-ion beam thinning. Micrographs were obtained with a HRTEM (model CM30, Philips) operating at 300 kV.
diameter

using

an

ultrasonic disc cutter and then

Energy-dispersive X-ray analysis (EDX) (VOYAGER III, Noran Instruments, Middleton, WI, USA) was used for elemental analyses of foreign phases on
the YSZ surface.

168

4.2

Experimental Procedures

XPS

sputter depth profiles

were

recorded in
=

Perkin-Elmer PHI 5400 ESCA

1253.6 eV). Using an electron take-off system using Mg Ka excitation (hv angle of 43, the analysed surface area was 1.5 mm2. Sputter depth profiling
was

performed using

argon ions at 3.3 keV. The

sputter

rate

was

calibrated

with reference films to

3.7nmmin-1

for

Si02.

The

sputter

rate ratio between

Zr02 and Si02 is 0.46 therefore giving a sputter rate of 1.7 nmmin-1 for Zr02. The depth profiles were acquired as a set of discrete sputter cycles inter

rupted by

XPS measurements of the Zr 3d, Y 3d, La 3d, Sr 3d and O Is

core-level lines. The atomic concentrations

reported

here

were

calculated

using PHI sensitivity

factors.

4.2.3

Electrochemical

Investigation

working electrodes (lxl cm, -20 pm thickness) and reference elec trodes were applied to YSZ single crystals by screen printing. Platinum gauzes (52 mesh, Fisher Scientific, Pittsburgh, PA, USA) were pressed by hand into the freshly printed perovskite layers. The gauze was fixed at the edges with a ceramic two-component binder (type 1500, Firag, Ebmatingen,
Perovskite

CH), and further coated with diluted

screen

printing paste

in order to have

good
wires

electrical contact between the cathode

layer

and the gauze. Platinum

(0.35

mm

diameter)

were

used to contact the gauzes. The counter elec

prepared from Pt paste (C 3605 P, Heraeus GmbH, Hanau, FRG) where we first dc-sputtered -50 nm of Pt on the YSZ surface (model SCD 040, Bal-tec, Balzers, FL). The in-plane conductivity of unsintered and sintered cathode layers, as well as the conductivity of dense cathode material, was measured with four-probe measurements. The layers were screen printed on
trodes
were

polished alumina potential probes.

rods

(3x3x40 mm).
were

Pt wires

were

used

as

current leads and

Electrochemical measurements

conducted in air
to 1373 K

temperature range of

723 K

(450C)

atmosphere over the (1100C) during heating and

cooling cycles. Steady-state current-potential curves and electrochemical impedance spectra were obtained (Model IM6, Zahner GmbH, FRG) in a three-electrode, four-lead configuration. The measurements were carried out < 105 Pa). in air or 02/N2 mixtures (5 Pa < Impedance measurements pQ were carried out at equilibrium potential Eeq (if not otherwise stated) in potentiostatic mode over a frequency range of 10 mHz to 100 kHz or less. The excitation voltage was 20 mV at T < 873 K (600C) and 10 mV at temperatures above. Short electrical wires were used to minimize inductive errors at high

169

La2Zr207

Formation

and

02

Reduction Kinetics

high temperatures due to low electrode impedances. The fre uncompensated electrolyte resistance Re was determined from the high data in a complex plane plot. The polari quency intercept of the impedance in the zation resistance Rp was obtained from the low frequency intercept of the complex plane plot. The dc resistance was obtained from the slope
frequencies
and

steady-state I(r\)

curve

at rj

0. A further

analysis

of

impedance

data will

be described in the discussion section.

4.3
4.3.1
A

Results
Cathode Microstructure and Electrical
electron
YSZ

Conductivity
a

scanning

micrograph

of

fractured

cross

section of

porous cath

ode
the

single crystal is shown in Fig. 4.1. The micrographs show typical morphology of the La0 85Sr015Mny03 layers obtained in this study.
layer
on a were

The cathodes
even was

without cracks and adhered well to the YSZ substrate,

after

only

15 min of

sintering.

The average

grain
on

size of the cathodes

in the range of 0.3 pm to 0.8 pm,

depending

the

sintering period.

Fig.

4.1

SEM of sintered

LSMT

02

cathode

on

YSZ

single crystal.-The sample

was

sin

tered at 1373 K

(1100C)

in air for 2 h.

(a)

Overview of the microstructure.

(b)

Necks
02

around the LSM

grains

and at the contacts between the YSZ surface and the

LSMj

grains

formed

during sintering.

170

4.3

Results

Neck formation between the cathode between the cathode

grains,

as

well

as

at the

interface

grains

and the YSZ

(Fig. 4.1b). SEM-EDX gave no spective of the composition of the cathode) at the interface or for interdiffusion of cations. The porosity of Lao^SiaisMn^^ cathodes changed from
T/C
1000 800

electrolyte surface, can be observed indication of formation of foreign phases (irre

600
r-.

500
i

400

105

D D

D
D D

:
.

_ _
_

10<

c*
o

mo*omD
4>
O
o

cooling
o

10J

7
.

~.

heating

dense

LSMQ 98
LSM0 9g
o o

porous, sintered
o

porous, unsintered porous, unsintered


i

LSMQ 9g
LSMQ 9g
i

(+4% Mn)
i

10^

0.8

1.2

1.4

103K/T
Fig.
4.2

4-probe electrical conductivity


were

of

LSMy

cathode

layers

in air.The
in air, held for 2

screen-

printed samples

heated with 3 K/min to 1223 K

(950C)

h, and

subsequently cooled to room temperature with 3 K/min. For comparison, the electrical 4-probe conductivities of dense bars (sintered at 1623 K (1350C)) and porous LSMo98 layers (sintered at 1373 K (1100oC) for 2 h) are given.

171

La2Zr207

Formation

and

02

Reduction Kinetics

-55% in the green state to -42% after 12 h of

sintering
=

at 1373 K
=

(1100C),

where the
observed
content

mean

pore diameter increased from d

0.32 pm to d

0.5 pm. We

by

SEM that cathodes densified faster the

higher

their manganese

was.

Nevertheless, the porosity did

not decrease to values less than

40% at
excess.

sintering temperatures

of 1373 K for cathodes with 10% manganese


our

The cathode materials in

study

with y

0.95 to 1.10

were

single

phase perovskites
ther

of rhombohedral structure. We could not detect any fur

phase in sintered cathodes by X-ray diffraction; however, cathodes with higher amounts of manganese (y 1.16) showed the presence of Mn304
=

grains

in the TEM.

conductivity of the cathode layers followed the general dependence for small polaron conductivity. Fig. 4.2 shows the variation of log(o T) vs. 1/T of freshly screen-printed porous layers of LSM098 and LSMX 02 on polished alumina substrates and compares the results of porous and dense LSMq 9g- Note that the cathode layers were not heated to 1373 K but only to 1223 K (950C). Nevertheless, the cathode layers cracked during cooling below 723 K (450C) due to the thermal expansion mismatch between alumina and slightly sintered porous LSMy. Note that the electrical conduc tivity of unsintered cathode layers is relatively high after the heat treatment at 1223 K in comparison with sintered cathodes. The addition of Mn ions to the screen printing paste has a beneficial influence on the electrical conduc tivity of unsintered cathodes at lower temperatures during heating. There is no significant difference in the conductivity of undoped and doped (+4% Mn) LSM0 98 after heat treatment at 1223 K.

The electrical

4.3.2

Interface

Development During Sintering


(y
=

Manganese

Deficient Perovskite

0.95).

Fig.

4.3

depicts

XPS
a

sputter
porous

depth profile from a YSZ surface which was sintered La0 85Sr015Mno 9503 (LSM0.95) cathode layer at 1373 K in air

with

for 2 h. The YSZ

single crystal was completely transparent after removal of the cathode. The surface layer (after 30 sec of Ar+ sputtering) of this sample is seen to contain primarily Zr, La, and O. The concentration of Sr decreases from ~1% at the
surface to less than 0.5% after 30
nm

of

sputtering.

In

comparison,

Y is

present
method

at the surface and its concentration increases to the nominal value of


nm

YSZ after ~30

of

sputtering.

Mn is below the detection limit of the XPS

(~0.1%).

The

composition

of the surface

layer

is

seen

to remain

172

4.3

Results

^sputter'1
0 20 40 60

10

20
/min sputtei

30

40

Fig. 4.3

XPS sputter

depth profile of a La-ridi surface layer on YSZ single crystal.


a

The first few nanometers of the surface show


tration of Sr is below 1%.

La/Zr ratio of -1.35. The atomic


~40
nm

concen corre

Beyond
s

sputter depth of
of

the

composition

sponds

to

the nominal

composition

(Y015)019-(Zr02)o.8i-

The

sample

was

first
sam

sputtered with Ar+ during 30 ple surface not shown) [32].

for removal of carbon

(composition

of 'as received'

approximately

constant

over

the first 20

nm

and the La/Zr atomic ratio is

During depth sputtering, electrostatic charg ing of the sample surface occurred after -15 nm of sputtering. The La/Zr ratio before Ar+ sputtering of the sample was -0.65, i.e. the Zr4+ concentra tion within the first (0.5... 1) nm was distinctly higher than the La3+ concen
nm.

-1.35 within the topmost 15

tration. However, the carbon concentration before

sputtering (as received

sample)
result. TEM

was

-50% and, therefore,

care

must be taken in

interpreting

this

images
4.4

of

cross-section of the YSZ surface studied with XPS


are

as

described above,

shown in

Fig.

4.4

Even under

low of

magnification
a

(Fig.

a)

it is clear that the YSZ surface contains

grains

new

phase

which

cover

the YSZ surface

entirely. Fig.

4.4b shows the Selected Area Elec-

173

La2Zr207

Formation

and

02

Reduction Kinetics

a)

o
o

9
ft
o

cf

t>

(5

Cf

%
.

O
5

9
O

O
O
<3
.

<*
o
i

*D

#
O
o

CP

*D
.

)
o

(i
o
.

O
<3

%
.

'
o

Q
o

P
o

Q
o

b)

Fig.
tal

4.4

TEM

images
and

of lanthanum zirconate islands grown

surface.(a) Bright

field

image

of LZO

grains

of uniform

(001) YSZ single crys thickness and size, (b) Sim


on a

ulated

(right side)

experimental (left) [Oil]

SAED of

epitaxial

LZO

on

(001)

YSZ

sur

face. The filled circles in the simulated pattern represent the YSZ reflexes where the open circles represent the LZO reflexes. Given (hkl) refer to LZO. The structural data from Deiseroth

[29]

were

used for simulation

(oxygen parameter:

0.295).

174

4.3

Results

Fig.

4.4

(continued) (c) High resolution image of lanthanum


a

zirconate

grain

in

[Oil]

direction. The inset shows

magnified

selection of the
is

top

of the island. An
into the inset for

experimen comparison

tally

obtained HR

image

of YSZ in

[Oil] direction

pasted

(darker square).

tron Diffraction

(SAED) pattern

of the surface
a zone

ulations for YSZ and diffraction spots


tion
are

La2Zr207
caused
as

with

region and compares with sim axis of [Oil]. The wide and intense
parameter which
is -2.08

by

the YSZ substrate whereas the weak diffrac


a

spots index perfectly


0.5142
nm

fee with

unit cell

times the lattice

parameter of the YSZ substrate (9.5 mol% Y203-stabilized;


consistent with the reaction

a0

[30]).
are

These

findings
nm

product
a

on

the surface

being
of of

lanthanum

zirconate,

La2Zr207,
is odd and

which

has

lattice

parameter
an

a0

1.0786
are

[29, 31]. The diffraction spots n{hkl} (n being


n

integer)
present

LZO

weak when
are

strong when [011]


beam

is

even

[31]. Although
are

the
in

{200} reflections
the SAED

not allowed with


was

direction, they

pattern. This

also observed

by

Clausen et al.

[18]

and is

175

La2Zr207

Formation

and

02

Reduction Kinetics

explained by
the

double diffraction,

(111)

(111)

(200). The diffraction pat


4.4 a grew

tern also reveals that the LZO

grains

shown in

Fig.

epitaxially

on

(001) YSZ surface

{001}LZO||{001}YSZ

<100>LZO||<100>YSZ
which is in

(4.2)
the

agreement with previous

LZO reflections

splitting of the reveals that the epitaxy is not perfect, but that a slight misoriresults

[17]. Finally,

entation exists between the YSZ substrate and the LZO

grains.

