A456 Journal of The Electrochemical Society, 148 共5兲 A456-A462 共2001兲

0013-4651/2001/148共5兲/A456/7/$7.00 © The Electrochemical Society, Inc.

Electrode Reaction of La1Àx Srx CoO3Àd Cathodes on

La0.8Sr0.2Ga0.8Mg0.2O3Ày Electrolyte in Solid Oxide Fuel Cells
Teruhisa Horita,a, z Katsuhiko Yamaji,a Natsuko Sakai,a,* Harumi Yokokawa,a,*
André Weber,b and Ellen Ivers-Tifféeb
a
National Institute of Advanced Science and Technology, Ibaraki 305-8565, Japan
b
Institut für Werkstoffe der Elektrotechnik, Universität Karlsruhe (TH), D-76131 Karlsruhe, Germany

The electrode reaction mechanism was investigated at the porous La1⫺x Srx CoO3⫺d 共LSC兲/La0.8Sr0.2Ga0.8Mg0.2O3⫺y 共LSGM兲
interface (x ⫽ 0.2, 0.3, 0.4). Direct current 共dc兲 polarization curves showed a linear relationship between the overpotential and the
current density at the lower cathodic polarization. The interface conductivity was adopted to examine the activity for oxygen
reduction at the LSC/LSGM interface, which was measured both from the dc polarization curves and the alternating current
impedance. The interface conductivity increased with Sr concentration in LSC and cathodic applied voltage. The higher Sr
concentration of LSC showed the lower oxygen partial pressure dependence of the interface conductivity. The activation energy
for the interface conductivity was almost the same for different Sr concentration of LSC 共137-142 kJ mol⫺1兲. A similar reaction
mechanism is assumed for the examined LSC. The interface conductivity has a relation with oxide ion diffusion in LSC, which can
be the main factor to determine the cathode reaction rates under cathodic polarization.
© 2001 The Electrochemical Society. 关DOI: 10.1149/1.1362540兴 All rights reserved.

Manuscript submitted November 15, 1999; revised manuscript received January 20, 2001.

