Solid State Ionics 106 (1998) 255–261

Properties of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 32x (LSCF) double layer

cathodes on gadolinium-doped cerium oxide (CGO) electrolytes
II. Role of oxygen exchange and diffusion

B.C.H. Steele*, Joong-Myeon Bae

Centre for Technical Ceramics, Department of Materials, Imperial College, London SW7 2 BP, UK
Received 6 March 1997; accepted 4 August 1997

Abstract

The area specific resistivity (ASR) of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 32x cathodes on Gd-doped ceria electrolytes has been
measured over the temperature range 325–7258C. The ASR values for single layer porous cathodes could be satisfactorily
interpreted in terms of available data for oxygen surface exchange coefficients. By introducing a thin ( | 1 mm) dense layer
of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 32x (LSCF) adjacent to the gadolinium-doped cerium oxide (CGO) electrolyte the resistivity values
were decreased by a factor of 2–3 times, which could be explained by increasing the effective interfacial contact area
between the LSCF and GGO. However calculations using data for oxygen self diffusion coefficients indicated much higher
ASR values than determined experimentally for these duplex layer cathode structures. It is necessary, therefore, to invoke
enhanced oxygen ion transport through the dense layer which could arise either due to the development of A-site deficient
LSCF material, or too rapid diffusion via grain boundaries.

Keywords: Oxide cathodes; Oxygen surface exchange; Oxygen self diffusion; Solid oxide fuel cells

1. Introduction change kinetics k (cm s 21 ). More recently a publi-

More than 10 years ago one of the authors [1]
emphasised the importance of oxygen exchange
kinetics in determining the magnitude of cathode
resistivity values. Subsequent publications [2–5]
have discussed semi-quantitatively the relative roles
of microstructural features, oxygen surface and bulk
diffusion D* (cm 22 s 21 ), and oxygen surface ex-
*Corresponding author. Tel.: 144 171 594 6744; fax: 144 171
584 3194; e-mail: b.steele@ic.ac.uk
cation by Adler et al. [6] has provided a detailed
quantitative interpretation of the behaviour of porous
mixed conducting oxygen electrodes which inte-
grates information about the various macroscopic
pathways available for the cathodic reduction of
oxygen. Evaluation of the Adler model using ex-
perimental AC impedance data for symmetrical
LSCF / CGO / LSCF cells has shown good agreement
with values predicted by the model using relevant
properties for the LSCF cathode material, providing
credence for this general approach. A number of
important implications follow from this model. In the
context of this paper we shall restrict our discussion

0167-2738 / 98 / $19.00  1998 Elsevier Science B.V. All rights reserved.

PII S0167-2738( 97 )00430-X
256 B.C.H. Steele, J.-M. Bae / Solid State Ionics 106 (1998) 255 – 261

to small cathodic overpotentials ( | 100 mV), which
is the situation prevailing for AC impedance mea-
surements (typical signal amplitudes are 50 mV), and
SOFC operation at 0.7 V.
The more important consequences of this theoret-
ical approach include the following:
(1.1) The steady state electron and vacancy elec-
trochemical potential profiles are depicted schemati-
cally in Fig. 1. The change, dme , at the current
collector / mixed conducting oxide interface will usu-
ally be small as the contact is essentially ohmic.
Moreover, the change in vacancy electrochemical
potential, dmv , at the mixed conducting oxide / elec-
trolyte interface can also be small according to the
observations of Kleitz and coworkers [7,8] using
silver electrodes. Most of the overpotential losses,
therefore, will be associated with the difference
between the thermodynamic potential responsible for
electron transport ( 2 me ) and the thermodynamic
potential responsible for vacancy transport ( mv ). The
origin of this gap (see Fig. 1) can be understood by
considering the equilibrium state of the following
reaction:
1
]
2 O 2 1 V o?? 1 2e 2 ⇒ O ox
i.e. Dms 5 1 / 2mO 2 1 mv 1 2me