It

was

not pos

sible to determine the cation concentration of the LZO


TEM-EDX due to the size of the and Mn in the YSZ

grains reliably
grains
a were

with

grains; however,

the concentrations of La

adjacent
our

to the lanthanum zirconate

below

the detection limit of


the surface

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


a

layer. Fig.

4.4c shows

HRTEM in

[Oil]

direction of

single

LZO

Fig.

4.5

AFM of

lanthanum zirconate
a

layer covering

YSZ

single crystal

surface.

(a) 2-dimensional
LZO grains

view of

(800x800)

urn area

Note the

preferential

orientation of the

[32].

176

4.3

Results

Fig.

4.5

(continued) (b)

Lower

right part

of

(a) shown

in

surface

plot

to

depict

the vari

ations in

layer height.
same

Note that

Fig.

4.3 and

Fig.

4.4 show the XPS

profile

and HRTEM

images

of the

sample surface, respectively.

grain.

Note that the surface of the

grain

shows

high-resolution (HR) pattern


grain
was

which is

apparently equal layers


of this

to the

pattern of the YSZ substrate (cf. inset of


LZO

Fig. 4.4c).

We found that every

investigated

covered with

few atomic

resolution contrast to the

phase. Note that the transition from the LZO high high resolution image of the surface phase is seen to
can

be continuous. No dislocations

be

seen.

Fig.

4.5 shows the

topography of the

same

YSZ

sample
of the

surface. It is

seen

from

the AFM

image

in

Fig.

4.5 a that the lanthanum zirconate


to the <100>
axes

grains

are

preferen
which is
size

tially
in

orientated with

respect

(001)

YSZ surface. The

average

height

of the surface

layer

shown in

Fig.

4.5b is

(18

3)

nm,

agreement with the XPS results reported

in

Fig.

4.3. The average

grain

of the LZO

grains

is about

(120

40)

nm.

Nucleation of LZO

grains

occurred

around the contact between the LSM after

grains facing

the YSZ surface. Even

sintering periods of less than 15 min, the YSZ surface was almost com pletely covered with islands of LZO of considerable thickness (-5 nm). The growth constant D of the reaction layer was evaluated through the Wagner
equation,
x
=

t, where
t.

is the average thickness

as

function of the
we

sintering

time
=

With

x=(183)nm
at 1373 K.

and

t=2h

estimate

logD/(m2-s_1)

-(19.35 0.15)

177

La2Zr207

Formation

and

02

Reduction Kinetics

Slight Manganese

Deficient Perovskite

(y

0.98).

Fig.

4.6

shows

AFM

images

of the

development

of lanthanum zirconate islands

at 1373 K

(1100C)

in air between cathode

layers

of

during sintering La0 85Sr0 isMn0 9803 and


grains
of the islands is

YSZ. It is discernible that the islands grow in between the cathodes and the YSZ surface towards the cathode. The cube-like and the islands show
a

shape

preferential orientationship with the YSZ substrate. By looking closely at the islands in Fig. 4.6a it can be seen that the large islands are made up of four smaller islands (embryos). During sintering the embryos grew in diameter and height until they faced each other and therefore formed a single island. These islands further grew in height and diameter until most of the YSZ surface was covered by a relatively thick layer

Fig.

4.6

AFM

images

of

(001)

YSZ

single crystal
on

surface covered with

cube-shaped
scale,

islands of lanthanum zirconate.The colourbar


taxial LZO

the

right

denotes the

(a) Epi
nm an

grains (1)

on

top

of the YSZ surface after 30 min of


is

sintering

at 1373 K

(1100C)

in air. The average island size

(0.50.1) pm

and the average


at
z
=

height
parent

is -35

after 30 min. Note that the YSZ level is


obvious orientation denotes the

approximately
phase.

60

nm

and that there is YSZ.

relationship

between the LZO

grains

with the

(2)

tpb

between YSZ, LZO, and the gas

178

4.3

Results

Fig.

4.6

(continued) (b)
is

Same situation
nm

as

in

(a) after

12 h of
is

sintering The original YSZ


nm

surface level

at

135

The average island

height

-125

of

cube-shaped
in the
z

lanthanum zirconate islands

(Fig. 4.6b).

Note also the differ

ences

scale of these two

figures

and compare with

Fig.

4.5. The initial

surface coverage after 15 min


to be -50%

was

estimated

numerically

from AFM

images

(Fig. 4.7b). length

This value increased to -90% after 12 h of

sintering

period.
the

The

of the

ter between the LZO

tpb, l^h, was obtained by estimation of the perime grains and the YSZ surface numerically. The length of

rapidly within the first 30 min of sintering and slowly decreases with increasing sintering time. A clear correlation between /w,b and Acov is seen. Fig. 4.7c shows the average height of the LZO islands, hav,
increases

tpb

which

was

obtained from the estimated volume amounts of LZO

on

the YSZ

surface, standardized with the corresponding surface coverage.

In this way
can

hav corresponds

to

an

apparent LZO layer thickness and the results

be

compared
a

with those of
as

LSM0 95.
case

The

growth

rate of the island

height

follows

different law

in the

where the LZO

layer

is dense.

179

La2Zr207

Formation

and

02

Reduction Kinetics

10

!
-

6
a
a.

T>

X^

a)
10 100

1000

t/min

15 min 30 min lh

ot
B
3.

A 2h
4h

12 h

D.

w> 1
A
A

b)
0.4
0.5

0.6

0.7
A
cov

0.8

0.9

Fig.
of

4.7

LZO island
versus

tpb

shown

50% of the

growth kinetics at 1373 K between LSM098 and YSZ.(a) Length sintering time at 1373 K in air. The region marked contains at least predictions, (b) Length of tpb shown versus YSZ surface coverage with LZO

islands.

180

4.3

Results

200
un-r\

"av

.t

u$l

D())(1373
100

K)

1.8710"22 nVs"1

a
> Rl

50

2.48

c)
20 10
t
sine

10
Vs

(continued) (c) Apparent layer growth numerically estimating AFM images.

Fig.

4.7

kinetics. The data

were

obtained

by

Fig.

4.8

shows

bright

field TEM of

LZO island. A
as

sharp boundary
dislocation net
com

between the YSZ and the lanthanum zirconate,


work around the

well

as a

grain boundary,

can

be

seen.

The LZO island grew

pletely towards the cathode side and not into the YSZ. The boundary is remarkably flat. The lattice constant of LZO was estimated from a [Oil] SAED
pattern
over as

a0

1.077
was

nm.

The cation concentration in the islands

(averaged

islands)

determined with TEM-EDX. We obtained


+

(40.30.1)% for

La, (6.50.2)% for Y, and (53.20.2)% for Zr. The Zr/(La

Y)

ratio is therefore

equal

to 1.14 at

Zr concentration of 19.3%. The Zr/Y ratio in the LZO

islands is 8.1, which is

larger

than in the YSZ


was

(nominal 4.26). The

amount of

Sr and Mn in the LZO islands


Mn detected in the

below the detection limits. The amounts of

topmost YSZ surface near and below the LZO islands was
less than 0.3%. Sr and La could not be detected in the
near

very low,

generally

YSZ. Note that the YSZ surface


nanometers

the LZO level

compared

with the

original

grain is lowered by a (cf. Fig. 4.8). This was

few also

181

La2Zr207

Formation

and

02

Reduction Kinetics

Fig.

4.8

Bright

field TEM of LZO island

on

(001) YSZ surface.The sample


zone

was

sin

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


beam. A

axis

parallel

to the electron

magnification

of the upper

right edge

of the island is shown in

Fig.

4.9.

observed in the AFM faceted after the

investigations.

In addition, the YSZ surfaces


treatment.

were case

often
with

high-temperature
a

Again,

as

in the

LSM0 95,
were a

we

found from HRTEM


thin

(Fig. 4.9)
10

that all

investigated

LZO islands

covered with

layer (<

nm)

of material of cubic

symmetry with
zones

unit cell

parameter of -0.5 times the lattice parameter of LZO. The layers

are

found to be

10-15 atomic

inhomogeneous in thickness. Relatively layers) are found at the top of the islands
grains
and the LZO islands is
can

thick

(up

to

where the contact


to be.

between the LSM

supposed
to the

Very
is

thin

regions (1-3
Note

atomic

layers)

be observed at the side walls of the islands.

again

that the transition from the LZO


no

phase

surface

layer

con

tinuous and that

dislocations

can

be

seen.

A-Site Deficient Perovskite


a

(y

1.02).
a

Fig.

4.10a shows

an

AFM

image

of

YSZ surface which

was

sintered with

porous

La0 ss^rg lsMnj 02O3


as

cathode

at 1373K

(1100C)

in air for 2 h. The surface

topography
well
the

is dominated

by

evenly

distributed

rings [32].

The thickness

as

height

of the
in

rings
mor-

increase

rapidly

with

increasing sintering

time. No distinct

changes

182

4.3

Results

+S9
i

l ^

vcv

.3

Fig.

4.9

HRTEM of LZO island surface The image shows the upper


in

right

area is

of the

island shown with


a

Fig
of
a

4 8

(rotated clockwise by 90) The

entire LZO island

covered

thin

layer

cubic

phase

with

lattice constant of -0.5 times the lattice constant

of LZO.

183

La2Zr207

Formation

and

02

Reduction Kinetics

phology

can

be noted with AFM up to 4 h of

sintering.
a

From XPS

measure

ments and HRTEM

investigations

we

found that the

rings

which formed at
defect

early sintering
obtained

times consisted of

Mn-doped
and

YSZ with

high
Mn

density.
over

The atomic concentrations of the islands

were

estimated with TEM-EDX. We

(13.8

0.8)% Y, (78.7
near

1.6)% Zr,
at 1373

(7.4

1.0)%

(average
in

islands, sample sintered for 2 h


substrate shows steps

K).

Note that the surface of the YSZ

the islands which is

clearly
in

see

Fig.

4.10b.

Around the island the surface of the YSZ is lowered with


time

increasing sintering
was

typically prolonged sintering (> h), we found again cube-shaped islands on top of the zirconia rings (Fig. 4.11). The change in morphology towards the cube-shaped islands can be well observed from this image. After
z
in

(cf.

scale bar

Fig.

4.10b). The step size


4

the YSZ

~5nm.

After

nucleation, these islands further grew and exhibited

characteristic cube

shape as (y 0.98).
=

observed
The rate of

in

the

case

of

the

manganese deficient

perovskite
one

growth

of these cube

shaped

islands

was

about

to

Fig.

4.10

AFM mages of
was

(001) YSZ surface


added to the

after

sintering with
area.

La0 85Sr015Mn, 02O3


was

cathode.Mn nitrate

starting powder (LSM098)


YSZ surface

to obtain the nominal

composition, (a)
for 2 h.

AFM image of

larger

The cathode

sintered

184

4.3

Results

Fig.

4.10

(continued) (b)

AFM

image

of

single

island after 4 h of

sintering.

Note the
z

slope

down of the YSZ surface towards the island. The

original

YSZ level is at

=0

nm.

two orders of

magnitude

lower than that of the LZO islands in the


information obtained from the AFM

case

of

LSM0 ggwe

From the

morphological
we a

images

supposed

that these cubic islands consist of lanthanum zirconate.

To prove this

hypothesis,

investigated sample
In

some

of these

samples

with the

HRTEM. Plan-view TEM of

sintered for 4 h reveals that every

large

island consists of several smaller islands

with the AFM

investigations. image.
fee with

(Fig. 4.12), which is in agreement addition, the stepped YSZ surface can be
SAED

clearly

seen

in this

The

[001]

pattern of this sample shows


times the lattice param

intense diffraction

peaks

from the YSZ


a

parent material (Fig. 4.12). The weak

reflections index

as

lattice

parameter -1.98

eter of YSZ. XPS measurements of this

sample

revealed about 4 atomic per diminished within 15


was
nm

cent of La within the surface. The La concentration

of

sputtering.

Note that XPS

probes

the entire surface which

in this

case

only partially
field TEM of
Both island

covered with islands.


a

Fig.