In the development of solid oxide fuel cells 共SOFCs兲, one of the
recent major targets is a reduction of operating temperature from
1273 K to lower than 1073 K. A reduction of operation temperature
will allow for a decrease in the serious problems of high temperature
operation, such as degradation of cell components. For reducing the
operation temperature, the cell resistance must be minimized in
terms of the following two points: the electrolyte resistance and the
electrode reaction resistance 共interface resistance兲 at the electrode/
electrolyte interface. The electrolyte resistance can be reduced by
preparing a thin electrolyte on a porous electrode support, or by
utilizing the higher ionic conductor than the conventional Y2O3 sta-
bilized ZrO2 共YSZ兲, such as doped CeO2 and doped LaGaO3. This
study correlates with the latter case and utilizes doped LaGaO3 as an
electrolyte. In recent years, LaGaO3-based perovskite materials have
first been utilized for SOFCs by Ishihara et al.1 and Goodenough
et al.2 LaGaO3-based electrolyte showed quite high oxide ionic con-
ductivity around the temperature range of 873-1073 K, and it is
suitable as an electrolyte for the lower operation temperature
SOFCs.3-15 With respect to the electrode reaction resistance at the
electrode/electrolyte interface, cathode reaction 共oxygen reduction兲
resistance shows relatively large values when the cell temperature is
reduced at the cathode/electrolyte interface. Because the cathode
reaction rates significantly decrease with a reduction of operation
temperature,1 the reaction resistance can occupy major parts of the
cell resistance. Therefore, it is desirable to optimize the microstruc-
ture at the cathode/electrolyte interface and to clarify the cathode
reaction 共oxygen reduction兲 mechanism.
La1⫺x Srx CoO3⫺d -based materials 共LSC兲 have been considered as
a cathode for SOFCs because of their high electronic and ionic
conductivity as well as high catalytic activity for oxygen
reduction.16-28 However, it has been reported that LSC tends to react
easily with a conventional YSZ electrolyte at high temperature to
form La2Zr2O7 or SrZrO3. 16,17 Thus, LSC is unsuitable as a cathode
on the YSZ electrolyte in SOFCs. On the other hand, LSC showed
high performance on the LaGaO3 electrolyte at 873-1073 K.1-15 Al-
though LSC has been utilized as a cathode on the LaGaO3-based
electrolyte, the exact cathode reaction mechanism has not been clari-
fied yet under voltage applied conditions. The clarification of reac-
tion mechanism could enable us to suggest the optimum interface of
LSC/LaGaO3-based electrolyte.
In this study, cathode reaction mechanism is investigated at the
* Electrochemical Society Active Member.
z
E-mail: t.horita@aist.go.jp
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porous LSC/LaGaO3 interface in the temperature rage from 873 to
1073 K. The cathode reaction rates were compared with different Sr
doping concentration in LSC.
Experimental
Samples.—Doped lanthanum gallate 共La0.8Sr0.2Ga0.8Mg0.2O3⫺y ,
hereafter denoted as LSGM兲 was adopted as an electrolyte since this
composition shows one of the highest oxide ionic conductivity in
this solid solution.7 Powders of LSGM were prepared by mixing the
appropriate ratio of La2O3, SrCO3, Ga2O3, and MgO. After ballmill-
ing for 24 h in an ethanol solution, the mixed powders were dried
and heated at 1223 K for 5 h in air. Calcined powders were again
ballmilled and pressed into pellets 共16 mm in diam in the green
state兲. The pellets were sintered at 1723 K for 5 h in air. The ob-
tained sintered pellet was a single phase of LSGM without any
impurities by X-ray powder diffraction 共XPD兲. The relative density
was over 97% of the theoretical density. The sintered LSGM pellet
was polished by a diamond paste to obtain the flat surface 共up to
0.25 ␮m grade兲.
La1⫺x Srx CoO3⫺d powders 共x ⫽ 0.2, 0.3, 0.4, LSC兲 were pre-
pared by mixing an appropriate ratio of La2O3, SrCO3, and Co3O4.
The mixed powders were ballmilled for 24 h in water. After drying,
the powders were heated at 1373 K for 5 h in air. The heated pow-
ders were single phase of perovskite without any impurities by
XPD. Powders of LSC were ballmilled again to control the particle
size for preparing the LSC porous cathode structures on LSGM. The
mean diameter of the powders is about 1-2 ␮m in this study by
particle size analyzer 共CIRAS 1064, Quantachrome GmbH兲. The
slurry of LSC powders was prepared by mixing with organic sol-
vents, and it was screen printed on the sintered surface of LSGM.
The screen printed LSC/LSGM samples were fired at 1473 K for 2
h in air. The thickness of the porous LSC cathodes was about 5 ␮m
on the LSGM electrolyte. The morphology of LSC cathode micro-
structures was observed by scanning electron microscope 共SEM兲
共ZEISS DSM940, OXFORD ISIS system兲, before and after the elec-
trochemical tests.
Electrochemical measurements.—The electrical conductivity of
LSC samples was measured by the four-probe direct current 共dc兲
conductivity measurement method. Samples of LSC with different
Sr concentration were pressed into pellets and sintered at 1673 K for
5 h in air. The sintered dense LSC samples were cut in the shape of
bar 共in the size of about 1 ⫻ 2 ⫻ 20 mm兲, and then the dc conduc-
tivity was measured as a function of temperatures 共773-1173 K兲 and
oxygen partial pressures (pO2 ⫽ 0.01-1.0 bar).
 Journal of The Electrochemical Society, 148 共5兲 A456-A462 共2001兲
Figure 1. Schematic diagram of the electrochemical test for porous LSC/
LSGM/Pt single cell.
Figure 1 shows a schematic diagram of the electrochemical test
for cathode reaction at the porous LSC/LSGM interface. A single
cell with a configuration of LSC/LSGM/Pt was fabricated to test the
performance of LSC/LSGM interface. The thickness of the LSGM
electrolyte was 0.08 cm. The geometrical area of the LSC electrode
was 0.28 cm2 共6.0 mm in diam兲 and the same size of Pt counter
electrode was attached on the opposite site of the LSGM. On the
LSC porous cathode, Pt mesh 共no. 80兲 was attached on the top of the
cathode as a current collector. A porous Pt electrode was made by
the screen printing method as a counter electrode. The reference
electrode, Pt, was attached on the counter electrode side at the edge
of the pellet. The dc polarization curves and alternating current 共ac兲
impedance spectra were measured in air using an electrochemical
interface instruments 共Solartron SI 1287, SI 1260兲. Under cathodic
polarized condition, ac impedance spectra were measured as func-
tions of cathodic applied voltage and temperatures. The applied ca-
thodic voltages to the LSC were changed from 0 to ⫺0.4 V vs. the
reference electrode 共from 0 to ⫺0.1 V of cathodic overpotential, ␩兲.
Results
Electrical conductivity of LSC.—Figure 2 shows electrical con-
ductivity of LSC samples as a function of temperatures. With an
increase of Sr concentration in LSC, the conductivity increases