Fig. 1. Schematic representation of charge transfer and chemical losses in porous mixed conducting oxide cathodes.
 B.C.H. Steele, J.-M. Bae / Solid State Ionics 106 (1998) 255 – 261
∴dmO 2 / 4 5 2 dme 2 dmv / 2.
This expression indicates that the difference between
dme and dmv / 2 corresponds to the deviation of the
oxygen chemical potential, and thus the degree of
chemical oxidation or reduction of the mixed con-
ductor (i.e. non-stoichiometry). As shown in Fig. 1,
this chemical redox of the electrode provides the
driving force for the reaction of the mixed conductor
with O 2 , transport of molecular oxygen in the pores
of the electrode, transport of molecular oxygen in the
gas phase boundary layer, and ambipolar discussion
of neutral combinations of vacancies and electrons
(or holes) within the mixed conductor. These chemi-
cal processes can contribute significantly to the
potential drop in the electrode. A schematic repre-
sentation of these chemical losses is also depicted in
Fig. 1.
(1.2) Our analysis [6] shows that the non-charge
transfer processes outlined in the previous section do
not contribute additively to the total cell impedance.
Thus ad hoc descriptions of these processes in terms
of equivalent circuit elements are generally not valid.
(1.3) Close to equilibrium the oxygen surface
exchange coefficient k (cm s 21 ) for the reaction:
1
]
2 O 2 1 V o?? 1 2e 2 ⇒ O ox
can be considered as an exchange neutral flux
density (cf. i o , the exchange current density). It
should be emphasised that this reaction is NOT a
charge transfer reaction. It follows that the quantity,
zFk /Vm , where Vm is the molar volume of oxygen in
the oxide, can be viewed as a characteristic electrode
current density ( j e ), although the analogy between j e
and i o , should not be carried too far [6]. However the
expression for j e does provide a qualitative means of
evaluating the importance of surface exchange kinet-
ics in the behaviour of porous electrode structures
[3,4]. For example, taking a typical value for k,
10 27 cm s 21 , yields a current density of 6 mA cm 22 .
It is thus important to increase the effective surface
area of a porous cathode at least 1003 to enable
current densities to be achieved that are of interest
technologically.
(1.4) For mixed conducting electrodes it is also
important to identify the relative importance of
surface exchange and bulk diffusion kinetics. This
can be achieved by defining a characteristic length
257
[3], Lc , which defines the change-over from surface
to bulk control. It can be shown that Lc 5D/k, and
typically Lc has a value around 100 mm [3]. As the
optimal grain size in porous electrodes is around 1
mm, it follows that the kinetics of oxygen surface
exchange will inevitably be the rate controlling step
in the behaviour of oxide cathodes.
An alternative way of evaluating the relative
importance of oxygen surface and bulk kinetics is to
determine the extension (l c ) of the triple phase
boundary (TPB) region due to diffusion within the
oxide cathode material. The following expression has
been derived in recent publications [6,9]
]]]]
l c 5œ(1 2 f )Lc /t s,
where Lc (D/k) is the critical length parameter
expressing the relative importance of bulk diffusion
and interfacial oxygen exchange, f is the fraction
porosity, r is the tortuosity factor and s cm 21 is the
length of the TPB region per unit area, or the pore
surface area for unit volume. Assuming a particle
dimension of 1 mm (s|20 000 cm 21 ), porosity (f )5
0.5, and tortuosity (t )55, then for a typical D/k
value of 10 22 cm (100 mm), the extension of the
TPB region will be about 5 mm. For a poor ionic
conductor such as LSM where D/k has a value of
25
10 at 10008C [6] the extension (l c ) of the TPB
region only amounts to 4310 28 m (ie. a few units
cells). It is also instructive to examine the enhance-
ment to the allowed ionic flux by the incorporation
of a porous electrode (coating) on top of the dense
ion conducting membrane.
The maximum enhancement is given by [9]:
]]]]
œLc s(1 2 f /t ) 1 f
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
rapid surface diffusion fluxes are invoked. For
example if the surface diffusion and oxygen ex-
change coefficients have values of 10 26 cm 2 s 21 and
10 26 cm s 21 , respectively, then the enhancement
factor becomes 45 for the same microstructural
parameters.
It appears that the charge-transfer of oxygen ions
across the interface between a mixed conductor and a
ceramic electrolyte is facile [7,8], and so the optimal
258 B.C.H. Steele, J.-M. Bae / Solid State Ionics 106 (1998) 255 – 261

design for a cathode appears to consist of a thin (|1

mm) dense layer of the electrocatalyst (e.g. LSCF)
next to the electrolyte, followed by a porous layer of
the electrocatalyst to collect and enhance the flux of
oxygen from the gas to the interfacial region. As-
suming a target area specific resistivity (ASR) of
0.15 V cm 2 for the cathode, then [3] it follows that:

R 5 0.15 5 Ld /s 5 LdVm RT /D*(zF )2 .