4.13a shows

cross-sectional
12 h of

bright

ring-shaped
show
a

island which formed


at the

during
and
a

sintering.

tips

sharp boundary

top

different contrast.

185

La2Zr207

Formation

and

02

Reduction Kinetics

From HRTEM

images (Fig. 4.13b)


SEAD

it is

seen

that the

tip

consist
was

mainly

of lan

thanum zirconate with small inclusions of from the

c-Zr02.

This

also confirmed

[Oil]

patterns
as

of the islands. The lattice constant of the LZO

phase

was

determined

-2.09 times the lattice constant of the YSZ

parent

material. The deviation from

perfect epitaxy samples

was

-1. Note also the difference

in the LZO lattice constant of the

sintered for 4 h and 12 h, respec

tively.
In addition,
we >

investigated
AFM

the behaviour of interfaces between

(001) YSZ
with

and

LSMV (y
and

1.02).
at

investigations
no

of YSZ surfaces after

sintering

LSM}10
12 h

LSMX16

showed almost
1373 K.

indication for LZO formation up to islands could be

of

sintering

Occasionally, cube-shaped
no

detected after 12 h. HRTEM and SAED gave


tion.

indication for LZO forma

Fig.

4.11
02

Density
cathode
z

sliced AFM

image
nm.

of YSZ surface after

long-term sintering.The
of the
a

LSM!
areas

was

smtered for 10 h. Note the These


areas

typical square-like morphology


also exhibit

at the

level above -250

typical

orientation rela

tionship

with the

(001)

YSZ

single crystal

surface.

186

4.3

Results

Fig.

4.12

Plan-view TEM of YSZ surface.The


are

The dark horizontal lines


dark

Bragg
on

contours.

sample was sintered for The c-Zr02 islands show


can

4 h at 1373 K.
as

clusters of
with the

rings.

Note how the

steps

the YSZ surface

be

clearly

seen

(marked

white

arrow).

The inset shows the

corresponding

SAED

pattern.

Fig.

4.13

(next pages) Bright-field


-7% Mn

TEM of

cross

section of

ring-shaped

island. The

sample was sintered for c-Zr02 which contains


left

12 h at 1373 K in air.

(a)

The lower part of the islands consist of

(referred

to the cation

concentration), (b)

HRTEM of

tip

shown in

(a).

187

La2Zr207

Formation

and

02

Reduction Kinetics

188

4 3

Results

189

La2Zr207

Formation

and

02

Reduction Kinetics

4.3.3

Electrochemical

Properties LSMq 98

Cathodes

impedance spectra were recorded during the heat treatment of La0.85Sr0 ^MrtQ 9803 (LSM0 98) cathodes on (001) YSZ single crystal electro lytes. The spectra were taken at the same temperature during heating and
Electrochemical

cooling. In Fig. 4.14 a typical electrochemical impedance of the La0 85Sr015Mno 9803, air I YSZ system before and after sintering at 1373 K (1100C) is shown in the complex plane. The frequency response of unsin

complex plane over the temperature range of 773 K (500C) to 1273 K (1000C). Also the frequency response of sintered cathodes is similar in the complex plane. In contrast, the frequency response of unsintered and sintered cathodes was completely different. Fig. 4.15 compares the frequency responses of unsin tered and sintered LSMq 98 cathodes in air taken at the same temperatures. It is clear that the phase maxima shifts to higher frequencies with increasing temperature. Note the marked broadening of the dispersion due to sintering, which becomes more pronounced at lower the temperatures [25]. The polari zation resistance Rp is increasingly dominated by the low frequency losses
tered cathodes is similar in the

La0.85^r0.15Mn0.98^3 6
air, 7
=

974 K

20
C4

YSZ

"

not

sintered

<&
Ik

S
o

337
o

10
10k

3k

.107
o
o

^34
o

7
0

V
*=

a)
-10

*e+*p

I.I.

20

40

Re(Z/Q-cm2)
Fig.
4.14

Typical complex plane plot


interface

of

the

electrochemical

impedance

of

LSMq 981 YSZ

obtained at 973 K

during heat treatment in air.The shown measurements (700C) in air. (a) Cathode impedance before sintering.

were

190

4.3

Results

80

-1

La0.85^r0.15^n0.98^3+8
air, r=974K

60 e
V N

sintered at 1373K for 2 h

U^
YSZ
o
o

40
o o

11

3
o

34.

o o

20

"

107

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 small-signal ments at equilibrium potential were in accordance with the R
from EIS measurements,

dc

measure

determined

below

indicating the probed frequency range.


an

that

no

polarization

losses occurred

Fig.

4.16 shows

Arrhenius

plot

from 773 K to 1373 K in air. The


-1000 K
are

conductivity, o~e apparent activation enthalpies, AH^,

of the cathode

below

significantly
are

lower than

AH^

above 1100 K. Note also that


are

AH^

of ae of unsintered and sintered cathodes


tures but that ture

comparable

at

high tempera
in

they dependence of Rp of different samples was similar to the one shown Fig. 4.16, although the absolute values of ce varied within a factor of two.
The influence of the oxygen

rather different at lower temperatures. The tempera

These
ments
sen

partial pressure p0 on oe is shown in Fig. 4.17. data were obtained from impedance measurements and dc measure on one sample during its heat treatment. The temperatures were cho

in order to obtain the pQ

dependencies
partial

where oe exhibited different

activation

energies.

The oxygen

pressure

dependencies

of ce, i.e.

191

La2Zr207

Formation

and

02

Reduction Kinetics

10"
7=779K

50

6
CI
-

10J

102
*

a)
101
10
!-l

10

101

102

103

104

103

u)/(2ix-s-1)
10J
7"=974K

50

10^

101

b)

10l
10

8o

o.o.P..P0.0

-1

10

101

10z

10J

10*

10

m/(2n-s~l)
10J
7= 1173 K

50

B
a
-

io1 10
t

c)
10,-l

oo' i.i..fg.?'.!

10"1

10

101

102

103

104

105

co/(2rc-s_1)
during heat treatment.The spectra were recorded at the same temperature during heating and cooling while keeping the temperature constant during the measurement. Electrochemical impedances shown at
Fig.
4.15

Bode

plots

of

LSMq 98 cathodes

on

YSZ

(a)

779 K

(506C), (b)
IZ I after

974 K

(701 C),

and

(c) T

1173 K

(900C). ()

IZ I before

sintering; (- -) sintering.

sintering; (o) phase angle

before

sintering; (*) phase angle

after

192

4.3

Results

77C
1100
900
decrease of ae

700

500

10'
during sintering

10',0

A//i=182kJ/mol

C4

B
C/3
<u

10,-1

AfT

190 kJ/mol
A//
=

10,-2

90 kJ/mol

10,-3

A//

125kJ/mol

0.8

io3K/r
Fig.
4.16

Arrhenius
room

plot of conductivity
to 1373

ae of

LSMq 9s

cathode.The

sample

was

heated from

temperature

K, held for 2 h, and subsequently cooled.

<5e

<*=

pQ

for the different

temperatures

are

given within

the

figure.

Note the

change of the slopes, m. A selection of the corresponding impedance data of unsintered and sintered cathodes is given in Fig. 4.18. With decreasing pQ the low frequency losses of the cathode increase, independent of the temperature.

193

10

rf^

N
i-t

o
m
=

10"
0.38

0.44

'0-2

0.22

i
>

o
N)

m m
=

0.50
m

10"

0.24

10 ,-3

a c
n
H

S
z
m
=

0.39

10"
O

10"
7=1123 K r=873K

7= 1223 K
m

a)

b)
10"

7= 1123 K

O
*

T=1093K
T= 893 K

to

10 i-5

10^

101

10^

10j
104
103

10U

10'

10^

103

104

103

Po2/Pa

Fig.

4.17

Oxygen partial pressure dependence of electrode conductivity of LSM0 98 cathode.(a) Results obtained during heating of unsintered cathode, (b) Results obtained during cooling from 1373 K. The measurements were obtained with a sample different from the one which results are shown in Fig. 4.15 and Fig. 4.16. The slopes of the curves in the log(K ) versus log(pQ ) m> were obtained
>

from

least-square

fits of the

experimental

data

over

the range indicated with the line.

IO2
unsintered, 7=873 K

10J
E
u

8 io2^
CI
N
-

IO1

101
2.410JPa

8 Pa

10' ,0

---

310Pa

10
102 103
IO4
10u
60
'
"

105Pa

105Pa IO1

io-2 IO2

lO-1

10

101

10 1-1

CO/(27l-S_1)
*

IO3

IO4

IO5

(0/(27I-S_1)
x

8 Pa
\

"

---

310Pa
A

----'-''

S
o

40

105Pa

,-''",'''

00

^^~
\\
\\
00

40

f
9-

20 20
-

\
IO2

10"2

IO-1

10

IO1

IO3 104 b)

(0/(27t-S"1)

a)

(jn/(2n-s~l)

Fig.

4.18

of the electrochemical

impedance

of

LSM098 cathodes.Unsintered

cathodes

at

(a)
CO

873 K

Oxygen partial pressure dependence (600C) and (b) 1123 K (850C).

4
10
x.

sintered, 7= 1093
K
x. X,
x
.

sintered, 7=893 K
*x

IO2

*^

X,

x*

% 10I3
XX^

x"x.

C!
2
^^x
^X>>*.

-^^^-0.5
^X*
Xfc

IO1

o
o

N
14 Pa

^^*xi>.
"

1
---

10
10'
..]
.
. . .

102Pa 3.5103Pa 105Pa


10

2.8103Pa 105Pa

10u
IO4
10"

10' IO3 10L

IO2

10J

10'

IO2

IO3

IO4

IO3

0)/(27t-s-')-h

CO/(27t-S_1)
O
m

80
-----

14 Pa
---

R
H
"v,.*

60

---

.-.;"-* ""iii^ ,''" /

5
^

180)
60
*
^^

80)
/
/
/ K / /

102Pa 3.5103Pa 105Pa

^
/
e-

40
40

"%>

^~*""x^
^"~~^~'

2.8103Pa 105Pa
N
J

'

'

""O 'n
m
/

^-

/
/ /
/ *

H
/ /

20
-

y y
10J IO4

y
IO3

20

to

""

""

^T

10^

10'

IO2

IO-1
d)

10

10'

IO2

IO3

IO4

IO5

c)

G0/(27I-S-')

(0/(27I-S_1)

Fig.
at

4.18

(continued) After sintering


1373 K within the

(1100C) for

2 h in air at

(c)

1123 K

(850C)

and

(b)

at 893 K

(620"C). The oxygen partial

pressures of the measurements

are

given

figures.

4.4

Discussion

4.4
4.4.1
Earlier

Discussion
General

investigations

of lanthanum zirconate formation between LSM and


a

layer of lanthanum zirconate causes the deterioration of the oxygen reduction properties of the cathode. It was concluded from XRD measurements that A-site deficiency in
YSZ led to the conclusion that low

conducting

dense

LSMy may prevent, or at least retard lanthanum zirconate formation between LSMy and YSZ. It was the main purpose of this study to identify the influence
of lanthanum zirconate at the

triple phase boundary (tpb)

upon the oxygen


answer

reduction kinetics of

LSMy/YSZ interfaces.

We further wanted to

the

questions of

the incubation time and the role of the manganese content in the
out here that

LSMy.
experimental approach differs on a number of points from earlier investigations. First, we studied the behaviour of porous cathodes on single crystal YSZ. Using single crystals has the advan tage, that the influence of impurities usually present in polycrystalline YSZ (e.g. Si02, see e.g. [33]), can be eliminated. Porous cathodes are representative of the actual cathode/electrolyte interface in SOFC. Second, actual sintering temperatures and periods were employed, in order to be able to study the electrochemical properties of the (well performing) interfaces. Last, we employed a number of sensitive surface and interface investigation tech niques in parallel to obtain a conclusive interpretation of the nucleation and growth mechanism of lanthanum zirconate between YSZ and
We would like to

point

our

clearly supported the hypothesis of an incubation time [6] with increasing Mn content. Additionally, we have found that the Mn content in LSMy drastically influences both the nucleation and the growth kinetics of LZO at the cathode/ electrolyte interface. From the electrochemical imped
ance

Our

findings

have

measurements

we

have demonstrated that the presence of LZO at the

tpb drastically

influences the oxygen reduction

properties

of the electrochem
can

ical interface. For the first time it has been shown that the AFM

be

suc

cessfully employed to obtain cathode/electrolyte interface.

information about the nanostructure of the

197

La2Zr207

Formation

and

02

Reduction Kinetics

4.4.2

Lanthanum Zirconate Formation

Bulk diffusion limited

growth.