above 1400 S cm⫺1 共for x ⫽ 0.3 and x ⫽ 0.4兲. The temperature
dependence of the conductivity shows a metallic behavior, espe-
cially above x ⫽ 0.3: An increase of the conductivity was observed
with a decrease of the temperatures. The electrical conductivity and
the temperature dependence of LSC are almost consistent with the
reported data.18 No distinct difference of the conductivity was ob-
served among different pO2 examined. Therefore, these values of
electrical conductivity in LSC show mainly the electronic conduc-
tivity 共hole or electron兲, not the oxide ionic one. It should be noted
that the electrical conductivity of LSC at 773-1173 K is much higher
than that of doped LaMnO3, which is a conventional cathode mate-
rials on YSZ.
Microstructure of LSC electrodes.—Figure 3 shows SEM images
of LSC porous cathodes with different Sr concentration on LSGM
used in this study 共Sr doping, x ⫽ 0.2, 0.3, and 0.4兲, after operation
test. These porous cathodes operated for more than 100 h, and
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A457
Figure 2. Electrical conductivity of LSC as a function of temperature.
(䊊: pO2 ⫽ 1 bar, 䊐: pO2 ⫽ 0.1 bar, 䉭: pO2 ⫽ 0.01 bar兲.
showed relatively stable performance within 100 h. The average
LSC grain size is about 1-2 ␮m, and the grains are connected each
other with a high porosity. The microstructure of LSC electrodes
varies slightly with Sr concentration: i.e., smaller particle size can
be observed in x ⫽ 0.2 than can be seen in x ⫽ 0.3 or x ⫽ 0.4. We
compare the electrode performances of these porous LSC cathodes,
though the microstructure of each cathode affects the performance
strongly. The effect of firing temperature on the microstructures will
be reported elsewhere in the near future.
Cathodic polarization curves.—Figure 4 shows examples of ca-
thodic polarization characteristics at the porous LSC/LSGM inter-
face with different Sr concentration of LSC. The cathodic overpo-
tential 共␩兲 in LSC is estimated from the following equation
␩ ⫽ E ⫺ J ⫻ Rb 关1兴
where E/V is the applied voltage between the LSC cathode and the
reference electrode, J/A current, R b /⍀ cm electrolyte resistance
from the ac impedance data. The cathodic polarization characteris-
tics show almost a linear relationship between ␩ and J in the small
␩ region. The polarization current density increases with an increase
of Sr concentration in LSC at the same cathodic overpotential. The
difference of the polarization current density comes from the differ-
ence of the activity for oxygen reduction at the LSC/LSGM inter-
face. Therefore, the higher Sr concentration in LSC promotes the
oxygen reduction. The polarization characteristics can be analyzed
by the Butler-Volmer-like equation in the low cathodic overpotential
range as a first approximation (0 ⬍ 兩 ␩ 兩 ⬍ 0.02) 29,14,15
J ⫽ J o共 nF/RT 兲 ␩ 关2兴
where J o is the exchange current density, n the number of electrons,
F the Faraday constant (9.6485 ⫻ 104 C mol⫺1), R the gas constant
共8.314 J mol⫺1 K⫺1兲, and T the temperature 共1073 K兲. For oxygen
reduction at the LSC/LSGM interface, the formation of one oxide
ion (O2⫺) needs two electrons (1/2 O2 ⫹ 2e⫺ → O2⫺). Thus, the
number of n in Eq. 2 is set as 2 in this study. The solid lines in Fig.
4 show the fitting of Eq. 2 to the measured data. The least square
fitting was performed in the rage of 0 to ⫺0.02 V of the cathodic
overpotential. The fitting lines are almost in a good agreement with
the measured data, though relatively large deviations can be ob-
 A458 Journal of The Electrochemical Society, 148 共5兲 A456-A462 共2001兲
Figure 3. SEM images of porous LSC cathode surface on LSGM electrolyte. 共a兲 x ⫽ 0.2, 共b兲 x ⫽ 0.3, 共c兲 x ⫽ 0.4.
served in the plots of x ⫽ 0.2 and x ⫽ 0.4 at the higher cathodic
overpotential. The characteristics of the LSC electrodes under ca-
thodic polarization seem different from that under equilibrium con-
ditions. This deviation is due to the introduction of ‘‘additional’’
oxygen vacancies in LSC by the cathodic polarization. The higher
concentration of oxygen vacancies can increase the activity for oxy-
gen reduction in LSC. From the slopes of the fitting lines at low
cathodic polarization, the exchange current densities (J o) were cal-
culated for a different Sr concentration in LSC. Table I summarizes
the calculated exchange current densities (J o) of the porous LSC/
Figure 4. Cathodic polarization characteristics at the LSC/LSGM interface.
共1073 K, 䊊: x ⫽ 0.2, 䊐: x ⫽ 0.3, 䉭: x ⫽ 0.4, solid lines indicate the
fitting curves兲.
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LSGM interface with different Sr concentration 共x兲 and tempera-
tures. The interface resistance (R E) at the porous LSC/LSGM is also
calculated by the following equation
1/R E ⫽ 2FJ o/RT 关3兴
The calculated two values 共J o and R E兲 indicate the oxygen reduction
activity of the porous LSC cathodes on the LSGM electrolyte. For
example, the LSC with x ⫽ 0.4 sample shows exchange current
density of J o ⫽ 0.519 A cm⫺2 at 1073 K, which is almost consistent
with the literature data.15
Impedance spectra.—Figure 5 shows typical Cole-Cole plots of
ac impedance spectra for the porous LSC/LSGM interface with dif-
ferent Sr concentration in LSC under no voltage applied condition
(E ⫽ 0 V). A simple electrochemical circuit, R E-constant phase el-
ement 共CPE兲 parallel plus series connection with R b , is assumed to
analyze the data. That is, the arcs of the semicircles correspond to
the interface resistance (R E) and the intercepts of real axis at high
frequency correspond to the ohmic resistance (R b). In this study, the
interface resistance can indicate the resistance for electrode reaction
共oxygen reduction兲 and the ohmic resistance can indicate the contact
and the electrolyte resistance. The fitting lines are also drawn in Fig.
5, which shows good matching. It is obvious that the higher Sr
concentration in LSC shows the lower interface resistance, while the
ohmic resistance is constant. The intercept value of 2.2 ⍀ corre-
sponds to 7.7 ⍀ cm at 1073 K, which is consistent with the conduc-
tivity data of LSGM.1,2 Therefore, the ohmic resistance indicates
mainly the electrolyte resistance. The contact resistance between Pt
mesh and LSC was negligibly small in this experimental condition.
From the arcs of these semicircles, the interface resistance was cal-
culated for the samples with a different Sr concentration in LSC.
The interface resistance calculated from these spectra are 0.36,
0.195, and 0.133 ⍀ cm2 for x ⫽ 0.2, x ⫽ 0.3, and x ⫽ 0.4, respec-
tively. These values are consistent with the calculated interface re-
sistance from the dc polarization curves 共Table I兲. Thus, this analy-
sis is valid in this measurement system. More precise analysis of
these impedance spectra could give us more information, such as the
previous reports.19,20 However in this paper, as a first estimation of
 Journal of The Electrochemical Society, 148 共5兲 A456-A462 共2001兲 A459

