SOLID

STATE
ELSEVIER Solid State Ionics 94 (1997) 239-248
loNKs

Behaviour of porous cathodes in high temperature fuel cells

B.C.H. Steele
Department of Materials, Imperial College, London SW7 2BP, UK

Abstract

The applicability of classical liquid electrochemical concepts to porous cathode structures used in high temperature fuel
cells is discussed. It does appear that the performance of molten carbonate fuel cell cathodes can be satisfactorily interpreted
in terms of conventional electrochemical engineering invoking thin films of molten electrolyte distributed in the partially
flooded porous cathode structure. In contrast, the behaviour of porous oxide cathodes deposited on ceramic oxide electrolytes
is dominated by interfacial oxygen surface exchange reactions and diffusive processes. The importance of the characteristic
length term, L, (D*/k), which indicates the change-over from surface to bulk control is emphasised. It is suggested that for
porous oxide cathode structures, in which the grain size is usually around 1 km, the oxygen reduction process will invuriab~y
be dominated by the interfacial oxygen exchange process. For mixed conducting cathodes, chemical processes such as
changes in the oxide stoichiometry, can contribute significantly to the overpotential within the electrode. This can lead to
erroneous interpretations if the I-Vcharacteristics are analysed in terms of conventional electrochemical expressions. Finally
the design of optimised solid state cathodes is discussed and the need for oxygen surface diffusion data is emphasised.

Kewords: Fuel cells; Cathodes; Oxygen surface exchange; Oxygen self diffusion

1. Introduction solid oxide fuel cell (SOFC), would be used with

Fuel cells designed for terrestrial applications are
expected to operate on hydrocarbon fuels for the
foreseeable future and so high temperature systems
offer significant advantages over their low tempera-
ture competitors which require to be supplied with
hydrogen. These advantages include higher ef-
ficiency as steam reforming of the hydrocarbon can
be accomplished within the stack, high temperature
heat for combined cycles or manufacturing processes
and relatively rapid electrode kinetics which can
eliminate the need for noble metal electrocatalysts.
Moreover CO is a reactant not a catalyst poison. It
was originally envisaged that both the high tempera-
ture systems, molten carbonate fuel cell (MCFC) and
coal gasification plants, and some features of present
configurations still reflect these early design consid-
erations even though natural gas is now the preferred
fuel.
Many surveys (e.g. [l-6]) have been published
about high temperature systems and the reader is
recommended to consult these for further informa-
tion about performance characteristics and specific
design details. The present contribution is principally
concerned with contrasting the behaviour of porous
cathodes associated with a liquid electrolyte (molten
carbonate fuel cell) and with a ceramic oxide elec-
trolyte (solid oxide fuel cell). This exercise provides
an opportunity to examine the relevance of classical
liquid electrochemical concepts to technological

0167-2738/97/$17.00 01997 Elsevier Science B.V. All rights reserved

PII SOl67-2738(96)00510-3
240 B.C.H. Steele I Solid State Ionics 94 (1997) 239-248

electrochemical power systems particularly those 2.2. Electrolyte retention and distribution
incorporating solid electrolytes.
A simple thin film model is often used to describe
the behaviour of partially flooded porous electrodes
2. Molten carbonate fuel cell (MCFC) in contact with liquid electrolytes as depicted in Fig.
2a. The gas dissolves into the electrolyte film and is
2.1. General features transported to active sites on the surface of the
electrocatalyst. For low temperature systems PTFE
The general features of the MCFC are depicted in
Fig. 1. The molten salt electrolyte, 62 mole%
L&CO, and 38% K,CO,, is retained in a LiAlO,
particle matrix. The cathode is porous NiO, the Electrolyte
anode is porous Ni and the bi-polar plate material is
usually stainless steel. The rheological properties of
the electrolyte structure depends upon the relative
amounts of molten carbonate and LiAlO,. The size,
shape and distribution of the LiAlO, particles also yc co&/d, = ye cose,/d, = ya cose,/d,
influence the carbonate retention, mechanical prop-
erties and ionic conductivity of the electrolyte struc-
ture. The most effective shape for the LiAlO,
particles appears to be long rods or fibres of submic- NiO Ni
ron diameter and at present the electrolyte structure Cathode Anode
usually consists of about LiAlO,-carbonate (40:60, Fig. 2. (a) Thin film liquid electrolyte/porous electrode structure.
w/w). (b) Fixed volume capillary equilibrium concept.

