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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-
cation by Adler et al. [6] has provided a detailed
More than 10 years ago one of the authors [1] quantitative interpretation of the behaviour of porous
emphasised the importance of oxygen exchange mixed conducting oxygen electrodes which inte-
kinetics in determining the magnitude of cathode grates information about the various macroscopic
resistivity values. Subsequent publications [2–5] pathways available for the cathodic reduction of
have discussed semi-quantitatively the relative roles oxygen. Evaluation of the Adler model using ex-
of microstructural features, oxygen surface and bulk perimental AC impedance data for symmetrical
diffusion D* (cm 22 s 21 ), and oxygen surface ex- 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
*Corresponding author. Tel.: 144 171 594 6744; fax: 144 171 important implications follow from this model. In the
584 3194; e-mail: b.steele@ic.ac.uk 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 observations of Kleitz and coworkers [7,8] using
is the situation prevailing for AC impedance mea- silver electrodes. Most of the overpotential losses,
surements (typical signal amplitudes are 50 mV), and therefore, will be associated with the difference
SOFC operation at 0.7 V. between the thermodynamic potential responsible for
The more important consequences of this theoret- electron transport ( 2 me ) and the thermodynamic
ical approach include the following: potential responsible for vacancy transport ( mv ). The
(1.1) The steady state electron and vacancy elec- origin of this gap (see Fig. 1) can be understood by
trochemical potential profiles are depicted schemati- considering the equilibrium state of the following
cally in Fig. 1. The change, dme , at the current reaction:
collector / mixed conducting oxide interface will usu-
ally be small as the contact is essentially ohmic. 1
]
2 O 2 1 V o?? 1 2e 2 ⇒ O ox
Moreover, the change in vacancy electrochemical
potential, dmv , at the mixed conducting oxide / elec-
trolyte interface can also be small according to the 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 – 261 257

∴dmO 2 / 4 5 2 dme 2 dmv / 2. [3], Lc , which defines the change-over from surface
to bulk control. It can be shown that Lc 5D/k, and
This expression indicates that the difference between typically Lc has a value around 100 mm [3]. As the
dme and dmv / 2 corresponds to the deviation of the optimal grain size in porous electrodes is around 1
oxygen chemical potential, and thus the degree of mm, it follows that the kinetics of oxygen surface
chemical oxidation or reduction of the mixed con- exchange will inevitably be the rate controlling step
ductor (i.e. non-stoichiometry). As shown in Fig. 1, in the behaviour of oxide cathodes.
this chemical redox of the electrode provides the An alternative way of evaluating the relative
driving force for the reaction of the mixed conductor importance of oxygen surface and bulk kinetics is to
with O 2 , transport of molecular oxygen in the pores determine the extension (l c ) of the triple phase
of the electrode, transport of molecular oxygen in the boundary (TPB) region due to diffusion within the
gas phase boundary layer, and ambipolar discussion oxide cathode material. The following expression has
of neutral combinations of vacancies and electrons been derived in recent publications [6,9]
(or holes) within the mixed conductor. These chemi- ]]]]
cal processes can contribute significantly to the l c 5œ(1 2 f )Lc /t s,
potential drop in the electrode. A schematic repre-
sentation of these chemical losses is also depicted in where Lc (D/k) is the critical length parameter
Fig. 1. expressing the relative importance of bulk diffusion
(1.2) Our analysis [6] shows that the non-charge and interfacial oxygen exchange, f is the fraction
transfer processes outlined in the previous section do porosity, r is the tortuosity factor and s cm 21 is the
not contribute additively to the total cell impedance. length of the TPB region per unit area, or the pore
Thus ad hoc descriptions of these processes in terms surface area for unit volume. Assuming a particle
of equivalent circuit elements are generally not valid. dimension of 1 mm (s|20 000 cm 21 ), porosity (f )5
(1.3) Close to equilibrium the oxygen surface 0.5, and tortuosity (t )55, then for a typical D/k
exchange coefficient k (cm s 21 ) for the reaction: value of 10 22 cm (100 mm), the extension of the
TPB region will be about 5 mm. For a poor ionic
1
]
2 O 2 1 V o?? 1 2e 2 ⇒ O ox conductor such as LSM where D/k has a value of
25
10 at 10008C [6] the extension (l c ) of the TPB
can be considered as an exchange neutral flux
region only amounts to 4310 28 m (ie. a few units
density (cf. i o , the exchange current density). It
cells). It is also instructive to examine the enhance-
should be emphasised that this reaction is NOT a
ment to the allowed ionic flux by the incorporation
charge transfer reaction. It follows that the quantity,
of a porous electrode (coating) on top of the dense
zFk /Vm , where Vm is the molar volume of oxygen in
ion conducting membrane.
the oxide, can be viewed as a characteristic electrode
The maximum enhancement is given by [9]:
current density ( j e ), although the analogy between j e
and i o , should not be carried too far [6]. However the ]]]]
œLc s(1 2 f /t ) 1 f
expression for j e does provide a qualitative means of
evaluating the importance of surface exchange kinet- and for a typical mixed conductor with the values
ics in the behaviour of porous electrode structures given above this expression has a value of about 5.
