Seung-Wook Baek

Changbo Lee
Joongmyeon Bae
1
e-mail: jmbae@kaist.ac.kr
Department of Mechanical Engineering,
Korea Advanced Institute of Science and
Technology (KAIST),
373-1, Guseong-Dong, Yuseong-Gu,
Daejeon, 305-701, Republic of Korea
Cathode Properties of
Sm
x
Sr
1x
Co,Fe,NiO
3
/
Sm
0.2
Ce
0.8
O
1.9
Composite
Material for Intermediate
Temperature-Operating
Solid Oxide Fuel Cell
Perovskite-structured cathode material containing samarium (Sm) has been recognized
as a promising electrode material due to its high electrocatalytic property for intermedi-
ate temperature-operating solid oxide fuel cell (IT-SOFC). This research investigated the
optimized composition of Sm
x
Sr
1x
(Co,Fe,Ni)O
3
/ Sm
0.2
Ce
0.8
O
1.9
on the Sm
0.2
Ce
0.8
O
1.9
electrolyte and the possible use of an optimized composite material for the IT-SOFC
system. The electrochemical and thermal properties of Sm
x
Sr
1x
(Co,Fe,Ni)O
3
and its
composite material with the Sm
0.2
Ce
0.8
O
1.9
electrolyte were investigated in terms of area
specic resistance (ASR) and thermal expansion coefcient at various temperature con-
ditions. Durability of the selected materials was veried by thermal cycling and long-
term degradation tests. Sm
0.5
Sr
0.5
CoO
3
and the Sm
0.5
Sr
0.5
CoO
3
/ Sm
0.2
Ce
0.8
O
1.9
(6:4)
composite cathode showed a very low ASR of 0.87 cm
2
and 0.30 cm
2
at 600C,
respectively. The composite type cathode for the Sm
0.5
Sr
0.5
CoO
3
material was more
attractive due to its thermal expansion compatibility with neighboring cell components.
DOI: 10.1115/1.3006308
1 Introduction
Electrode polarization loss of cell on solid oxide fuel cell
SOFC has a large effect on the performance of fuel cell systems.
Performance of the cathode is an important parameter due to oxy-
gen reduction relative to the hydrogen oxidation reaction on the
anode 1. Strontium-doped lanthanum manganite LSM is most
commonly used for cathode material for high temperature-
operating SOFC 2. However, the LSM p-type conductor, has a
relatively low electrocatalytic property although it is stable at a
high temperature. Mixed ionic and electronic conductor MIEC
cathodes, such as strontium-doped lanthanum cobalt oxide LSC
and strontium-doped praseodymium cobalt oxide PSC with per-
ovskite structure, have been introduced 36. These materials,
although unstable, have been widely used and studied at low tem-
perature due to their high electrocatalytic properties. B-site sub-
stitution on the cathode material, such as strontium-doped lantha-
num cobalt iron oxide LSCF, and the introduction of the cathode
material with spinel structure have been used to lower the thermal
expansion coefcient TEC 710. However, an Fe-doped
perovskite-structure material on the B-site and spinel-structured
material has a disadvantage of low electrocatalytic property.
In this paper, B-site substituted materials with Fe and Ni, in-
stead of Co, Sm
x
Sr
1x
Co,Fe,NiO
3
, were studied, and the com-
posite cathode of the electrode and electrolyte material,
Sm
0.5
Sr
0.5
CoO
3
/ Sm
0.2
Ce
0.8
O
1.9
, was introduced to obtain a high
electrocatalytic property and a low thermal expansion. Electro-
chemical property and thermal expansion were measured by elec-
trochemical ac impedance spectroscopy EIS and dilatometer for
every composition. Thermal cycling and long-term performance
were tested to conrm the thermal stability and electrocatalytic
activities of the composite cathode for specic compositions.
2 Experimental Methods
2.1 Powder Preparation. Powder compositions were synthe-
sized by using the modied glycine nitrate process GNP method.