Thus knowing the oxygen self diffusion D (cm s 21 )

value allows the maximum permitted thickness (Ld )
of the dense interfacial layer to be calculated.

2. Results and discussion

In a companion paper [10] it was reported that

cathode area specific resistivities (ASR) as low as 0.5
V cm 2 could be obtained at 5208C with LSCF /
CGO20 assemblies.
The strategy adopted was to ensure SiO 2 free
electrolyte / electrode interfaces [10], and also to use
a double LSCF cathode layer incorporating a thin Fig. 2. Oxygen surface exchange (k) and selfdiffusion (D 0* )
dense interfacial layer of the mixed conducting coefficients for La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 32x
oxide. Preparation and experimental details have
already been provided [10], and the present paper is
concerned with interpreting the ASR data using
available information for oxygen surface exchange k
(cm s 21 ) and bulk diffusion D (cm 2 s 21 ) kinetics for
LSCF and relevant microstructural parameters.
Using the isotopic exchange diffusion profile
technique [11] on the composition
La 0.6 Sr 0.4 CO 0.2 Fe 0.8 O 32x , the following expressions
have been derived [12] for D and k:

D 5 30.2 exp(21.93 eV/kT ) cm 2 s 21 ........[A]

k 5 0.66 exp(21.09 eV/kT ) cm s 21 .........[B]

These data are depicted graphically in Fig. 2.
The general macroscopic pathways available for
oxygen reduction processes on porous cathode / solid
electrolyte structures were already being discussed
more than twenty years ago [13], and can be
summarised in the accompanying diagram (Fig. 3).
Reaction pathway (j 1 ): Reaction of molecular
oxygen with electrolyte surface (a). Data [14] indi-
Fig. 3. Cathodic reaction pathways for oxygen reduction and
injection into ceramic electrolytes.
cates that this can be neglected for the present
system as k values for CGO surfaces are very low.
Reaction pathway (j 2 ): Dissociative-adsorption of
oxygen molecules and surface diffusion towards the
 B.C.H. Steele, J.-M. Bae / Solid State Ionics 106 (1998) 255 – 261 259

triple-phase-boundary (TPB) designated (b) in Fig.

3.
Reaction pathway (j 3 ): Surface reaction followed
by dissolution and diffusion of oxygen ions towards
cathode / electrolyte interface (c). The solid state
transport of oxygen ions would include normal bulk
lattice diffusion together with contributions from
grain boundary and dislocation core pathways if
appropriate.
It has already been mentioned above that a
quantitative model has been derived [6] to reproduce
experimental data for selected LSCF / CGO struc-
tures. However in the present paper the semi-quan-
titative approach used in earlier papers [3–5] has
been adopted to illustrate more easily the relative
importance of the various parameters used in the
current investigation.
Fig. 4. Area specific resistivities of single and double layer LSCF
Inspection of Table 1 indicates that D/k (Lc ) cathodes on etched CGO20(SSC) electrolytes. A log 2 scale is
values are in between 10 23 and 10 24 cm (1 mm) and provided for comparison between the two data sets.
so much of the LSCF particles (1 mm size) next to
the electrolyte can be involved in carrying the
oxygen flux to the electrolyte interface. It follows high oxygen surface exchange coefficients k (cm s 21 )
that reaction pathways, j 2 and j 3 , (Fig. 2), are both measured for LSCF mixed conductors. These collec-
involved in the cathodic current, and for this situa- tion length values provide good agreement for the
tion a very simplistic model [3–5] provides the single layer electrode ASR between the measured
following expression for the cathode ASR value: (e.g. 0.18 V cm 2 at 7008C) and calculated (0.24
V cm 2 ) values. There is also satisfactory agreement
R c 5 R s 3 w /(2 3 l h ), between the activation energies for the k values
(1.160.1 eV) and electrode resistivities (1.260.1 eV)
where l h is the collection length. As R s 5RTVm / to support the assumption that the rate determining
(zF )2k, values of R e can be calculated for various step in the cathode kinetics is the surface exchange
collection lengths (Table 1). reaction. These results provide another example of
Examination of Table 1 indicates that it is neces- the drawbacks in interpreting electrode kinetic data
sary to propose collection lengths (l c ) of around in terms of classical electrochemical concepts [5].
10–100 mm to account for the observed single layer Also included in Fig. 4 are the data for the double
cathode ASR values reported in Fig. 4. These are layer electrodes, and inspection shows that the
reasonable values taking into account the relatively resistivities are decreased by approximately 2–3