e-

(H2, CO)
ANODE Wrous Ni (+ Cr)

BUBBLEBARRIER small unlfom w-es

ELECTROLYTE
MATRIX in
600-700°C LiA102 matrlx

CATHODE wrous llthlated

NlO

(02# CO*) t; ~ p;J;

600-700oc

e-

Fig. I. Schematic diagram of molten carbonate fuel cell

 B.C.H. Steele I Solid State Ionics 94 (1997) 239-248 241

serves as a binder and hydrophobic phase to maintain monstration plants around 100 kW have already been
the integrity of the electrode structure and to estab- constructed and tested in the USA and Japan and a 2
lish a stable electrolyte/gas interface. A different MW plant has recently (May, 1996) been commis-
approach has to be adopted for MCFC in that a sioned at Santa Clara, California. However although
‘fixed volume capillary equilibrium concept’ is used performance degradation has been reduced to ap-
to control electrolyte distribution. By correct adjust- proximately 3 mV/lOOO h, there still remain major
ment of the pore diameters in the electrolyte and uncertainties as to whether lifetimes in excess of
electrode phases, an appropriate distribution of the 10 000 h can be obtained particularly at fuel conver-
electrolyte can be achieved (Fig. 2b). At thermo- sion levels above 75% and with operation at elevated
dynamic equilibrium, the diameters of the largest pressures.
flooded pores in the porous components are related
by the equation:
3. Solid oxide fuel cells
y,c0s0~ Id, = y,cosO, Id, = y,cos0, Id,,
3. I. General features
where y is the interfacial tension (liquid-gas), 13the
contact angle of the electrolyte, d the pore diameter Compared to other fuel cells, the solid oxide fuel
and the subscripts indicate the porous components cell (SOFC) possesses many advantages in that it is
(cathode, electrolyte, anode) by their first letter. The a two phase (gas/solid) system. This overcomes
distribution of pores has to be achieved by empirical many of the problems associated with liquid elec-
means as the morphology of the cathode is difficult trolytes such as corrosion, flooding, electrolyte dis-
to predict as the NiO cathode is fabricated from a tribution and maintaining a stable TPB region.
porous Ni plaque which is oxidised in situ. The Moreover ceramic ion conducting electrolytes can in
porosity of the plaque before oxidation is about principle operate over a wide range of temperatures:
70-80% with a mean pore size of 6-10 pm. After 500- 1000°C. Inevitably operation at elevated tem-
oxidation and lithiation, the NiO cathode appears to peratures introduces its own problems including
consist of agglomerates of NiO particles, with the interdiffusion, grain growth of particulate electro-
electrolyte filling the space (micropores) between the catalysts and thermomechanical restraints due to the
particles. The agglomerates are separated by gas- inherent brittleness of the ceramic components.
filled spaces (macropores), which correspond to the However, providing the properties of the relevant
pores of the original metal plaque. It is obviously materials are optimised for the particular design
important to select an economic fabrication tech- configuration, then it has been demonstrated that
nique that can provide reliable control over the SOFC stacks can be operated for longer than 60 000
distribution and size of pores and tape-casting is now h with acceptable degradation values 171. Further
the preferred route. Using this process technology, information on materials selection and performance
cell areas over 1 m2 have been successfully manu- for SOFC systems is provided in recent publication
factured and tested. [4,5,8-lo], as the present contribution is principally
It does appear [2] that the performance of MCFC concerned with solid state electrochemical aspects of
cathodes can be interpreted in terms of conventional SOFC stacks.
electrochemical concepts. The rate-determining step
appears to be the supply of molecular oxygen in the 3.2 Solid state electrochemistty
thin film molten electrolyte to the electrocatalytic
sites on the lithiated NiO cathode. Increasing the An immediate question arises about the relevance
operating pressure increases the solubility of oxygen of the concepts of classical liquid electrochemistry to
and produces an enhanced performance but at the solid state systems. This topic was the subject of an
expense of increased NiO solubility and other unde- international symposium 20 years ago [ 1 l] and is
sirable side reactions such as carbon deposition in being considered again at the present meeting.
the anode. Simple calculations [ 121 indicate that the Debye
Finally it should be emphasised that MCFC de- length is about the same size (- 10.~ “’ m) as the
242 B.C.H. Steele I Solid State tonics 94 (1997) 239-248