High purity nitrates SmNO
3

3
6H
2
O, SrNO
3

2
, CoNO
3

2
6H
2
O,
FeNO
3

3
9H
2
O, NiNO
3

2
6H
2
O and glycine were weighed by
mole ratios, and dissolved in de-ionized water. Powders were cal-
cined for 1 hour at 1250C, after the solution was heated to
300C, to remove residual carbon and impurities, and to crystal-
lize. Powders were separated using a 36 m diameter sieve and
analyzed by an X-ray diffractometer Rigaku, D/MAX-IIIC, Ja-
pan to conrm the perovskite structure as shown in Fig. 1. The
Sm
0.5
Sr
0.5
CoO
3
/ Sm
0.2
Ce
0.8
O
1.9
SSC55/SDC composite cath-
ode was obtained after ball milling for 24 hours with an ethanol
base. Sm
0.2
Ce
0.8
O
1.9
SDC Praxair was used as the electrolyte
and mixed material for the composite. Compositions and abbre-
viations of the powder are shown in Table 1.
2.2 Half Cell Preparation. Cathode materials were screen-
printed on the SDC electrolyte pellet, which is 1 mm in thickness
and 23 mm in diameter, and sintered for 1 hour at 1200C in air.
The SDC electrolyte pellet was made by the uni-axial mold press-
ing method with 50 kg
f
/ cm
2
in weight and sintered for 4 hours at
1500C.
2.3 Experimental Set-Up. The electrochemical ac impedance
measurement was applied. Measurements were conducted over a
temperature range of 400900C in air. A spring force was ap-
plied to each side of the cell to assure contact between the cathode
1
Corresponding author.
Manuscript received June 18, 2007; nal manuscript received February 20, 2008;
published online May 14, 2009. Review conducted by Nigel M. Sammes. Paper
presented at the 5th International Fuel Cell Science Engineering and Technology
Conference FUELCELL2007, Brooklyn, NY, June 1820, 2007.
Journal of Fuel Cell Science and Technology AUGUST 2009, Vol. 6 / 031010-1
Copyright 2009 by ASME
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and the Pt mesh. Measuring equipment of impedance was com-
posed of alumina and quartz tubes 40 mm in diameter. Impedance
spectra were analyzed by the Solartron 1287/Solartron 1260 elec-
trochemical interface/impedance, gain-phase analyzer and the Z
VIEW program. Measuring frequency was from 5 MHz to 100
mHz. An ac amplitude of 50 mV was used for measurements.
TEC was measured by the dilatometer TMA Thermomechani-
cal Analyzer, Linseis, USA over a range of 25900C, with a
ramping rate of 5C/ min.
3 Results
3.1 A-Site Substitution in Perovskite Structure.
Sm
x
Sr
1x
CoO
3
was the starting material for the Sm-based ox-
ides. Area specic resistances ASRs and the activation energy
E
a
are shown in Fig. 2, when Sr
2+
was substituted for Sm
3+
on
the A-site of Sm
0.5
Sr
0.5
CoO
3
at 0.3 mol and 0.7 mol ratios.
Sm
0.5
Sr
0.5
CoO
3
showed the best performance, 0.17 cm
2
at
650C. Cathode properties of ASR and E
a
were impaired as the
substituted Sr amount increased above 0.5 or decreased below 0.5.
3.2 B-Site Substitution in Perovskite Structure. The results
of ASR and E
a
according to the substitution of B-site on
Sm
0.5
Sr
0.5
BCo, Fe, NiO
3
are shown in Fig. 3. Fe was substi-
tuted to B-site Co site on the Sm
0.5
Sr
0.5
CoO
3
SSC55 base,
with the amounts of 0.3 mol, 0.5 mol, 0.7 mol, and 1 mol. SSC55
Fig. 2 Area specic resistances according to the amount of x
in Sm
x
Sr
1x
CoO
3
Fig. 3 Area specic resistances according to the substitution
of the B-site in Sm
0.5
Sr
0.5
BCo, Fe, NiO
3
Fig. 1 XRD patterns of the prepared powders: a Sm
0.5
Sr
0.5
Co, FeO
3
and Sm
0.2
Ce
0.8
O
1.9
. b Sm
0.5
Sr
0.5
Co, NiO
3
.
*Sm
0.5
Sr
1.5
CoO
4
: spinel-structured reference powder.