Table I. Exchange current density „J oÕA cmÀ2… and interface resistance „R E Õ⍀ cm2… at the porous La1Àx Srx CoO3Àd ÕLSGM interface from the
dc polarization curves at 873-1073 K. The activation energy for the interface conductivity „␴ E… are also listed in the bottom of the table.

Temperature 共K兲 x ⫽ 0.2 x ⫽ 0.3 x ⫽ 0.4

⫺2 ⫺3 ⫺3
873 o
J /A cm 2.20 ⫻ 10 5.51 ⫻ 10 9.62 ⫻ 10⫺3
R E /⍀ cm2 17.1 6.82 3.86
923 J o/A cm⫺2 6.71 ⫻ 10⫺3 1.71 ⫻ 10⫺3 2.92 ⫻ 10⫺3
R E /⍀ cm2 5.93 2.33 1.29
973 J o/A cm⫺2 1.91 ⫻ 10⫺2 3.66 ⫻ 10⫺2 6.28 ⫻ 10⫺2
R E /⍀ cm2 2.20 1.14 0.668
1023 J o/A cm⫺2 3.64 ⫻ 10⫺2 9.48 ⫻ 10⫺2 0.149
R E /⍀ cm2 1.21 0.465 0.296
1073 J o/A cm⫺2 0.121 0.256 0.519
R E /⍀ cm2 0.382 0.185 0.089
Activation energy of 142 137 139
␴ E (E a /kJ mol⫺1)