Sintering
(1100C)

of porous

LSM0 95 cathodes

on

(001) YSZ single crystals


in

at 1373 K

in air results almost

immediately

fine-grained, homogeneous layers of La-rich LZO on the YSZ surface (Fig. 4.4a). The reason for the low activation energy for La2Zr207 nucleation
be found in the close lattice match of the The

can

(001) surfaces of YSZ and

pyrochlore structure may be compared to a fluorite structure with one out of every eight oxygen ions missing. If these vacant sites were also occupied, the formula type would be A2B208 instead of A2B207 [31]. From the [Oil] SAED pattern (Fig. 4.4b) we find that the lattice constants of
La2Zr207.
[001] and [010] direction agree with those of pure La2Zr207 from the literature [31,29, 34]. We find a misalignment of the [100]Lzo ax*s
the LZO

grains

in

referred to the

[100]Ysz ax*s

f ~1-

Although we found from powder XRD measurements that the LSM0.95 was single phase, we suppose that traces of La203 were present in the powder. It
is well known that the detection limit of the XRD method is ~3 vol%. Excess

La203

from the Mn-deficient

LSMy

is

chemically

active and reacts immedi

ately at high temperatures with YSZ to form LZO. Nucleation and growth of LZO is facilitated by the use of porous cathodes which allows surface diffu sion of cations and unhampered oxygen exchange with the surrounding

atmosphere.
Let
us

From this information, certain conclusions

can

be drawn about

the mechanism of LZO nucleation and

first consider the

growth (cf. Fig. 4.19). phase diagram of the Zr02-La203 system [34].
La2Zr207
exists and has
a

At

temperatures below

2100 K,

wide solid solution

La203 concentrations, pyrochlore co-exists with Zr02, where a hexagonal lanthanum oxide ss appears at higher La203 concentra tions. Cubic ss of both the CaF2 and T1203 type exist at temperatures above 2200 K. With increasing temperatures, excess La203 may be transported to
(ss) range.
At lower

the interface either

by

surface diffusion of cations

or

by

densation mechanism. The

hypothesis
was

of the second mechanism is


covered with LZO

vaporization-con supported
grains
at the

by beginning

the fact that the YSZ surface of the

rapidly

and/or the YSZ


and its presence

sintering process. The presence of Mn within the LZO layer surface adjacent to the LZO grains was not demonstrated is not expected, because the La is provided from the excess
once a

layer forms, further layer growth is limited by bulk and/or grain boundary diffusion of Zr4+ and/or La3+ across the LZO layer. From our AFM and HRTEM measurements we found that the
La203. Obviously,
dense

198

4.4

Discussion

LZO

layer

grew almost

exclusively

towards the cathode and

only

to

minor

extent

(ratio -10:1)

into the YSZ. Is this tantamount to the statement that the


rate of

bulk

(or grain boundary) diffusion

Zr4+

is

controlling

the LZO

layer

growth kinetics in the early growth state? Brugnoni et al. [35] investigated the LZO layer growth kinetics at the inter face between porous La0 85Sr015Mn03 and YSZ polycrystals at temperatures between 1573 K (1300C) and 1773 K (1500C). By interpolating their data to constant the for obtain 1373 K we layer growth (1100C)
logD
1373 K

/(m

2
s

-19.9, which is in rather close agreement with the

result

we

obtained. Nevertheless,

they
than

measured the LZO


we

significantly higher temperatures


nesses

did, and
et al.

growth kinetics at they obtained layer thick


[35] concluded from
their

in the range of micrometers.

Brugnoni

a)

I-

(001) YSZ
200
nm

b)

Zr

4+

Fig.

4.19

Schematic view of the LZO

layer

formation at the interface of


near

LSMq 95

and

YSZ.(a)

Nucleation of

epitaxial

LZO islands starts

the

LSMq 95 grains.

Growth of

LZO islands takes

place along quent layer growth is limited by bulk diffusion of Zr4+ depending on the distance to the nearest LSMg 95 grain.
the YSZ surface until
a

dense

layer is obtained, (b)

Subse

and surface diffusion of

La3+,

199

La2Zr207

Formation

and

02

Reduction Kinetics

SEM-EDX measurements of the interfacial

region

that the diffusion of

La3+

determining step, as was concluded by others [4] (though these authors used dense diffusion couples), but which is in contradiction to our experimental findings. Both authors found reaction layers which almost completely grew towards the YSZ. Our XPS measurements of the freshly prepared sample (before Ar+ sputter ing) showed that the topmost surface layer was strongly enriched in Zr4+. In through
the reaction

layer

is the rate

addition, HRTEM images indicated the presence of


cubic
and
a

few atomic

phase

on

top of the LZO grains (cf. Fig.


of the

4.4 c). From the

layers of a phase diagram

high resolution images of this surface region with experimentally obtained high resolution images of YSZ, we conclude that the surface layer consists of cubic-stabilized Zr02 (c-Zr02). It is known that La can be dissolved in YSZ up to a few at% [5], which leads to a slight increase of the lattice constants. However, La is not known to stabilize Zr02 in cubic symmetry [34] but it is likely that La3+ and Mn2+/3+ are present in the top most layer. The cubic stabilization may be due to these doping elements and the influence of the cubic LZO lattice facing the c-Zr02 layer. Let us come back to the question whether the LZO layer growth is deter mined by the Zr4+ diffusion through the layer. It is probable that the Zr4+ transport takes place predominantly through the grain boundaries, which are generally 3-5 times thinner than the LZO grains (cf. Fig. 4.5b). Subsequent distribution of Zr4+ takes place by surface diffusion. The mean distance
comparison
between the LSM

(cf. Fig. 4.1), which is about 10 times the mean LZO grain size. Accordingly, the supply of Zr4+ is supposed to be much faster than the supply of La3+ by surface diffusion. This may

grains

is of the order of 1 pm

explain
Zr4+

the appearance of the

c-Zr02 layer
From the

found

on

the LZO

grains:

excess

reacts with

oxygen to intermediate
is

c-Zr02

and later transforms to LZO


it is not

when sufficient

La3+

present.

present experimental data

predictions about the layer growth mechanism at higher temperatures or in a later growth stage. It may be that the mechanism changes as soon as the excess La203 is consumed and, therefore, La3+ must be supplied by a different mechanism.
possible
to make

Surface diffusion limited

growth.

Sintering
(1100C)
on

of porous

LSM0 98 cathodes
a

on

(001) YSZ single crystals


in

at 1373 K

in air results after

few minutes

epitaxial, cube-shaped
images
we

LZO

grains

the YSZ surface. From the AFM and

the TEM

conclude that the LZO islands grow


and the YSZ surface. The most

between the

LSM0 98 grains

interphase striking feature of


as an

200

4.4

Discussion

the LZO islands is its very

clearly

visible cube

shape

on

the

(001) YSZ single


axes

crystal
grains
ance

surface. It is
are

likely
the

that the orientation of the cube


axes

of the LZO

parallel

to

[100] and [010]

of the YSZ surface. The appear

of the island did not


and the
scan

depend

on

the relative orientation between the

sample
as an

direction of the AFM

probe,

i.e. it
we

can

not be

considered

artifact. We would also like to mention that

obtained similar results


can

with

polished

YSZ

polycrystalline samples
when the LZO
was

and that these observations

also be carried out with the SEM. In contrast, Tricker and Stobbs
observed

[17]

epitaxy only

formed

during operation,

other

incoherently. They concluded that an oxygen ion flux in the vicinity of the interface during operation must be controlling LZO nucleation
wise LZO formed

process. Our observations contradict these conclusions.

sharp boundary between the islands the YSZ parent material we conclude that the growth of the LZO islands is controlled by surface diffusion of Zr4+ along the LZO side walls towards the top of the LZO islands. This explains the growth law obtained for the apparent LZO layer thickness, hav, which is clearly different from the growth law of dense layers. An exponent of 2 is expected in Wagner's law, if volume diffusion is rate limiting. Higher exponents are indicative for surface diffusion [36]. LZO islands growth is, therefore, expected to be much faster as in the case where an initial dense layer forms. But even after 12 h of sintering at 1373 K, the LZO layer is not dense and Zr4+ tiansport can still take place by surface diffusion. As soon as the YSZ surface is entirely covered with LZO, further growth is bulk diffusion limited and the mechanism is similar with the important difference that in this case as in the case with LSMq 95, dense layer growth starts at a layer thickness which is about two orders of magnitude larger (~200 nm) compared with dense LZO layers obtained with LSMo.95shape
Nucleation of the LZO islands does not, the
at
as one

From the

of the LZO islands and the

would expect,

occur

where

LSMq 98 grain and the YSZ surface are in immediate contact but it occurs the tpb (cf. Fig. 4.20). Similarly, Clausen et al. [18] has found from TEM
nucleation takes
our

investigations of YSZ-LSM phase boundaries that LZO place at the interface. This does not agree completely with

findings,

but

they

observed LZO islands in

late state of
can

growth (after sintering


be observed. We

at 1573

K)

typically find embryos around the contact sites. The reason for this phenomena can be explained as follows: because the region near the tpb of unsintered LSM grains on YSZ surfaces is highly curved, the free surface energy can be
not

where the actual location of nucleation


four LZO

201

La2Zr207

Formation

and

02

Reduction Kinetics

a)
I-

(001)
200
nm

YSZ

Fig. 4.20 Schematic view of LZO island formation and growth at the interface between LSMo98 and YSZ.(a) Nucleation near the tpb. (b) Growth is limited by surface diffu sion of Zr4+ along the LZO islands. La3+ is supplied from the LSMq 98 grain.

diminished

by decreasing
this

the curvature of the contact. At

relatively

low sin

tering temperatures
(see
and
a

occurs

predominantly by surface
and references

diffusion of cations

textbook about
are

sintering, e.g. [37]

therein). Because Zr4+

likely to form LZO in presence of oxygen, nucleation of LZO nuclei takes place in this convex interface region (cf. Fig. 4.20). Supporting this hypothesis is the experimental fact that the YSZ surfaces were stepped
after
a

La3+

heat treatment

(even

at

low

temperatures

as

1373

K) and that the YSZ

surface

sloped

down towards the LZO islands. The first fact is due to the

slight misorientation of the (001) single crystals, where the second fact is clearly related to the surface diffusion of cations from the YSZ parent mate rial. Further support is given by the HRTEM observation of the LZO islands. These were covered with a few atomic layers of c-Zr02. Although the sam ples were not quenched to room temperature from 1373 K (but only to 1073 K, cf. the experimental description), it seems that the high temperature

202

4.4

Discussion

preserved. A few atomic layers of c-Zr02 are seen on the side walls of the LZO grains, whereas a relatively thick region of c-Zr02 is seen on top of the island. By closer examination of HRTEM images of the island shown in Fig. 4.8 we find that the thickness of the c-Zr02 layer on the side wall does not depend on the crystallographic orientation of the habitus plane. We further observe that the LZO cube surface, which is supposed to be in contact with the LSMq 98 grains during sintering, is covered with c-Zr02 of
situation
was

-10 atomic From

layers (Fig. 4.9) as well. these experimental findings


rate would decrease with

we

would

expect that the LZO island


because the manganese
the

growth
activity
islands

increasing time,
in the

is

supposed

to increase

markedly
we

vicinity of

growth
near

front

of the LZO islands. The concentration of Mn in the YSZ surface


was

the LZO

distinctly below by
TEM
or

1% and

could not detect any Mn in the LZO


no

islands with TEM-EDX. We could also find

manganese

containing precip

itations, either

(although they ing the removal of the porous cathode). These findings the reductive formation of La2Zr207 [21]
AFM

could have

disappeared dur can be explained with

(Lax _xSr )Mn03


=

zZr02 + [(5

5')/2

3z/4]02(g)
(4.3)
In order to

(La1_x_2Sry)Mn03_8. + (z/2)La2Zr207
originated
from the A-site

where the reaction

nonstoichiometry.
reacts with

lower the A-site occupancy and to oxidize the manganese ions

(Mn3+

Mn4+)

in the

perovskite,

La in the

perovskite

Zr02

to form

La2Zr207. In addition, the reductive dissolution (cf. Eq. (4.1)) seems to play to a certain extent.
manganese

of manganese ions in YSZ


Due to the

relatively large

deficiency in LSMq 98, rather substantial amounts of LZO can be expected. Additionally, supply of manganese deficient LSMq98 is ensured because the LZO islands grow towards the unreacted LSMq 98. Accordingly, a decline of the growth rate is not expected until a dense LZO layer forms and further supply of Zr4+ is controlled by grain boundary or bulk diffusion through the LZO layer. Our findings about the stoichiometry of the LZO islands are in excellent
agreement with the results of Clausen
LZO in
et al.