Table 1 Powder compositions and abbreviations of the
cathode
Structure Composition Abbreviation
Perovskite
Sm
0.3
Sr
0.7
CoO
3
SSC37
Sm
0.5
Sr
0.5
CoO
3
SSC55
Sm
0.7
Sr
0.3
CoO
3
SSC73
Sm
0.5
Sr
0.5
Co
0.3
Fe
0.7
O
3
SSCF5537
Sm
0.5
Sr
0.5
Co
0.5
Fe
0.5
O
3
SSCF5555
Sm
0.5
Sr
0.5
Co
0.7
Fe
0.3
O
3
SSCF5573
Sm
0.5
Sr
0.5
FeO
3
SSF55
Spinel
Sm
0.5
Sr
0.5
Co
0.5
Ni
0.5
O
3
SSCN5555
Sm
0.5
Sr
0.5
NiO
3
SSN55
Composite
Sm
0.5
Sr
0.5
CoO
3
: SSC55/SDC9:1
Sm
0.2
Ce
0.8
O
1.9
SSC55/SDC6:4
=9: 16: 4
031010-2 / Vol. 6, AUGUST 2009 Transactions of the ASME
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with no substitution showed the best performance. SSCF5537
among the SSCF series showed the good cathode property. The
TEC decreased due to a stronger electrostatic attraction force to
oxygen of Fe than Co Fig. 4. SSCN5555 and SSN55 containing
Ni showed low TEC values of 15.610
6
/ K and 13.310
6
/ K,
respectively, but showed remarkably increased ASRs Figs. 3 and
4.
3.3 Composite Cathode. SSC55 and SDC electrolyte materi-
als were mixed to obtain a lower thermal expansion coefcient
and a higher mixed ionic and electronic conductivity. The amount
of added SDC was varied from 10% to 50% in weight. The ASR
and TEC values are shown in Figs. 5 and 6. The composite cath-
ode of SSC55/SDC showed lower ASR and E
a
than SSC55.
SSC55/SDC8:2 showed the best electrochemical cathodic per-
formance 0.162 cm
2
ASR at 600C below 600C. The ther-
mal expansion property was remarkably improved. SSC55/
SDC6:4 showed a TEC value of 12.310
6
/ K, which had a
similar value with the SDC electrolyte.
The cross section images of the SDC electrolyte and cathode
material coated after sintering at 1200C was observed by scan-
ning electron microscopy SEM Hitachi, S4300, Japan Fig. 7.
The microstructures of SSC55 and SSC55/SDC6:4 had suf-
cient porosity for oxygen gas diffusion. The thickness of the
SSC55 layer on the SDC electrolyte was 30 m and 50 m on
SSC55/SDC6:4, using two times screen printing.
3.4 Thermal Cycling and Long-Term Performance Test.
The thermal cycle test results are shown in Fig. 8. The test was
conducted at temperatures of from room temperature to 650C,
and with decreasing temperatures of from 650C to room tem-
perature. The rate of the increasing temperature was 5C/min and
Fig. 4 Thermal expansion experimental results according to
the substitution of B-site in Sm
0.5
Sr
0.5
BCo, Fe, NiO
3
Fig. 5 Area specic resistances according to the amount of
added SDC on SSC55
Fig. 6 Thermal expansion experimental results according to
the amount of added SDC on SSC55
Fig. 7 Microstructure of a SSC55 and b SSC55/SDC6:4
Journal of Fuel Cell Science and Technology AUGUST 2009, Vol. 6 / 031010-3
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2C/min for the decreasing temperature. The ASR value of
SSC55 gradually increased by about 200% after 13 thermal
cycles. The ASR of the composite cathode did not change. The
SSC55/SDC6:4 composite cathode showed very good thermal
and electrochemical properties at 600C and 650C. Results of
the long-term performance test, which was conducted at 600C
for 132 hours to analyze the performance of the composite cath-
ode, are shown in Fig. 9. Normal performance degradation was
related to the operating time; the ASR value was two times higher
than the initial value after operating for 132 hours.
4 Discussion
A cathode sintering temperature at 1200C, which is a rela-
tively high temperature compared with the general cathode sinter-
ing temperature for a single cell, may cause a decrease in cathode
activity. However, degradation of long-term performance and un-
predictable performance change of the cathode will be minimized,
and cathodic properties will be maintained during fuel cell opera-
tion. Reliability and uniformity in the comparison of experimental
results will be obtained from high temperature cathode sintering.