[3,4]. For example, taking a typical value for k, Significant enhancements can only be obtained if
10 27 cm s 21 , yields a current density of 6 mA cm 22 . rapid surface diffusion fluxes are invoked. For
It is thus important to increase the effective surface example if the surface diffusion and oxygen ex-
area of a porous cathode at least 1003 to enable change coefficients have values of 10 26 cm 2 s 21 and
current densities to be achieved that are of interest 10 26 cm s 21 , respectively, then the enhancement
technologically. factor becomes 45 for the same microstructural
(1.4) For mixed conducting electrodes it is also parameters.
important to identify the relative importance of It appears that the charge-transfer of oxygen ions
surface exchange and bulk diffusion kinetics. This across the interface between a mixed conductor and a
can be achieved by defining a characteristic length 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. Fig. 3. Cathodic reaction pathways for oxygen reduction and
The general macroscopic pathways available for injection into ceramic electrolytes.
oxygen reduction processes on porous cathode / solid
electrolyte structures were already being discussed
more than twenty years ago [13], and can be cates that this can be neglected for the present
summarised in the accompanying diagram (Fig. 3). system as k values for CGO surfaces are very low.
Reaction pathway (j 1 ): Reaction of molecular Reaction pathway (j 2 ): Dissociative-adsorption of
oxygen with electrolyte surface (a). Data [14] indi- 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- The use of dense mixed conducting layers to
crease of around 2 as all the electrolyte / electrode improve the performance of SOFC cathodes has
interfacial region is now available to carry the often been mentioned in the literature (eg. [17–19])
oxygen flux into the electrolyte. However the simple and the present contribution provides a further
cubic grain model probably overestimates the grain example. Finally it should be noted, that as a general
area actually in contact with the electrolyte, and so it principle, dense mixed conducting layers (e.g. doped
is not surprising that the enhancement in cathode UO 2 , ITO, etc) can also act as diffusion barriers.
conductivity can be up to 3 times. Such an application allows the relatively poor
Assuming this general approach to be satisfactory, electrocatalyst, doped LaMnO 3 , to be replaced by the
then it is necessary to calculate the contribution (R d ) more catalytically active doped LaCoO 3 , which
to the cathode resistance due to the thin dense mixed reacts when placed in direct contact with YSZ.
conducting layer. The value of R d is given by:
2
R d 5 LdVm RT /D * (zF ) , 3. Conclusions

(where Ld is 0.5 micron) . . . [C] and appropriate The area specific resistivities (ASR) of single layer
values are listed in Table 1. Clearly, using the porous LSCF cathodes have been measured and the
measured self diffusion values, relatively large val- values attributed to control of the oxygen flux by the
ues (e.g. 1.058 V cm 2 at 7008C) for the double-layer oxygen surface exchange reaction. The incorporation
cathode are calculated whereas the measured values of a dense thin (|mm) layer next to the electrolyte
are around 0.18 V cm 2 . In fact it is necessary to reduced the ASR values by a factor of 2–3. To
postulate diffusion coefficients greater than account for this improvement in the cathodic be-
10 28 cm 2 s 21 , to ensure that the dense layer does not haviour it was necessary to propose that oxygen ion
make a significant increase to the cathode resistivity. mass transport through the dense layer was enhanced
It is clear, however, that the thin dense layer of by either the formation of A-site deficient LSCF or
LSCF adjacent to the electrolyte is reducing rather by rapid diffusion via grain boundaries.
than increasing the electrode resistivity, and so the
partial oxygen ion conductivity must be higher than
that calculated using the data in equation [A].
Acknowledgements
A possible explanation for the better than expected
mass transport properties of the dense LSCF is to
The authors gratefully acknowledge financial sup-
suggest that the electrostatic spray assisted vapour
port by the Korean government and Johnson Matthey
deposition (ESAVD) fabrication technique is re-
Co. in the UK.
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- References
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