mobile electroactive species, and so excess charge is Gas Electrode Gas

apparently confined to the first lattice layer of a solid j2

electrolyte. This leads to a double layer capacitance \

value of the order of 1 p.F cm-2. The behaviour of j3 13
selected specific interfaces, e.g. Au/Na-P-Al,O,, C/
---.I
RbAg,I, appears [12] to be in accordance with this
simple model.
However, the situation for porous gas electrodes
in contact with ceramic oxide electrolytes,
Zr(Y)O,_,,CeGdO,_,, used in solid state tech-
nological devices (fuel cells, oxygen pumps, am-
perometric sensors) is very different. The thin film Fig. 3. Schematic diagram of reaction pathways available for
models developed to interpret the behaviour of gas oxygen reduction in porous solid oxide cathode/ceramic elec-
electrode structures incorporated into liquid elec- trolyte structures.
trolyte fuel cells (see Section 2.2) assume that the
pores of the electrode are partially filled with elec-
trolyte containing gas molecules. The gas molecules Reaction pathway (j,): Dissociative-adsorption of
diffuse to the pore walls where the electrocatalytic oxygen molecules and surface diffusion towards
reaction occurs. The rate-limiting step is usually the the triple-phase-boundary (TPB) designated (b) in
supply of the reactant since the solubility and Fig. 3.
diffusion coefficient of the molecules is much small- Reaction pathway (j,): Surface reaction followed
er than that of the ions. In contrast, for porous by dissolution and diffusion of oxygen ions
electrodes on solid electrolytes the situation for the towards cathode/electrolyte interface (c). The
ionic and molecular fluxes is reversed. The diffusion solid state transport of oxygen ions would include
coefficient for ions (< 10m6 cm* s-r) in the solid is normal bulk lattice diffusion together with contri-
orders of magnitude smaller than that for the gas butions from grain boundary and dislocation core
molecules (- 1 cm2 ss’) in the pores and usually the pathways if appropriate.
rate-limiting step is the interfacial gas/solid ex-
change reaction. Accordingly, a different approach Although there is agreement about the reaction
has to be adopted for the solid state situation, and pathways there remains uncertainty and disagreement
from recent publications [9,13,14] a consensus is about the rate-controlling mechanisms. This in part is
emerging about the micro-modelling treatment of the due to difficulties in separating the relative effects of
Z-V characteristics of porous cathodes on oxide microstructure and electrocatalytic activity. Changes
electrolytes which is discussed in the next section. in the porous electrode morphology can produce
changes over three orders of magnitude in the length
of the triple-phase-boundary (TPB), e.g. lo*-lo5
4. Reduction of oxygen in porous cathodes on cm cm-*. Moreover it is easy to demonstrate that
ceramic electrolytes there must be a spatial extension of the TPB region
to accommodate the high current densities required
4.1. General comments for fuel cell operation.
A major feature of this model is that the overall
The general macroscopic reaction pathways avail- kinetics are dominated by the reaction:
able for oxygen processes on porous cathode/solid
electrolyte structures were already being discussed
more than 25 years ago (e.g. [15]) and can be
to,+ Vi + 2e- = 0”0. (i)