[18]. Y substitutes for La

in the

significant

amounts. This is known to enhance the concentration of

oxygen vacancies
order of

[38] which
at 1173

increases the ionic

magnitude

K) and

conductivity (approximately one transport numbers. Y-doped LZO is

203

La2Zr207

Formation

and

02

Reduction Kinetics

considered

as

mixed
In

p-type and

ionic conductor in air at

temperatures

above -1000 K

[38].

addition, the Zr/Y

ratio in the LZO is about two times

higher
Let
us

than in the YSZ,

indicating

that the YSZ

facing

the LZO must be

enriched in Y.

finally compare the behaviour of LSMq.95 and LSMq 98. In the first case, thin and dense LZO layers are obtained after short sintering periods, whereas in the second case large islands are obtained. We want to address the ques tion why LSMq 98 does not form dense layers immediately, too? This might be due to traces of La203 in the original powder which reacted immediately with hardly any inhibition with the YSZ surface to form LZO. In the case of LSMq 98, only solid state reactions between manganese deficient LSM and YSZ or LZO occur. Accordingly, higher amounts of Mn should further inhibit
the formation of LZO.
Retardation of nucleation and

LSM102
amount

was

prepared

from

delayed growth. Keep in LSMg98 powder by adding

mind

that

the

the

appropriate

of manganese nitrate, i.e. the additional manganese is expected to be distributed on the LSMo98 surface and within the organic part of the

expected that the incorporation of excess manga nese into the perovskite phase takes place to a certain extent when the tem perature is raised. Accordingly, the manganese deficient perovskite grains are doped with manganese and change stoichiometry. Certainly, manganese also diffuses into the YSZ single crystal surface at elevated temperatures. In any case, the manganese activity is raised at the interface between the cathode grains and the YSZ. Similar arguments were given by Clausen et al. [18] who
screen-printing paste.
It is

stated that the

excess

Mn must not to be contained within the

perovskite

to

develop its efficiency in suppressing LZO formation (cf. Fig. 4.21). Although we know from the previous results that Zr4+ heavily diffuses
the YSZ surface towards the

on

tpb

to

decrease the free surface energy of the

interface, it is surprising
after

to see

how the

magnitude

of

transported

YSZ

even

only (2

to

4) h

at 1373 K

(cf. Fig. 4.10a). The result of Zr4+ surface diffu


4.10b. The YSZ diffused towards the

sion is

excellently

seen

in

Fig.

sintering

leaving a easily imaginable that a single LSMX 02 grain was positioned within the zirconia ring before dissolu tion. This can also be seen in SEM images of the interface (cf. Fig. 4.1b). The Zr/Y ratio within the formed Mn-doped YSZ rings is almost equal to the nominal ratio of the YSZ, indicating that the surface diffusion of Y is not sigbehind

neck which formed between the LSM

particle

and the YSZ surface,

lowered and faceted YSZ surface. It is also

204

4.4

Discussion

Fig.

4.21

Schematic view of LZO island formation and

growth at the

interface between

YSZ.(a) Nucleation of epitaxial (Mn)-YSZ starts near the LSM102 grains. Zr4+ and Y3+ diffuse along the surface of YSZ. Excess Mn from the LSMj 02 is incorpo

LSM102

and

rated into the


to form LZO.

sintering
(c)

necks until

La203

forms which

(b)

reacts

with the YSZ

tip

necks

Further

growth

of LZO islands is retarded.

nificantly hindered,

as one

could have concluded in the


no

previous

case

where

the LZO islands contained

Y. Cubic stabilization of the

with the presence of Y. In contrast to the situation with

rings is explained LSMq 98, manganese


takes

dissolution

from

the

perovskite

into

the

YSZ

heavily

place
can

(cf. Eq. (4.1)).


be

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


at 1373 K in

expected (-7%

air) from the thermodynamic calculations of

205

La2Zr207

Formation

and

02

Reduction Kinetics

Yokokawa [20]. These

large

amounts of Mn at the

tpb

may have

beneficial
the inter

effect upon the oxygen reduction and face. Note that the Mn concentration

incorporation properties of

corresponds to the equilibrium concen tration. Higher concentrations could only be obtained by increasing the sintering temperature (which would adversely increase the LZO formation tendency)
The
or

with

non-equilibrium methods,

topographic

information obtained from

ion-implantation [39]. plan-view TEM is in full agree


such
as

ment with the AFM measurements.

Nucleation of LZO islands is also

con

firmed from the

[001]

SAED pattern from the shown in

plan-view
a

(Fig. 4.12).
the SAED

The SAED

pattern

Fig.

4.12b shows

sample superposition of
TEM

patterns from the YSZ matrix, the Mn-YSZ islands, and the LZO
strong reflections
are

nuclei. The

due to YSZ. Its variation of the reflection

intensity
that

is characteristic for the fluorite structure

type.

It further is known

Mn-doping
nm.

of YSZ contracts the YSZ unit cell

slightly.

From the results


=

given by
-0.513

Yamamoto et al.

[5]

we

estimate

decrease of a0

0.514

nm

to

This

change

does not become apparent in the SAED pattern. Sur

prisingly,

the lattice constant of the LZO nuclei is

only

~2 times

larger

than

the lattice constant of YSZ


tern shown in

(instead of
almost

2.09

times).

From the

[001] SEAD pat

Fig. 4.12b,

an

perfect overlay

of both the YSZ and LZO be observed. This indi

pattern
cates

can

be seen; however, the misorientation

can

that the interface between YSZ and LZO nuclei is

although not strain-free. The minimization of the interfacial bly achieved through the slight misorientation of both lattices.
between the two lattices is obtained This value is small, and
as

fully coherent, energy is proba


The misfit
=

(ciLZq/2

aYSZ)/'flysz

4.88%.

accordingly, the mean distance between misfit dislo cations is expected to be large. Indeed, misfit dislocations can be observed in the cube-shaped LZO grains (cf. Fig. 4.8). But in this case, the lattice constant
of the LZO islands
was

estimated to be close to the theoretical value.

During sintering
This leads to
soon as a

at 1373

K, the zirconia rings grow in diameter and height.

further decrease of the Mn concentration in the

the critical Mn concentration

only be maintained by the reductive Eq. (4.3)). This leads to the nucleation of LZO grains on top of the Mn-YSZ rings, as observed in the AFM (Fig. 4.11) and HRTEM (Fig. 4.13). The further growth of these LZO islands was significantly retarded with respect to the LZO islands in the case of LSM0 98. This can be explained with the rate con trolling factor which in this case must be the reductive decomposition of the

perovskite. As is attained, a further Mn supply can decomposition of the perovskite (cf.

206

4.4

Discussion

perovskite,
images of
took

i.e. the

the

supported by the HRTEM tips of the Mn-YSZ rings (Fig. 4.13b). Although LZO formation
supply
of La. This is also

place

at the

tips, relatively large regions

of

c-Zr02 can be

seen.

4.4.3
General.

Oxygen

Reduction Kinetics at LSMn


a

98/YSZ

Interfaces

experimental studies (see e.g. [28, 40-46] YSZ have on the oxygen reduction of Sr- or Ca-doped LaMn03 cathodes on been performed, there is still relatively little known about the actual reaction mechanism at equilibrium potential. It is generally accepted that the overall reaction is composed of a multi-step reaction [45-47]. Adsorption of oxygen
Although
number of

[46], ing

dissociation of adsorbed molecular oxygen

[40,45,48]

and surface diffu

sion of oxygen

species [42, 45, 49] have been considered


of the

to be rate determin

the overall reaction rate. It has been found that the kinetics of the oxygen

reduction is
whereas

morphology of perovskite cathodes, the reaction rate has been found to be essentially proportional to the
literally independent tpb [42].
on

length

of the

It has also been

argued

that the electrode behaviour of

LSM cathodes

02(g) I YSZ system [1], where it has been shown that the dissociative adsorption of oxygen mole cules and/or the surface diffusion of atomic oxygen are rate limiting [50],
YSZ is similar to the behaviour of the Pt,
on

depending comparing
[51].

the

operating

conditions. However,

care

must be taken when

these two systems, because the oxygen

adsorption

process
on

on

oxide materials at

high temperatures impedance

is

completely

different from that

Pt

Our electrochemical

measurements of the

LSMq 98,02(g)

I YSZ

sintering at 1373 K in air and that the frequency response changes markedly (Fig. 4.15 and Fig. 4.16). From the tem R~ we conclude perature dependence of the electrode conductivity, ce that the rate-limiting reaction steps are different at low and high tempera tures. It is suggested that the formation of the LZO islands at the tpb due to
system show that

Rp

increases due to

sintering
oxygen

is the main

cause

for the

change

of the electrode

partial

pressure

dependence

of oe may therefore

properties. The provide more infor

mation about the reaction mechanism.

Cathode microstructure,

conductivity,

and

tpb length.

From

the

SEM

(Fig. 4.1) we see that the perovskite/YSZ interface corresponds to an actual cathode/electrolyte interface of a SOFC. The oxygen activity at the interface can therefore be compared to a
images
of
the

cathode

microstructure

207

La2Zr207

Formation

and

02

Reduction Kinetics

real cell. One

might expect that the electronic conductivity of unsintered cath

odes is insufficient and orders of

magnitude
it

below the electronic conductiv

ity
we

of sintered cathodes; therefore,


are

is

expected

that the

polarization

resistance of unsintered cathodes

below those of sintered cathodes. First,

have shown that the difference in electronic

conductivity

of unsintered

and sintered

LSMy

cathodes is

(cf. Fig. 4.2). Second, from


even a

considerably less than one order of magnitude the conductivity measurement we can see that
as

heat treatment at temperatures

low

as

1223 K

(950C)

is sufficient to

increase the electronic

conclude that the electrochemical

conductivity compared to electronic conductivity has only


because the

unsintered cathodes. We
a

minor influence

on

the

polarization resistance R of sintered cathodes is markedly higher than the polarization resistance of unsintered cathodes, in contiast to what might be expected. Our numerical estimates of the tpb length are in agreement with results reported in the literature from comparable cathode microstructures [42, 49]. We would like to point out, however, that the approach we employed per mits a rather accurate estimation of the tpb length. Similarly, the SEM can be used to obtain this information from electrolyte surfaces, as recently shown by others [52]. It is surprising that the tpb length of LSM0 981 YSZ interfaces reaches its maximum value (-5-106 m/m2) already after -30 min of sintering (cf. Fig. 4.7a). We have observed a similar behaviour for the LSM} 02 cath odes. With increasing sintering time at 1373 K (1100C) the tpb length decreases, although only by about a factor of two within 10 h. There have
properties,
been
some

attempts

in the literature to demonstrate

correlation between the

polarization resistance of perovskite cathodes (see e.g. [52-54]). Despite it is experimentally very difficult to obtain samples where the only difference is the length of the tpb. From the results discussed above we see that increasing sintering times or increasing sintering tempera tures not only influence the microstructure, but also lead to second phase for mation with altered microchemistry at the interface. In addition, one must be aware of the fact that slight differences in the stoichiometry of the LSMy (as it might be the case when using different powders of different grains sizes) may have a pronounced and unexpected (and unnoticed) effect, as we see from the comparison of the three perovskite compositions. It is, therefore, important to characterize the raw materials sufficiently. length

of the

tpb

and the

208

4.4

Discussion

Towards

reaction mechanism of unsintered interfaces.