the interface property of LSC/LSGM, a simple semicircular approxi-
mation has been adopted. The precise analysis will be made in the
near future.
Cathodic overpotential dependence of the interface conduct-
ivity.—From the interface resistance of LSC/LSGM (R E /⍀ cm2),
the interface conductivity (␴ E /S cm⫺2 ) is defined by the following
equation
␴ E ⫽ 1/R E
The interface conductivity (␴ E) was adopted to examine the activity
for oxygen reduction at the porous LSC/LSGM interface. Under
cathodic polarization, the applied cathodic voltage 共cathodic over-
Figure 5. Typical ac impedance spectra at the LSC/LSGM interface. 1073
K, E ⫽ 0 V, the number in the plots indicate the frequency, 䊊: x ⫽ 0.2,
䊐: x ⫽ 0.3, 䉭: x ⫽ 0.4, solid lines indicate the fitting curves兲.
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potential兲 reduces the oxygen activity around the interface of LSC/
LSGM. When the reaction rate is controlled by a chemical reaction
or a chemical diffusion process around the O2 /LSC/LSGM inter-
face, the overpotential 共␩兲 of LSC cathode is given by the difference
in the oxygen activity between the LSC/LSGM interface and the
reference Pt/LSGM interface. The oxygen partial pressure at the
LSC/LSGM interface, pO2, is thus calculated in the following equa-
tion, assuming that the activity coefficient is unity
关4兴
pO2 ⫽ 0.2 ⫻ exp共 4F␩/RT 兲 关5兴
Figure 6a shows the interface conductivity (␴ E) as a function of
oxygen partial pressure at the LSC/LSGM interface 共measured from
the ac impedance spectra兲. The oxygen partial pressure is defined by
the Eq. 5, which is attained by the applied voltages 共E兲 关That is,
cathodic overpotential 共␩兲, ⫺0.1 V ⬍ ␩ ⬍ 0 V兴. The interface con-
ductivity increase with a decrease of oxygen partial pressure 共with
an increase of cathodic overpotential兲 in the all samples. The slopes
of the plots change with x values in LSC: The higher Sr concentra-
tion in LSC shows the lower dependence of oxygen partial pres-
sures. For comparison, the oxygen vacancy concentration in LSC is
plotted as a function of oxygen partial pressure with different Sr
concentration of LSC 共Fig. 6b兲.26 A similar oxygen partial pressure
dependence is observed between the interface conductivity and the
oxygen vacancy concentration in LSC. This indicates that the inter-
face conductivity can be related to the concentration of oxygen va-
cancy in LSC.
Temperature dependence of the interface conductivity.—Figure 7
shows temperature dependence of the interface conductivity with a
different Sr concentration of LSC 共at E ⫽ 0 V兲. With an increase of
the temperature, the interface conductivity increases logarithmically:
the interface conductivity (␴ E) shows the Arrhenius type of the
temperature dependence. The solid lines in Fig. 7 indicate the least
square fitting for observed data. From the slopes of fitting lines, the
activation energy for the interface conductivity was calculated to be
137-142 kJ mol⫺1 in this experimental condition 共in Table I兲. The
activation energy of these three LSC samples is similar values in
magnitude. Thus, the reaction mechanism is similar among different
Sr concentration of LSC on LSGM.
For comparison, literature data of the interface conductivity for
LSC/LSGM13,15 and LSC/CeO2-YSZ25 are also plotted in Fig. 7. A
similar temperature dependence of the interface conductivity is ob-
served from some literature data,15,25 though a considerable differ-
ence is observed in other literature.13 The difference of the activa-
tion energy for the interface reaction has not been clarified yet.
However, it can be related to the microstructure of the porous LSC
cathode, which affects gas diffusivity and the adhesion of a porous
cathode on the LSGM electrolyte.
 A460 Journal of The Electrochemical Society, 148 共5兲 A456-A462 共2001兲

Figure 7. Temperature dependence of the interface conductivity at LSC/

LSGM. 共1073 K, 䊊: x ⫽ 0.2, 䊐: x ⫽ 0.3, 䉭: x ⫽ 0.4兲.