summarised in the following diagram (Fig. 3). The importance of this process in cathodic reduction
mechanisms has already been emphasised [ 16,171
l Reaction pathway (j,): Reaction of molecular and it can be shown [ 16,171 that a characteristic
oxygen with electrolyte surface (a) length, L,, which indicates the change-over from
 B.C.H. Steele I Solid State Ionics 94 (1997) 2.79-248 243

surface to bulk control, is given by the ratio D*lk,

where D* is the oxygen self-diffusion coefficient
(cm’s_‘) and k (cm ss’) is the surface exchange
coefficient. Both these quantities can be determined
by isotopic exchange techniques [18] and Fig. 4 has N l.OOE-02 --
been compiled using data determined at Imperial $ 1 .OOE-03 !’
College. Because of oxygen surface exchange limita- d

tions oxygen fluxes through thin sections of I

c

I
s
La,,,Sr,,Co,,Fe,,,O, are larger than through the 8, l.OOE-05
other materials which possess higher oxygen diffu- E I
O l.OOE-06 --P- LSCF 6/4/Z/6
sion coefficient (ionic conductivity) values.
A collection (Fig. 5) of k and D data compiled
from reference [ 191 suggests that a correlation exists
between these quantities and that values for L, (D/k)
usually exceed 1 Frn with most values clustered
IE-06 1E-05 IE-04 0.001 0.01 0.1 1
around 100 km. This implies that for optimised
Membrane thickness I cm
porous cathode microstructures (i.e. grain sizes
around 1 pm. and TPB lengths greater than lo4 Fig. 4. Calculated oxygen fluxes [I91 through perovskite mem-
branes at 800°C based on expression [ 171 j,, =qI(LV,,RT/
cm ’ ) the oxygen reduction process will invariably
D*z’F’+RTVmIh’FZ).
be dominated by the interfacial oxygen exchange
process (see Eq. (i)) unless the surface transport of
oxygen ions to the TPB region becomes rate-control- For a single grain,
ling. This statement is examined in more detail in j, X 4w = j, X 4w X I,,
subsequent sections.
that is,
4.2. Suqace diffusion cathodes (pathway 2)
j, =.i, X 1,
Assuming this pathway to be dominant then it is with j, ‘v/R,, where 71 is the overpotential and
possible to examine the parameters including the R,=R~‘V,I(ZF)~~ ([ 16,171). Hence
electrode kinetics using the simple array of cubic j, = 7lR, X 2/w X 1h’
grains adopted in Ref. [9]. If the edge of the cubic
grain has a length w cm, the length of the triple The value of the collection length is unknown.
phase boundary (TPB) per unit area=s cm-’ =2/w However available data suggest that useful electrode
-I
cm thicknesses are limited to about 20-30 pm. Allow-
It follows that the macroscopic current density (je: ing for tortuosity and effective catalytic area factors,
A rn- ‘) is given by: then a collection length of 100 p,rn would not be
unreasonable. It is necessary to emphasise that in
j, =,j, X 2/w assigning a collection length of 100 km it has been
assumed that the oxygen surface diffusion coefficient
where j, is the current through the TPB region is not rate-determining.
(A cm--‘) Using data [20] for La,,Sr,,,,MnO, (LSM) as an
For electronically conducting oxide surfaces the example,
predominant oxygen species at elevated temperatures
will be O’-. The flux of ions towards the TPB k = lO~‘cm~ at 1000°C (1273 K),
region will therefore be restricted by the interfacial
oxygen exchange process (j,: A mp2), and so it will V, (molar volume of ABO, oxide)
be necessary to specify an area over which the
= 30 cm3 (typical value),