At

873 K

(600C)

we

find

pQ

dependence

of oe for the unsintered

LSMq 98

cathode

(cf. Fig. 4.17a). In the literature a variety of pQ dependencies can be found (values from 1/4 to 1 have been found for the oxygen pressure exponent; see
references cited

above). Most reported


K is

measurements

were

obtained at tem

peratures between 1073


p0

(800C) and 1273


attributed to

K
a

(1000C).

one-quarter power

reac charge tion, where the dissociative oxygen adsorption obeys the Langmuir isotherm [55]. The same pQ dependence has been often found with Sr-doped LaCo03 perovskites (see e.g. [40]). In contrast to these conclusions we have to assume

dependence

generally

transfer controlled

from

our

EIS measurements that the cathodic reaction at 873 K

(600C)

is not

charge transfer controlled, but that it is controlled by a surface diffusion proc ess. Let us analyse our experimental results presented in Fig. 4.18 a in more
detail.

impedance spectroscopy of solids it is often assumed that a double layer capacitance Cd\ is associated in parallel with the Faradaic impedance ZF(jco) (cf. Fig. 4.22 and e.g. [56, 57]). We have discussed the possible reasons for the occurrence of Cd\, its consequences on the electrochemical impedance, and its order of magnitude elsewhere [58]. Typical values for Cdl are in the range of (1...20) pF/cm2. Usually, Cdl is esti mated by fitting equivalent circuits to experimental data. Unfortunately, this procedure requires an a priori choice of such a circuit which itself influences the result of Cdl. Berthier et al. [59] have presented a method for estimating Cdi without the need to assume an equivalent circuit for the electrode reac tion. The authors have also presented some illustrative examples. We briefly summarize the main concepts in the following. Electrochemical impedance spectroscopy has been considered as a promising tool for identifying complex reaction mechanisms in solid state electrochem istry (see e.g. [56] and references therein). However, the interpretation of spectra is generally difficult and it is further complicated by the influence of the double layer capacitance. There is nowadays no generally accepted method for dealing with this problem. EIS spectra of electrode processes have been interpreted for a long time in terms of equivalent electrical circuits and it has been only recently, where micro-kinetic models have been employed to
In the

theory

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 [58,60-62]. In the general theory of EIS a number of quantities are of interest
some

and

important
the

relations

can

be derived

[63, 64]:

(i)

polarization resistance R of an electrode is a characteris tic measure of electrode performance. Its value corresponds to the small-signal dc resistance of the considered elec trode/electrolyte system. Accordingly, there is no need to obtain impedance spectra if one is only interested in the

polarization resistance. R is defined for arbitrary operating points on the current-overpotential curve, Ip(T|). R shows as the low frequency intercept with the real axis in a complex plane plot of impedance data Z(jco) (cf. Fig. 4.23).

210

4.4

Discussion

-i

7=873K

80

Z(JQ

<N

Zf0<o)

I40
650

ZQa
39 160

*>

1.4

..o

% A1

0
R.

/?c

Ze(0)
R_

40

80

120

160

Re(Z/Qcm2)
Complex plane plot of Impedance Z and Faradaic impedance ZF of unsin 105 Pa. The double layer capaci tered LSMo981 YSZ interface at 873 K (600C).p0 tance Cdi is obtained by applying the method from Berthier et al. [59]. We estimate Cdl 1.34 pF/cm2, Rt 7.32 Q cm2, Re 3.42 Q cm2, and Rp 141 Q cm2. Both Z and ZF are shown with the electrolyte resistance Re subtracted.
Fig.
4.23
=
=

(ii)

charge-transfer resistance Rt is a further important quan tity. The well known exchange-current density, i0, is related to Rt by i0 RT/(2F) 1/Rt. However, Rt is defined for arbitrary operating points, i.e. overpotentials, whereas i0 must be considered as an steady-state quantity [58]. Unfortu nately, Rt is not directly accessible from electrochemical measurements, but it must be extracted from EIS data by esti mating the associated double layer capacitance Cdl (see Fig. 4.23 and Refs [58, 59]).
The
=

(iii) The difference between the polarization

resistance and the

charge-transfer

resistance is attributed to the concentration


=

polarization, Rc
to chemical

Rp Rt. The origin of Rc


-

can

be attributed
or

processes
on

on

the electrode surface,

to mass

transport processes

the electrode surface 'or in the gas

phase.

211

La2Zr207

Formation

and

02

Reduction Kinetics

(iv) Once Cdl and Rt


can

are

known, the Faradaic impedance

be obtained from the

Z(jco)

raw

data. It is

ZF(jco) important to

dynamic properties of an electrode/elec trolyte system are entirely described by ZF(jco), and not by Z(jco). A discussion of EIS data should, therefore, always be performed on the ZF(jco) data (cf. Fig. 4.23).
understand that the
We
now

apply

these concepts to the

present data. Fig.

4.23 shows both the

impedance ZF(jco) of the LSM0 98 cathode in oxygen at 873 K. It is readily seen that the polarization resistance Rp is not dominated by the transfer resistance Rt, but that Rp is controlled by a concentration polarization Rc. Therefore the idea of a charge transfer controlled reaction must be abandoned. The value for Cdj was esti
electrochemical

impedance Z(jco)

and the Faradaic

mated

as

-1.3

pF/cm2 and

it

was

virtually independent of the


we

oxygen
an

partial

pressure. This result is in agreement with what

expect for

unsintered

(i.e. unbonded) interface, where


about 70%

we

guess the actual electrode /electrolyte

coverage to be less than -10%. After

sintering,

i.e. when the contact


to be about
one

area

is

(cf. Fig. 4.7a),

we

expect the value for Cdi

order of

magnitude higher. We would like to point out that we understand the origin of the double layer capacitance to be entirely caused by the contact of an elec tronic conductor (the perovskite grains) and a dielectric material (the YSZ single crystal). We neither interpret the double layer capacitance as a "pseudo-capacitance" [65], nor is it ascribed to the heterogeneous electrode reaction [1]. The dynamics of the oxygen reduction are completely described by the Faradaic impedance, and it is this contribution in which we are actu ally interested [64]. More information about the type of the concentration polarization is there fore obtained by looking at the frequency dependence of |ZF|. In the log(|Z|) vs. log((o) plot of Fig. 4.18a a slope close to -0.5 is found. This is better seen from the numerical derivatives of log(|Z|) and log(|ZF|) with respect to over a broad log(co) (Fig. 4.24). |ZF| is approximately proportional to corange of frequencies even in pure oxygen atmosphere. With decreasing pQ the concentration polarization increases and |ZF| is almost perfectly propor 8 Pa (Fig. 4.24). tional to co"1/2 from 10 Hz to -5 kHz at pQi It is well known that at high frequencies under surface diffusion control of atomic species, the following holds (see e.g. [66], or [67])
=

212

4.4

Discussion

T=873K

1
JO

-0.2
B
n

#
S

pn u2

=105Pa
D a

8
i

88o0

^
CN

-8 Pa

oo0

aa

-0.4

po2"8Pa

*.g

oSQV0
D

-0-6

. ...^ /.
a

g1

-0.8

ZF(j(D)
ZCjco)

-1.0

10"1

10

101

102

103

104

105

Q)/(2tc-s"1)
Fig.
Frequency dependencies of IZ I and IZFI of the unsintered LSMq 981 YSZ interface at 873 K (600C).The Faradaic impedance ZF is obtained as described in the
4.24
text and the

partial pressures are given within the figure. decreasing impedance measurements with increasing fre quency. At high frequencies |ZF| should reach its limiting value Rt, and therefore the frequency dependence of |ZF| should diminish. Generally, this is only partially the case due to the influence of the electrolyte impedance upon the electrode impedance at high frequencies.
legend of Fig.
4.22. The oxygen

Note the

accuracy of the

ZF(j)

Kwaf1/2x(l-j)

RT
=

\n F

CqJ2D

a>1/2x(l-j)

(4.4)

species, C0 is its equilibrium surface concentration, Kw is called the Warburg constant, and the other symbols have their usual meaning. Obviously, the experimentally determined to dependence of |ZF| supports the hypothesis of a surface
diffusion controlled kinetics. follow the
a

where D is the surface diffusion coefficient of the mobile

By

contrast, it has been

p02

dependence

if surface diffusion is rate

argued that oe should limiting [40, 68]. But at


were

same

time it should be mentioned that those results

obtained for the

213

La2Zr207

Formation

and

02

Reduction Kinetics

Pt,

Oz(g)

I YSZ system. We know that it is

misleading

to

use

results obtained

for noble metal/solid

electiolyte systems directly


e.g. at 1123 K

for the

interpretation
3/8 a

of

perovskite cathodes.

depend above -102 Pa (Fig. 4.17a). By consideration of ZF(jco) and ence of oe at p0 10 Pa if is seen mat the polarization resistance Z(jco) at p0 Rp is to a large extent due to the charge transfer resistance Rt (Fig. 4.25). With decreasing Pq the concentration polarization Rc increases, but the contribution from Rt remains significant. At pQ lower than 10 Pa, surface diffusion becomes dominant as described above, although less pronounced in contrast to the sit
we

At

higher temperatures,
=

(850C),

find almost

pQ

uation at 873 K

(600C).

At pQ

5 Pa

co-

dependence

of

|ZF|
a

is found

from -100 Hz to -5 kHz. The pQ pressures is in


tion between

dependence

of ae at low oxygen

agreement with this observation. We conclude that

partial competi

charge

transfer and surface diffusion dominates the electrode

behaviour at oxygen

partial

pressures between

(103...105)

Pa and

tempera-

......

7= 1123 K

II
II

rn

i
1 1

Z(jw)

L-H /?,

1- z80

S
o

a
N N

Zp(J<B)
3k
,

XZ,<joJ)

I3k#

#750

oooOoooOOoVS0
*t

45k

*p_
1 1

12

Re(Z,
Fig.
4.25

ZF/(a-cm2)
=

unsintered

Rt

Complex plane plot of Impedance Z and Faradaic impedance ZF of the LSM0 981 YSZ interface at 1123 K (850C). We obtain Cdl 5.1 pF/cm2, 2.17 Q cm2, Re 0.32 Q cm2, and Rp 4.88 Q cm2. Both Z and ZF are shown with
=
=

the

electrolyte

resistance

Re subtracted.

214

4.4

Discussion

partial pressures below 102 Pa, surface diffu sion of atomic oxygen becomes rate deternuning again, as at lower temperatures over the entire oxygen partial pressure range. Note that we have assumed that atomic oxygen species are diffusing and that the preceding reaction steps, i. e. adsorption and dissociation, are not playing a significant role in the overall reaction path. Let us consider the conse quences of these assumptions. Only if the elementary reactions are in
hires above -1100 K. At

oxygen

sequence,

can we

expect that the slowest


in

reaction

step determines the overall

reaction rate. But, surface diffusion of atomic oxygen and dissociation of oxy

parallel on the perovskite surface. Obviously, if the dissociation rate near the tpb is much slower than the surface transport rate towards the tpb (which is normally the case a high temperatures), the overall reaction will be dominated by the faster supply rate, i.e. the surface diffusion
gen molecules
occur

step. This
cathodes
were

is in

agreement with the results obtained with unsintered LSMq 98

on

YSZ.

By
the

contrast, if

we

assumed that molecular oxygen

species

perovskite surface, we would expect that the necessary dissociation step near the tpb (before the incorporation step) would be rate limiting, which is experimentally not observed. It is finally seen from the complex plane plot in Fig. 4.14 a that the low frequency part has no circular shape, but that the impedance starts as a straight line with almost a -135 angle with respect to the real axis. This is observed over a broad range of tem peratures and may be explained with the phenomenon of spherical surface diffusing on
diffusion

[69].