chemical diffusion of oxygen 共oxide ion diffusion兲 through the LSC

electrode via the oxygen vacancies, 5. transfer of oxide ion (O2⫺) at
the interface of LSC/LSGM, 6. incorporation of adsorbed oxygen
via the three phase boundary 共TPB兲. Steps 2 and 6 are the charge
transfer reaction with a formation of oxide ions (O2⫺). In this study,
step 1 is fast enough because of high porosity and high diffusivity of
O2 gas in the porous LSC. From the dc polarization curves, the
deviation from the linear relationship of ␩-J was observed in the
higher cathodic polarization. At low polarization 共close to the equi-
librium condition兲, the reaction process is thought to be limited to
the process of 2 → 3 → 6 in Fig. 8. However, at the higher ca-
thodic polarization, the formation of oxygen vacancies in LSC can
enhance the oxygen reduction, and the surface of the LSC electrode
can be the active sites for oxygen reduction as well as the TPB. That

Figure 6. Oxygen partial pressure dependence of the interface conductivity

(␴ E) at LSC/LSGM 共a兲 and that of oxygen vacancy concentration in LSC 共b兲
after Ref. 26.

Discussion
Electrode reaction (cathode reaction) mechanism.—To analyze
the electrode reaction at the porous LSC/LSGM interface, consider
the reaction steps around the interface. Figure 8 shows a schematic
diagram of cathode reaction at the O2共gas兲/LSC/LSGM interface. Figure 8. Schematic diagram of oxygen reduction at the LSC/LSGM inter-
The cathode reaction can be divided into elemental steps, as indi- face. 共1兲 gas diffusion of O2 gas, 共2兲 adsorption of O2 on the LSC surface and
cated in Fig. 8: 1. gas phase diffusion of oxygen molecules, 2. oxy- incorporation into LSC, 共3兲 surface diffusion of adsorption oxygen, 共4兲 dif-
gen adsorption on LSC surface and incorporation into the LSC elec- fusion of oxide ions, 共5兲 transfer of oxide ions from LSC to LSGM, 共6兲
trode, 3. diffusion of adsorbed oxygen on the LSC surface, 4. incorporation of adsorbed oxygen via the O2 /LSC/LSGM TPB.