oxygen ions have been collected by introducing a
collection length, I,. we obtain
244 B.C.H. Steele I Solid State tonics 94 (1997) 239-248
Oxygen Self Diffusion Coefficient. D (cm-’ set-‘)
Fig. 5. Values [ 181 of oxygen surface exchange
K, = 8.314.1273.30/(2.96500)2 X lo-‘.
For w = 1 km and I, = 100 km,
j, = 7.2.35,
indicating an effective R, of 0.42 0 cm*.
This value is within the range (0.2-0.5 fl cm2)
reported for SOFC stack (> 1 kw) cathodes operating
at 1000°C and incorporating La,,,Sr,,,MnO, as the
electrocatalyst.
This simple model not only predicts the correct
order of magnitude for the cathode resistivity but
also indicates a linear relationship between current
density and overpotential which is often observed
experimentally. Implicit in this model is the assump-
tion that the surface exchange coefficient (k) derived
from isotopic oxygen measurements under equilib-
rium conditions can be used in a chemical rate
expression. This is discussed by Adler et al. [31].
Providing the chemical potential driving force is not
too large (e.g. 100 mV which is approximately equal
to a APO2 of 102), then it appears appropriate to treat
k as an exchange neutral flux density analogous to
the exchange current density. Further support for this
approach is provided by the observation that k is
usually only weakly dependent upon the imposed
oxygen partial pressure, and for technological fuel
coefficient (k cm s -‘) and self-diffusion (D* cm* SC’) for selected oxides
cell operation it is also important to ensure that the
overpotential be kept as small as possible (< 150
mV).
If k values are indeed rate-limiting then the
activation energy value for the cathodic reduction of
oxygen should be around 1.4 eV [20]. Chen et al.
[21] report values of 1.42 eV for LSM/YSZ struc-
tures, and using dense sintered samples of
La,,,Sr,,,MnO, cathode material, Youngsblood et al.
[22], have also reported apparent activation energies
around 1.4 eV However other investigators using AC
impedance measurements on porous fine grain elec-
trodes obtain activation energies in the range 1.6-1.8
eV. The isotopic exchange depth profiling (IEDP)
technique used at Imperial College is carried out on
dense sintered samples and the measured k values
obviously reflects the properties of the associated
surface. It is possible that the composition and
behaviour of the surface of fine particles (-1 pm)
will differ from that of the sintered ceramic material
and so k values and the associated activation energy
could be different. It is obviously important to obtain
oxygen isotopic exchange data for La,,Sr,,,MnO,
powders to examine the dependence of k upon
particle size.
An alternative explanation for the different activa-
tion energies may be associated with the oxygen
 B.C.H. Steele I Solid State lonics 94 (1997) Z.i9-248
surface diffusion process. For long collection dis-
tances (> 100 Fm?) the surface diffusion flux to the
TPB could become rate limiting, although it is
unlikely that this mechanism would have such a
relatively high activation energy (-2 eV>.
Further support for a surface exchange limited
process comes from the experiments of those inves-
tigators [e.g. [23,2411 who have shown that additions
of dispersed precious metals can enhance the per-
formance of LSM cathodes as such additions are
likely to increase the relevant k values. It is also
probable that the use of A site deficient LSM [2S]