Influence of

sintering

on

electrochemical

1373 K for 2 h in air,

we

still find almost

properties. After a dependence pQ

sintering

at

of ae at 1223 K

(950C) (Fig. 4.17b). The change of the oxygen partial pressure dependence

readily explained by oxygen gas diffusion in the electiode pores [41]. In the complex plane a second semi-circle develops (Fig. 4.26) at low frequencies (from 1 mHz to -1 Hz) with decreasing pQ The resistance
is
.

towards pQ

related with this low

showed almost

no

frequency dispersion was proportional to temperature dependence from 1223 K to 1273 K,


partial
=

pQ

and

which is

distinctive for gas diffusion limitation. The contribution from gas diffusion

decreasing temperatures. < At T 1123 K (850C) it became apparent (but not significant) at pQi 10 Pa. At T 1123 K (850C) and T 1093 K (820C) a p* dependence of oe is found at high oxygen partial pressures. With decreasing pQ a slight change towards a pQ dependence is found. This change is also shifted to lower
was
= = ,

shifted to lower oxygen

pressures with

215

La2Zr207 Formation

and

02

Reduction Kinetics

ou

r=1223K

40
~

s
o

CI

?5
i

20

\
_J

P02

93Pa

_J

20

40

60

80

100

Re(Z/Q-cm2)
Impedance Z of sintered LSM0 981 YSZ 1223 K (950C) and low oxygen partial pressures.The numbers within denote the frequencies in Hz. The frequency range was limited to 20 mHz.
Fig.
4.26

Complex plane plot

of

interface at the

figure

decreasing temperatures (cf. Fig. 4.17b). It would be most straightforward to conclude from the pQ dependence of oe that a competition between charge transfer and surface diffusion exists, as is
oxygen

partial

pressures with

the

case

for the unsintered interface. However,

we

have shown that islands of

during sintering (cf. Fig. 4.6) and we know that the frequency response of sintered LSM098/YSZ interfaces is significantly different from that of unsintered interfaces (Fig. 4.15). It is, therefore, obvious
lanthanum zirconate formed
to ascribe these

idea,

we

changes further analyse

to the presence of the LZO islands. Based

on

this

and discuss the

impedance

results of the sintered

interface.
Towards reaction mechanism of sintered interfaces. both the

Fig.

4.27

shows of

a a

complex plane plot of sintered LSMq 981 YSZ


shows almost
a

impedance

an

the Faradaic

impedance
At

interface at 893 K

(620C)

in oxygen. The 20

spectrum

perfect quencies, ZF displays a -45 angle

semi-circle at low

frequencies (<
(cf.

Hz).

high

fre

with the real axis

inset in

Fig. 4.27). Rt

216

4.4

Discussion

is

extremely low, therefore the overall reaction rate is limited by concentra tion polarization, as in the case before sintering at 873 K (600C) (cf. Fig. 4.23). Let us now again analyse the co dependence of |ZF|. If the reaction was surface diffusion limited,
a

clear

co

Fig.
can

4.28 it is

seen

that this is not

dependence should be noticeable. From undoubtedly found. Nevertheless, a co~


frequency range.
1 kHz to 20

be observed from -1 kHz to -10 kHz, which is also reflected in the -45 the real axis in this
It
seems

angle between ZF and

that the

co

dependence
quency
ent

from the unsintered cathode is contained within the

spectrum of
a

the sintered cathode

(compare

from

co

kHz). The stronger fre


differ
to

dependence of |ZF|

between 10 Hz and 500 Hz indicates that

process than surface diffusion must be

contributing
is
a

the overall

electiode resistance.
A

slope

of -1 in the

log(|ZF|)
chemical

versus

log(co) plot
on

clear indication of
surface

first-order

(electro-)
means

reaction

the

perovskite

[64].

"First-order"

that

single
1

adsorbed

species
1

is relevant and

responsi-

200

7=893K

18

<<T

100

,6

S
C!
0

51/

30 283.
.

/-26k

ZQa

2
730

\/0.4'

.*

10

1.5k

o%

-100-

//v
0 10
20

30

4()

100

200

300

400

500

Re(Z/Q-cmz)
Fig.
4.27

tered

Complex plane plot of Impedance Z and Faradaic impedance ZF of the sin LSMq 981 YSZ interface at 893 K (620*^) in oxygen.The interface was sintered in
set

air at 1373 K for 2 h before

data

is

shown

in
=

cooling to measuring temperature. A Bode plot Fig. 4.18d. We obtain Cdl 5.5 pF/cm2, Rt
=

of the
4.5 Q

same

-cm2,

Re

2.5 Q

-cm2, and Rp

455 Q

cm2.

217

La2Zr207

Formation

and

02

Reduction Kinetics

ble for the electrode

dynamics.
are

Due to

coupling

between surface diffusion


are

and the chemical reaction, i.e. the relaxation between -1 and -1/2

frequencies

too

close, slopes

expected. This is what is seen in Fig. 4.28a and what gives rise to the "depressed" semi-circle, i.e. that the semi-circle has its centre below the real axis (cf. Fig. 4.27). We now would expect that a slope of -1 could be reached upon lowering the oxygen partial pressure. Fig. 4.28b 0 8 behaviour 10 Pa. It is clearly seen that a a) shows the analysis for pQ predominates over more than one order of frequency magnitudes. This sup ports the hypothesis that surface diffusion is in competition with a chemical reaction on the cathode surface. In addition, by comparing the graphs in Fig. 4.24 with the graphs in Fig. 4.28 it is seen that the relaxation frequencies contained within the surface diffusion process are spread over a wide range of frequencies, in particular at low p0 It is concluded therefore that the sur
'

face diffusion process interferes with the chemical process in the spectrum
and therefore neither
a

distinct (o~

dependence

nor a

distinct co"

depend-

s
11

r=893K,/> u2
o
o o

=105Pa
o

/""Xy

3,
60

-0.2

JD
'O

o o

^
<N

-0-4

o
o

E
o

-0.6
o

o O
O

g(izi
o

V
-0.8
w

v.
o

o.'.

**

5
^O

ZpCJW)
Z(ja>)

"

IO"1
a)

10

IO1

IO2

IO3

IO4

10-

CO/(27C-S_1)

Fig.
face

4.28

Frequency dependence of IZ I and IZFI of the sintered LSMq q8 IYSZ inter 10 Pa and (b) at 893 K (620C) at different oxygen partial pressures.(a) pQ
= =

pO2

10Pa.

218

4.4

Discussion

0
o

"-r

Zp(jC0)
Z(jo>)

7-=893K,p0

10 Pa

3,

-0.2-

^
B
o

-0-4
-o

g
o

-0.6

o0 o

-0-8

00o OoO#<

O
i

0
*

-1.0

10 ,-1

10''

101

102

103

104

10!

CO/(27C.S_1)
b)
Fig.
4.28

(continued)

ence

of IZJ is measured. We find

similar behaviour of the sintered interface


-1/2

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

the nature of the chemical step


not

we

conclude that the dissociation step, and


is

the associative
seen

adsorption step,
spectra.

responsible

for the concentration

impedance

in the

It is, however, not

yet clear why the electro


cathodes differs
so

chemical behaviour of unsintered and sintered

LSM0 98
we

strongly, especially question.

at low

temperatures, and

will

finally

address this

Discrimination of reaction steps.


unsintered

We have

seen

that the overall reaction of

by surface diffusion of an atomic oxy gen species at T < 1123 K (850C). With increasing T, a competition between charge-transfer and surface diffusion develops. This is easily explained with the difference in activation enthalpies of surface diffusion, AHd, and

LSMq 98

cathodes is limited

219

La2Zr207

Formation

and

02

Reduction Kinetics

charge-transfer, AHct. From the experimental results it is concluded that AHd is higher than AHct, which is comparable to the situation in the Pt, 02(g) I YSZ system (see e.g. [55, 70]). Obviously, the adsorption and dissociation processes take place in parallel to surface diffusion on the cathode surface close to the tpb [42]. Furthermore, the surface diffusion rate of Oad towards the tpb is much larger than the direct supply rate of Oad from the adsorption/dissociation near the tpb (Fig. 4.29a). We assume that the surface diffusion coefficient of Oad on LSM is in the same order of magnitude as for Oad on Pt [66]. Accordingly, we find that the Nernst diffusion layer thickness 8, i.e. the distance where perturba tions of Oad near the tpb are propagated, is in the order of (50 to 150) nm at temperatures between 823 K (550C) and 1273 K [58]. The supply of ofd within 8 is realized by the surface diffusion process of atomic species and to a

LSM

Pore

O8" ^ 0*-(ad)

(D

|
(4)
e~
^

(2)

^^
,

02(g)

O5- zl
(3)

0f"(ad) ^^

O5"

YSZ

o2-

Fig. 4.29 Model of the oxygen reduction interfaces.(a) Oxygen adsorbs (1) on the

at unsintered

and sintered

LSMq 98/YSZ
step (2)
is

LSM surface. The dissociation

expected
O
at
are

to be slow. Both the

transfer. The LSM surface above the

adsorption tpb

and dissociation
acts
as a

step

are

coupled

reservoir for atomic oxygen

the

supplied by tpb. Note that

surface diffusion

(3)

and

the Nernst diffusion

finally layer 8 is

electronated and
in

charge species. incorporated (4)

with

expected

to be in the order of

100

nm.

220

4.4

Discussion

LSM

Pore

O8"

ofrCad)

LZO

0^

offCad)

2<g)

e~

O8"

YSZ

\
o2at the

i
1

i
I

100

nm

Fig.

4.29

(continued) (b) LZO islands

tpb

hinder both the dissociation

step and the


of

final electron-transfer

step (denoted with the smaller arrows). In consequence, the equi


on

librium concentration of O
O is
on

the LZO is smaller

compared

to the concentration

the LSM above. Surface diffusion of O

from the LSM surface towards the

tpb

considerably retarded,
the direct

because the thickness of the LZO islands is in the order of 8.

Accordingly,

supply

of O

via the

adsorption/dissociation

process becomes

dominant. See the main text for further

explanations.

minor

part by the adsorption/dissociation process. Note that the adsorp tion/dissociation process also takes place near the tpb, but the rate of this

supply is generally far below the surface transport rate (compare with the Pt, 02(g) I YSZ system [50, 58, 64]). It is furthermore important to recognize
that the electrode material

completely

determines the rate

(and type) of oxy

adsorption magnitude for


gen Oxides:
In the
case

and dissociation and that the rates may vary many orders of

different cathode materials (see e.g. for Pt: [71], Au: [72],

[51, 73]).
of sintered

LSM0 98 cathodes,

8 is in the order of the thickness of the

the lanthanum zirconate

(LZO) islands which formed between

LSM0 98

grains

and the YSZ surface after 2 h surface diffusion and


on

Accordingly,

sintering (see Fig. 4.6a and Fig. 4.7c). adsorption/dissociation take place pre
surface

dominantly

the

lanthanum

zirconate

after

sintering

(see

221

La2Zr207

Formation

and

02

Reduction Kinetics

Fig. 4.29b).
cient of

From YSZ it is known that it has

low surface

exchange

coeffi

02(g) [74]. It is expected that the surface exchange properties of LZO are comparable with those of YSZ, because LZO and YSZ are of similar struc ture. Accordingly, the rate of adsorption/desorption near the tpb decreases
due to the presence of LZO. We suppose that the surface diffusion coefficient
of adsorbed atomic oxygen is not altered

drastically. However,

because the

large reservoir of Oad on the LSMq 98 surface is -100 nm apart from the tpb it is expected that the Oad supply by surface diffusion strongly decreases. Accordingly, the direct supply of Oad through the adsorption/dissociation process becomes increasingly significant. This interpretation is in agreement with the experimental observations. It is further supported by the fact that
the differences
in

ae, unsintered and sintered cathodes, increase with

decreasing temperatures (Fig. 4.16). This can be explained with the decreas ing supply rate of Oad by surface diffusion, because 8 decreases with decreasing temperature. Having discriminated the relevant reaction steps of the oxygen reduction at LSM/YSZ interfaces, we give the following model description
(i)

02(g)

adsorbs

on

the LSM surface

according

to

[73] (4.5)

02(g)
where
s

e"

+ s <^

02(ad)
and
e

denotes free

adsorption sites,

electrons from

the electrode.

(ii)

The adsorbed

02(ad) species subsequently turns 02(ad)


+

into O"

e"

20"(ad)
(or LZO) surface, before
reaction
near

(4.6)
it is

(iii) and may diffuse

on

the LSM
in the

finally incorporated tpb according to


0"(ad)
+

charge-transfer

the

e"

Vo<^>Oo + ad.