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 Journal of The Electrochemical Society, 148 共5兲 A456-A462 共2001兲
is, the process of 2 → 4 → 5 is promoted under the higher cathodic
polarization, as well as is the process of 2 → 3 → 6 in Fig. 8.
From the cathodic applied voltage dependence 共oxygen partial
pressures at the porous LSC/LSGM interface兲, the interface conduc-
tivity (␴ E) has a relation with the concentration of oxygen vacancy
in LSC under cathodic polarization. Since the oxide ion diffusion in
""
LSC is proportional to the oxygen vacancy concentration ( 关 V O 兴)
and the vacancy diffusion coefficient (D V), the interface conductiv-
ity can be related to the oxygen diffusion coefficient (D o) in LSC
共assuming that the vacancy diffusion coefficient is constant against
the change of the oxygen partial pressures兲. The relationship of the
above parameters can be written as follows
""
␴E ⬀ 关VO 兴 ⫽ D oC o /D V
where C o indicates the concentration of oxygen in LSC, which is
assumed to be unity. D o is related to the diffusivity of oxide ions in
LSC, and step 4 correlates with the measured interface conductivity.
The temperature dependence of the interface conductivity also
showed similar activation energy with that of the oxygen vacancy
diffusion coefficients reported so far.19-24 Summarizing these results,
the interface conductivity has a strong relation with step 4 among
steps 2-6. In other words, step 4 is the main rate-determining step in
this experimental condition. Adler has reported the active length for
oxygen reduction at the LSC/CeO2 interface.20 The thickness of the
porous LSC electrode in this study is comparable level of the esti-
mated active length 共less than 10 ␮m兲. Hence, steps 2 and 3 are fast
enough in the present study, and all the surface of LSC can be the
active for oxygen reduction in this study.
According to the previous studies, it has been reported that LSC
shows a low activity of surface reaction on a ceria (CeO2) electro-
lyte by the ac impedance data under nonpolarized condition.19,20,29
In order to determine the surface oxygen exchange rates on the LSC
surface 共step 2兲, isotope oxygen exchange ( 16O/18O exchange兲 ex-
periment was examined by secondary ion mass spectrometry 共SIMS兲
analysis.29,30 From the measured data of the surface exchange rates
by SIMS analysis,30 the activation energy for the surface oxygen
exchange rates are 127 kJ mol⫺1 and 78 kJ mol⫺1 for x ⫽ 0.2 and
x ⫽ 0.5 in La1⫺xSrx CoO3⫺d , respectively. These values are not al-
ways consistent with the activation energy for the measured inter-
face conductivity at the porous LSC/LSGM in this study. Therefore,
the surface reaction rates 共step 2 in Fig. 8兲 were thought to be too
fast than the other processes in this study, probably due to a high
catalytic activity of oxygen adsorption at Pt mesh. The Pt mesh has
a good contact with the porous LSC without blocking the O2 gas.
Effect of Sr concentration in LSC on the electrode reac-
tion.—Among the examined LSC cathodes, the higher Sr concentra-
tion of LSC showed the higher activity for oxygen reduction on the
LSGM electrolyte. Since the microstructures are almost the same for
these porous LSC cathodes, the difference of the activity comes
from the interaction of O2 gas with LSC surface or the diffusion of
oxide ions in LSC. Based on the experimental results and the con-
sideration in the previous section, the higher Sr concentration in
LSC can increase the reaction rates for oxygen reduction, especially
the diffusion of oxide ions in the porous LSC. The difference of the
reaction rates comes from the concentration of oxygen vacancies in
LSC, which increases the oxide ion diffusion in LSC. The tempera-
ture dependence of the interface conductivity showed similar acti-
vation energy among the different Sr concentrations of LSC 共Fig. 7兲.
Therefore, the reaction mechanism is expected to be similar among
the different Sr concentrations of LSC.
The present results showed the importance of the oxide ionic
conductivity in LSC for oxygen reduction at the LSC/LSGM inter-
face. This leads to the necessity of high oxide ion conductors as well
as the electronic conductor in this system. Recently, alternative cath-
ode materials have been investigated with LnCoO3 based perovskite
共Ln ⫽ Pr, Nd, Sm, etc.兲.4 These materials show high performances
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A461
as a cathode on LSGM. Clarification is needed as to the reaction
mechanism at these cathode/LSGM interfaces. Of course, we have
to consider another important factors for preparation of a ‘‘good’’
porous cathode microstructure, not only the electrochemical prop-
erty of cathode material itself: preparation rotes of cathode powders,
firing temperature of cathode on the LSGM electrolyte, etc.
Another important requirement for LSC cathode is the thermal
expansion matching with LSGM electrolyte. Although no delamina-
tion or removal of LSC porous cathode was observed in this study,
thermal expansion mismatch between LSC and LSGM can be prob-
lem for large-scaled cells. The thermal expansion coefficient of LSC
measured is about 20 ⫻ 10⫺6 K⫺1 , which was too large compared
with that of LSGM ( ⬇ 10 ⫻ 10⫺6 K⫺1 ). Therefore, it is also
needed to reduce the mismatch of thermal expansion between cath-
关6兴
ode and LSGM.
Conclusions
The electrode reaction mechanism was investigated at the porous
LSC/LSGM interface (x ⫽ 0.2, 0.3, 0.4) prepared by a conven-
tional screen printing method. The dc polarization curves showed
linear relationships in the plots of overpotential-current density
(␩-J) at the lower polarization (⫺0.02 ⬍ ␩ ⬍ 0), which suggested
the monotonous reaction mechanism. The interface conductivity
(␴ E) at the LSC porous/LSGM was calculated both from the dc
polarization curves and the ac impedance spectra to compare the
activity of LSC. The obtained ␴ E values from two methods showed
a good agreement each other. The ␴ E values increased with in-
creases the Sr concentration in LCC and cathodic overpotential. The
higher Sr concentration of LSC showed the lower oxygen partial
pressure dependence of ␴ E values at the LSC/LSGM interface. The
activation energy for the ␴ E values was almost same for different Sr
concentration of LSC. Therefore, a similar reaction mechanism is
assumed with different Sr concentration of LSC. Oxide ion diffusion
in LSC can be related to the oxygen reaction rates at the porous
LSC/LSGM interface under cathodic polarization.
Acknowledgment
This work was part of the research fellowship supported by the
Alexander von Humboldt Foundation, Bonn, Germany. The corre-
sponding author 共T.H.兲 sincerely thanks the Foundation for the sup-
port of the research fellowship 共from December 1998 to January
2000兲.
NIMC assisted in meeting the publication costs of this article.
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