will enhance the cathodic performance as this materi-
al will have a higher oxygen ion vacancy con-
centration. This will result in a larger oxygen self-
diffusion coefficient (D*) and probably a significant
increase in the oxygen surface exchange coefficient
(k) according to the correlation noted by Kilner [ 181.
It has already been mentioned [19,26] that the
oxygen diffusion coefficient in LSM is very low
(-1O-‘Z cmlsm’ ) at 1000°C and so there is little
opportunity for oxygen ions to enter the ceramic
electrolyte via bulk diffusion (pathway j, in Fig. 3).
It follows that the TPB length must be as long as
possible and Fig. 6 depicts the relationship between
overpotential and TPB length for LSM-YSZ struc-
tures 1131. It is evident that any modification which
increases the length of the TPB region, such as
dispersing zirconia particles in the electrode struc-
ture. can produce improvements to the cathode
behaviour [ 13,271. Thus by using A site deficient
0 0.1 0.2 0.3 0.4 0.5
Ltpb(pm/ pm*)
Fig. 6. Plots (131 of overpotential at 400 mA cm-’ versus length
of TPB per unit area at 850°C. Solid line calculated by model;
pure LSM electrode, (0) composite LSM-YSZ electrode.
24s
material, and increasing the effective TPB length it
has been demonstrated that excellent cathodic per-
formance can be achieved with thick film supported
electrolyte structures and power densities in excess
of 0.6 Wcm-’ at 800°C have been reported 1281.
This pathway (see Fig. 3) effectively increases the
width of the TPB region and results in an enhanced
cathodic performance. As the individual electro-
catalytic grains typically have dimensions around I
pm then due to the D/k (L,) parameter it is likely
that the oxygen surface exchange reaction will still
be rate-limiting. There will also be a limit to the
height over which the surface reaction can provide
oxygen ions for the internal oxygen ion flux due to
resistive losses associated with the bulk oxygen ion
diffusion coefficient [91. The advantages of
mixed conduction have been demonstrated foi
La,, ,Sr,, jCo,, ,Fe,, ,O,(LSCF)/Ce,,,Gcl,, ,O, q5 and
similar cathode structures 1101. and are also clearly
evident in the behaviour of La,,,Sr,, ,MnO, at higher
overpotentials 1291. Recent publications 1303 I ] have
provided phenomenological models for the behaviour
of porous mixed conducting oxide electrodes and
coatings. The following expression is derived in both
these publications:
I, is the extension of the TPB region and Lc (D/k) is
the critical length parameter expressing the relative
importance of bulk diffusion and interfacial oxygen
exchange, d is the fraction porosity. r is the tortuosi-
ty factor and s cm ~-’ is the length of the TPB region
per unit area. or the pore surface area for unit
volume. Assuming a particle dimension of 1 pm
(s-20 000 cm ’ ), porosity (4) =0.5 and tortuosity
(r)=5, then for a typical D/k value of 10~’ cm (100
km), the extension of the TPB region will be about 5
p,m. For a poor ionic conductor such as LSM where
D/k has a value of 10m5 at 1000°C 191 the extension
(lc ) of the TPB region only amounts to 4 X IO ’ m
(i.e. a few units cells). It is also instructive to
examine the enhancement to the allowed ionic flux
(0) by the incorporation of a porous electrode (coating)
on top of the dense ion conducting membrane.
246 B.C.H.Steele I Solid State tonics 94 (1997) 239-248