(4.7)

Although the structure of this model complies with our experimental find ings, we know very little about the rate constants and activation enthalpies involved. However, investigating the properties of this micro-kinetic model similarly as described elsewhere [64], could help to obtain more information from experimental data (cf. [58, 64]).

222

4.5

Conclusions

4.5
The

Conclusions
thermodynamic

study

was

limited

to

the

investigation

of

La0 85Sr015Mny03/YSZ
no

interfaces under

equilibrium conditions,

i.e. where

through the interface was flowing. It is well known [21] that cur rent-produced overpotentials at the cathode influence the oxygen chemical potential in the electiolyte in particular in the vicinity of the cathode grains. It is also known from recent TEM studies that the reverse reaction of Eq. (4.3) can take place to some extent, and that therefore initially formed LZO islands
current

may
the

disappear during

cell

operation [75]. However,


can

we

have shown that the

formation of lanthanum zirconate

be

sintering temperatures
excess

to -1373 K and

effectively suppressed by reducing by doping the La0 8sSr015Mn03


excess

with

manganese. We have demonstrated how the

manganese

controls the nucleation and From the electrochemical


were

growth of the lanthanum zirconate. investigation of the LSMq 98, 02(g) I YSZ system
Dissociation adsorbed oxygen ions,

we

able to discriminate the relevant reaction steps of the oxygen reduction

mechanism at

LSMy/YSZ interfaces.

sur

face diffusion of atomic oxygen, and the

polarization resistance, depending


tions. We believe that
a

on

the

charge transfer contribute operating and fabrication


a

to the

condi

successful identification of

reaction mechanism

requires first a detailed microstructural investigation of the cathode /electro lyte interface. We have also shown that the interpretation of the frequency

straightforward and may lead to ambiguous conclusions. We, therefore, suggest that impedance data not be analysed in terms of equivalent circuits but from a more fundamental perspective.
However,
data
we

dependence

of oe alone is not

believe that

we are

still far from

state and

parameter

estima

tion of the
are

LSMy, 02(g) I YSZ


on

system, mainly because little physico-chemical

available

the interaction of oxygen with


is
even more

perovskite

surfaces. Fur

ther work in this

area

necessary than further electrochemical

investigations.

Acknowledgments.
portation,

The financial

support from the Swiss Department of Energy, Trans

and Telecommunication is

much indebted to Dr. M. Cantoni The authors wish to thank present

gratefully acknowledged. The authors are very who performed most of the HRTEM measurements.

many useful discussions. In


batical from

colleagues in the Chair of Nonmetallic Materials for particular, we are indebted to Prof. Dr. D. Bonnell, on sab
our

Pennsylvania University, and Dr. M. Godickemeier, carefully reading the manuscript and giving valuable comments.

laboratory,

for

223

La2Zr207

Formation

and

02

Reduction Kinetics

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ganite

SOFC-cathodes.

Sci., pages 473-478, Roskilde, Denmark, 1996. Rise National

Laboratory.

229

La2Zr207

Formation

and

02

Reduction Kinetics

230

Part

IV

End Matter

232

Chapter

Outlook

5.1

General
(SSID) have found application in a large number of the future, solid oxide fuel cells (SOFC) are believed to
for
a

Solid State Ionics Devices different


offer
an areas.

For

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

cleaner and

efficient way of energy


is still in

work in this

area.

Outlook

5.2

Identification of Reaction Mechanisms


just
as an

The identification of reaction mechanisms is from intuition,

art as

science.
a

Apart

persistence,

and luck

we

found that

following

certain route

may

help finding

the solution faster. We would

give

the novice the

following

advice:

(i)

Collect
tem

as

much information any

as

possible

related with the sys

before

experimental
can

work is carried out. Note that

much information
is not

often be found in the literature which

directly related with SOFCs or SSIDs. Try to understand what people have done before and realize the essence. This might be difficult at the beginning, but ask people.
(ii)
Do not hesitate to translate your ideas into models.
ment your

Imple

ideas into the computer and the models of others


as a

run

simulations.

Re-implement

the behaviour of the models

starting point. Study by simulation. Play!

(iii) Start modelling seriously. Define what your models should


account for and what is

beyond.

Collect the

priori

known

qualitative understanding from the overall process and recognize the relevant elementary steps. Translate your qualitative models into a quantitative models.
a

information. Obtain

Transform the structural

quantitative

models into

form suitable for

investigation

and

computer

implementation.
Obtain

Implement

the models into the computer.


structure of the models.

(iv) Investigate the

steady-state and iour, as well as the behaviour under limiting conditions, such as high overpotentials, low oxygen partial pressures, and low or high temperatures. Compare your results with those reported in the literature. From simulations, further relation
expressions describing
the

analytical dynamic behav

ships

may become apparent. Use simulations also in order to

check your

analytical

results

(and the implementation). Is the

model structure in

agreement with the reported data? If not,

why?

234

5.3

Modelling

and

Simulation

(v)

Design
from

your

experiments according

to

the

information
in the models
or

obtained above. Estimate unknown

parameters

experimental
(iv)

data. Validate your results. Refine

reject

the models. Note that steps


iment needs

(i)

to

consume

most of the time available. The ideal exper

no

more

thoughts mentioned

single sample. more closely.


than
a

Let

us

consider

some

of the

5.3

Modelling
and model
an

and Simulation

Modelling learning

difficult steps for that the method

implementation are probably considered as the most experimentalist. However, the pain necessary when
can

these tasks is worth the results which

be obtained. We believe

developed

in this thesis

can

be

applied

without

an

extraordi

nary mathematical

Although
cation
as

the

background. method of digital supposed


in the

simulation of electrochemical systems for this

was

introduced
it

more was

than 30 years ago, the method has not found its wide
The
reason

appli

might lie in early days. the fact that considerable programming skills of a low level programming language have been necessary (e.g. Fortran). This has changed these days. The programming environment of Matlab and Simulink offers a high level programming environment which requires only moderate programming knowledge, as every chemist or materials scientist should possess. This ena
bles to focus model
reuse a on

the actual the

equations,

problems. The straightforward implementation extendability of the Simulink models, the possibility

of
to

programming blocks,
can

and the numerical environment of Matlab, make

strong tool. The complete process of modelling, simulation, and parameter


be

estimation

accomplished
the process

within

presented. However,
gation.

simulation must be considered

as

single environment, as we have of modelling, structural investigation, and the first (and mandatory) step of an investi
one

235

Outlook

5.4

Materials and

Samples
(or badly known) parameters
are

Sintered, porous electrodes have been widely employed for kinetic studies.
However,
a

number of unknown

intro

duced in this way. First, the microstructure, i.e. the

length

of the

triple phase
accu

boundary (tpb)

and the

porosity,

can

not be determined with reasonable

quantitative parameter estimation difficult, as we have shown. Second, during sintering a number of undesired processes may occur. It is therefore very important to monitor every single step in sample fabrica
racy. This makes
tion. If
not
one

is not interested in these reactions,

they

must be avoided which is

always possible. Third, even if a large number prepared, their polarization resistance will hardly
two. This is due to the factors mentioned above.

of "identical"
scatter below

samples
a

is

factor of

To circumvent these
most

problems,
a

number of routes have been


cone

proposed.

The

popular

of them is the

use

of

shaped

or

wire electrodes. However,


a

it is doubtful whether

perfect

contact is obtained with

defined

length

of

employ electiodes with simple geometries, i.e. pattern electrodes. This should work without larger problems for metal electrodes which can be sputtered and subsequently etched. The length of the tpb is determined to high accuracy and the influence of porosity (gas phase diffu
the

tpb.

We propose to

sion) rules
the

out.

However,

one

must be

aware

of the limitations of this type of


is limited to

electrode. First, the electrochemical

investigation

potentials

near

equilibrium potential, because of the relatively high electronic resistance of the thin metal stiips. Second, the temperatures of investigation must be somewhat low, in order to avoid a drastic microstructural change of the metal
pattern. However, the
use

of

one or

another type of electiode is determined

by the kind of information one is seeking for. Starting with simpler geometries is good advice. In addition, use single crystal material if ever available and use high quality materials with well known levels of impuri ties. Always check powders for composition.

5.5
Once

Electrochemical
one

Investigation Techniques

understanding of the materials and their interactions during preparation and operation, electrochemical measurements should be attempted. There has been much praise for electrochemical impedance spec
has
a

sound

troscopy (EIS)

as

the tool for identification of electrode reaction mechanism.

236

5.5

Electrochemical Investigation Techniques

However, there has been made


oretical basis of EIS is not

no

significant
reason

progress in the

investigation

of

SSID electrodes. We believe that the

for this lies in the fact that the the

experimentalists. Therefore, it is generally concluded that the interpretation of experimental data is difficult. Furthermore, fitting data to equivalent electrical circuits does not help to understand the physical processes involved in the electrode reac sufficiently
understood

by

the

tion mechanism. In order to make


use

of the powers of EIS, micro-kinetic models of the

assumed electrode reaction mechanism must be actual

employed.
data,
not

In addition, the have shown. the system

system response
one

must be

extracted from

raw

as we

Any

further

interpretation

and

modelling
aware

must be based
can

on

give answers to any question, and that even conventional steady-state current-voltage investiga tions may give some useful and complementary (and possibly accurate) information. But, be aware of the requirements necessary for a successful application of this method. We propose to consider always a number of dif ferent experimental techniques. Certainly, the choice depends on the preced ing theoretical analysis.

response. However,

should be

that EIS

237

Outlook

238

Curriculum Vitae

Personal
Date and Place of Birth: Marital Status:

February 19,1966, in Winterthur,


Married with Denise Swiss

Switzerland

Nationality:
Education
4/82-2/86:
3/1986:

Kantonsschule Aarau

7/86-10/88:

Typus E Military Services


Matura

11/88-10/92:
11/92-2/93:

Student of Materials Science, Swiss Federal Insti

Technology, Abt. Ill D, ETH Zurich Diploma thesis with Prof. Dr. Urs P. Wild, Institute of Physical Chemistry, Department of Chemistry; Topic: "EinzelmolekulspektroskopiePentacen in para-Terphenyl"
tute of

3/93:

Diploma

in Materials Science

6/93-10/93:

Research associate, Chair of Nonmetallic Materi

als, Department of Materials Science,


ETH Zurich

11/93-10/97:

PhD thesis with Prof. Dr. L.

J. Gauckler, Head of

the Chair of Nonmetallic Materials,


of Materials Science, ETH Zurich

Department

Curriculum Vitae

Publications
[I]
A. Mitterdorfer and L.

J. Gauckler. State space modelling of metal electrodes


In U.

in

solid state
W.

electrochemistry.

Stimming,

S. C.

Singhal,

H.

Tagawa,

and

Lehnert, editors, Proceedings of the Fifth International Symposium on Solid Oxide Fuel Cells (SOFC-V), pages 421-430, Pennington, NJ, 1997. PV 97-40, The Electro
chemical

Society,

Inc.

[2]

J. Gauckler. La2Zr207 Formation Between Yttria-Stabilized Zirconia and Lag ^Stq 15Mn03 at 1373 K. In A. Jacobsen, P. Davies, and T. V. and
A. Mitterdorfer and L. C. Toradi, editors, Solid State

burgh, PA,
[3]
terface.
B.

1997. Materials

Chemistry of Inorganic Materials, Research Society.

volume 453, Pitts

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

Zachau-Christiansen, editors, High Temperature Electrochemistry: Ceramic and MetalsProc. of the 17th Ris0 Int. Symp. on Mat. Sci., pages 357-362, Roskilde, Den mark, 1996. Rise National Laboratory.

[4]

J. Gauckler. LSM-Kathoden fur Festelektrolyt-Brennstoffzellen. In Werkstoffwoche '96, Symposium3: WerkstoffefiirdieEnergietechnik, 28A. Mitterdorfer

and

L.

Stuttgart/Germany, mationsgesellschaft mbH.


31.5.96,

pages 460-469, Frankfurt,

Germany,

1996. DGM-Infor-

[5]

A.

Mitterdorfer, M. Cantoni, and L. J. Gauckler. Interphase formation between yt

tria-stabilized zirconia and porous

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241

Curriculum Vitae

242