Table 1
Calculations of area specific resistivity values using available surface exchange and diffusion data
T(K) D cm 2 s 21 k cm s 21 D/k mm R s V cm 2 w mm l h mm R c V cm 2 R d V cm 2
973 3.3310 29 1.5310 26 22 4.75 1 100 0.024 1.058
973 3.3310 29 1.5310 26 22 4.75 1 10 0.24 1.058
973 3.3310 29 1.5310 26 22 4.75 1 1 2.4 1.058
873 2.2310 210 3.4310 27 6 18.91 1 100 0.09 14.82
873 2.2310 210 3.4310 27 6 18.91 1 10 0.94 14.82
773 7.8310 212 5.2310 28 1 109 1 100 0.54 365
773 7.7310 212 5.2310 28 1 109 1 10 5.45 365
260 B.C.H. Steele, J.-M. Bae / Solid State Ionics 106 (1998) 255 – 261
times. The simple model [4] would predict a de-
crease of around 2 as all the electrolyte / electrode
interfacial region is now available to carry the
oxygen flux into the electrolyte. However the simple
cubic grain model probably overestimates the grain
area actually in contact with the electrolyte, and so it
is not surprising that the enhancement in cathode
conductivity can be up to 3 times.
Assuming this general approach to be satisfactory,
then it is necessary to calculate the contribution (R d )
to the cathode resistance due to the thin dense mixed
conducting layer. The value of R d is given by:
2
R d 5 LdVm RT /D * (zF ) ,
(where Ld is 0.5 micron) . . . [C] and appropriate
values are listed in Table 1. Clearly, using the
measured self diffusion values, relatively large val-
ues (e.g. 1.058 V cm 2 at 7008C) for the double-layer
cathode are calculated whereas the measured values
are around 0.18 V cm 2 . In fact it is necessary to
postulate diffusion coefficients greater than
10 28 cm 2 s 21 , to ensure that the dense layer does not
make a significant increase to the cathode resistivity.
It is clear, however, that the thin dense layer of
LSCF adjacent to the electrolyte is reducing rather
than increasing the electrode resistivity, and so the
partial oxygen ion conductivity must be higher than
that calculated using the data in equation [A].
A possible explanation for the better than expected
mass transport properties of the dense LSCF is to
suggest that the electrostatic spray assisted vapour
deposition (ESAVD) fabrication technique is re-
sulting in an A-site deficient LSCF. The enhanced
electrode performance already reported [15,16] for
the A-site deficient material may be due to the
presence of an increased anion vacancy concen-
tration which would be associated with larger values
for D 0* . An alternative explanation could involve an
enhanced grain boundary contribution due to the
relatively small grain size of the thin layer associated
with the EASVD fabrication route. Indeed significant
oxygen transport via grain boundaries in LSCF
samples was observed [12] at lower temperatures
when examining 18 O / 16 O isotopic diffusion profiles.
It should also be noted that with a 50 mV signal the
value of D 0* would be not be expected to change
significantly across the dense LSCF layer.
The use of dense mixed conducting layers to
improve the performance of SOFC cathodes has
often been mentioned in the literature (eg. [17–19])
and the present contribution provides a further
example. Finally it should be noted, that as a general
principle, dense mixed conducting layers (e.g. doped
UO 2 , ITO, etc) can also act as diffusion barriers.
Such an application allows the relatively poor
electrocatalyst, doped LaMnO 3 , to be replaced by the
more catalytically active doped LaCoO 3 , which
reacts when placed in direct contact with YSZ.
3. Conclusions
The area specific resistivities (ASR) of single layer
porous LSCF cathodes have been measured and the
values attributed to control of the oxygen flux by the
oxygen surface exchange reaction. The incorporation
of a dense thin (|mm) layer next to the electrolyte
reduced the ASR values by a factor of 2–3. To
account for this improvement in the cathodic be-
haviour it was necessary to propose that oxygen ion
mass transport through the dense layer was enhanced
by either the formation of A-site deficient LSCF or
by rapid diffusion via grain boundaries.
Acknowledgements
The authors gratefully acknowledge financial sup-
port by the Korean government and Johnson Matthey
Co. in the UK.
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