The maximum enhancement is given by [30]: (a) Charge Transfer Losses

E
j/L, . s *(1 - 4)/r + f#J
-k,
ectronic charge-transfer
and for a typical mixed conductor with the values
given above this expression has a value of about 5.
Significant enhancements can only be obtained if
ionic charge-transfer
rapid surface diffusion fluxes are invoked. For
example if the surface diffusion and oxygen ex-
, ionic migration
change coefficients have values of 1O-6 cm* s -’ and
lop6 cm s-‘, respectively, then the enhancement
factor becomes 45 for the same microstructural
parameters.
It appears that the charge-transfer of oxygen ions (b) Chemical Losses
across the interface between a mixed conductor and a
ceramic electrolyte is facile [32], and so the optimal
design for a cathode appears to consist of a thin (- 1 chemical
pm) dense layer of the electrocatalyst (e.g. LSCF) reaction

next to the electrolyte, followed by a porous layer of

the electrocatalyst to enhance the flux of oxygen
across the interfacial region. This type of cathode
microstructure has been adopted by Bae et al. [33] in
SOFCs operating at intermediate temperatures (500-
600°C)
The continuum models [30,31] can provide an
appropriate description of the Z-V characteristics of
porous cathodes on oxide electrolytes without invok-
ing classical liquid electrochemistry concepts. They
can also reproduce the data obtained by AC impe-
dance measurements and provide an explanation for
the large capacitances (lo-‘-10 Fcm-*) often
measured for mixed conducting porous electrodes. It
may be concluded, therefore, that the electrode
behaviour is dominated by interfacial chemical re-
actions and solid state diffusion. Adler et al. [31]
have discussed the steady state electron and vacancy
electrochemical potential profiles in porous mixed
conducting oxide electrodes. These are reproduced in
Fig. 7, and it will be noted that there is a gap within
the mixed conductor between the thermodynamic
potential responsible for electron transport (- 8,~~)
and the thermodynamic potential responsible
vacancy transport (SILC,).
The origin of this gap can be understood
considering the equilibrium state of the following
reaction:
+O,+V,+2e-=O” 01
gas phase
diffusion
Fig. 7. Thermodynamic potential profiles [30] in electrode as
predicted by model. These profiles show the origin of voltage
losses, (a) charge transfer losses associated with ionic transport
and interfacial charge transfer and (b) chemical losses associated
with diffusion and chemical reaction.
i.e.
so that
This expression indicates that the difference between
S,U~ and &~I2 corresponds to the deviation of the
oxygen chemical potential, and thus the degree of
chemical oxidation or reduction of the mixed con-
ductor. As shown in Fig. 7, this chemical redox of
for the electrode provides the driving force for reaction
of the mixed conductor with O,, transport of molec-
by ular oxygen in the pores of the electrode, transport of
molecular oxygen in the gas phase boundary layer
and ambipolar diffusion of neutral combinations of
vacancies and electrons (or holes) within the mixed
conductor. These chemical processes can contribute
 B.C.H. Steele I Solid State Ionics 94 (1997) 239-248
significantly to the potential drop in the electrode,
although they are not associated directly with the
flow of current.
If the interfacial process is the principal rate-
determining reaction, then assuming the mixed con-
ductor is a good electronic conductor, i.e. [e-l and
[O,], are essentially constant, then
AC = RT In P,, = - 4vF,
i.e.
7 = (RTI4F) ln(PoJ = (RTI4F) ln(V,)*.
As the current flux is proportional to [Vi] it follows
that 7 0~(RTI2F) In i.
Thus although the interfacial reaction dominates it
may be possible to obtain an apparent Tafel relation-
ship, and certain investigators have interpreted their
observation as indicating that the electrode kinetics
are controlled by charge-transfer kinetics rather than
the chemical interfacial reaction.
5. Electrochemistry of anodic reactions
A porous Ni-ZrO, cermet has been adopted as the
anode structure for most technological applications
of SOFC stacks. However the performance of the
Ni-ZrO, cermet is very dependent upon the associ-
ated microstructure, and because of the complexity
of possible reaction mechanisms little progress has
been made in our detailed understanding of the
anode behaviour [34], and so it is not possible at
present to comment on whether classical chemical
liquid state electrochemistry has a role in the inter-
pretation of SOFC anodic behaviour.
6. Conclusions
Thin film electrolyte models developed to interpret
the behaviour of partially flooded porous electrode
structures used in liquid electrostatic fuel cells can
satisfactorily reproduce the characteristic Z-V fea-
tures of molten carbonate fuel cells. In contrast
chemical reaction/diffusion processes appear to
247
dominate the electrochemical behaviour of porous
oxide cathode deposited on ceramic oxide elec-
trolytes producing large effective ‘chemical’ resis-
tances and capacitances. The mechanisms involved
are more similar to the situation for heterogeneous
catalysts than classical liquid electrochemical con-
cepts. At present it is difficult to integrate micro- and
macro-modelling approaches to solid state porous
electrodes because of lack of data about the surface
diffusion of oxygen ions and the applicability of
using k values determined for dense ceramic samples
to particulate electrocatalyst structures. Clearly the
acquisition of oxygen surface exchange data under
dynamic conditions is also an urgent requirement as
the present IEDP technique measure k values at
equilibrium. Although it is possible to propose [3 11
rate-equations based on heterogeneous catalyst ap-
proaches and to suggest [ 161 interfacial resistive
terms such as, RTV,,,lz2F2k, it is clearly necessary to
demonstrate the range of overpotential values (- 100
mV?) for which such expressions are valid.
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