A small peak shift was found with X-ray diffraction XRD by
the substitution of elements. This phenomenon is due to the ex-
pansion and distortion of the lattice by the substitution of aliova-
lent cations, such as Fe 1114. Sm
0.5
Sr
0.5
NiO
3
and
Sm
0.5
Sr
0.5
Co
0.5
Ni
0.5
O
3
, which are substituted by Ni on the
B-site, showed typical spinel structures, the same as those for
Sm
0.5
Sr
1.5
CoO
4
structure. Oxide structure containing abundant
Ni easily formed spinel structure after synthesis, since Ni is a
transition metal that has the lowest stability according to the high
oxygen release compared with other transition metals 10.
SSCN5555 and SSN55 with a spinel structure showed low TEC
values, but showed poor ASR values. Materials containing abun-
dant Ni also showed poor adhesion property to the electrolyte.
Partial substitution of Sr
2+
for Sm
3+
on the A-site brings in-
creased ionic and electronic conductivity by additional oxygen
vacancy and hole formation, according to charge neutrality
8,1517. Oxygen vacancy formation is mainly related to an in-
crease in ionic conductivity, while hole formation is related to
electronic conductivity. ASR reects the cathodic properties, such
as the oxygen reduction, the adsorption/desorption reaction of
oxygen atom, the oxygen ion conduction, etc. The ASR value
varied when 0.5 mol of Sr
2+
was substituted. This tendency is
considered as the change of vacancy formation mechanism 18.
Oxygen vacancy seemed to dominantly increase at 0.5 mol sub-
stitution. However, hole formation dominantly increased at
0.5 mol substitution. SSC55 substituted with 0.5 mol Sr
2+
was
considered as the excellent starting material.
ASR and TEC, according to the B-site substitution on
Sm
0.5
Sr
0.5
CoO
3
, were investigated. Adding Co with a weak
electrostatic attraction force for oxygen, compared with Fe and
Mn, increased oxygen vacancy and enhanced ionic conductivity.
Partial substitution of Fe or Ni decreased the formation of oxygen
vacancy by charge neutrality compensation, causing the ionic con-
ductivity of the cathode to decrease. Thermal expansion may be
decreased due to the decrease in oxygen vacancy. However, this
trend was not clearly observed in this study. The substitution of
B-site on the ABO
3
structure has a large inuence on electronic
conductivity, rather than on ionic conductivity 8,16. Moreover,
electronic conductivity is as large as two or three orders of mag-
nitude compared with the ionic conductivity. Electronic conduc-
tivity shows a larger decrease relative to the ionic conductivity, as
the amount of substituted Fe increases.
Thermal expansion could be adjusted to that of the electrolyte
by varying the added amount of the SDC electrolyte material, as
in the case of the composite cathode. This was conrmed by the
thermal cycling characteristic along with very good adhesion be-
tween the electrode and the electrolyte. Moreover, SDC addition
to SSC55 had a signicant effect on the enhancement of ionic
conductivity. Very low activation energy of composite cathode
below 1.00 eV implied that the addition of SDC was helpful in
enhancing the surface exchange property and the bulk diffusion
property of oxygen.
Two semicircles, which are distinguished by a specic fre-
quency, were exhibited at the impedance spectrum for the long-
term performance at 600C. The left semicircle, at medium fre-
quency, represents the electrolyte grain boundary, and the right
semicircle, at low frequency, represents the cathode resistance
19,20. The resistance of the electrolyte grain is negligible at a
temperature of 600C. As a result, the semicircle, at high fre-
quency, is diminished. The size of the right semicircle, which
represents the oxygen reduction reaction of the cathode, is gradu-
ally increased by cathode performance degradation. Degradation
of the cathodic property is related to the oxygen diffusion limit by
the agglomeration of powder. The long-term operating perfor-
mance of the composite cathode was not satisfactory, although the
advantages of the composite cathode were very attractive.
5 Conclusion
SSC55, with no substitution at the A-site or B-site, showed a
good electrochemical property of 0.87 cm
2
at 600C. However,
SSC55 had a very high TEC value, 19.610
6
/ K, and showed a
relatively poor adhesion property on the electrolyte. ASR and
TEC were not satisfactory in the case of the cathode material
substituted by Fe or Ni on SSC55. The composite cathode of
Fig. 8 Thermal cycle comparison of the ASR for SSC55 and
SSC55/SDC6:4
Fig. 9 Long-term performance test for SSC55/SDC6:4 by im-
pedance spectroscopy at 600C
031010-4 / Vol. 6, AUGUST 2009 Transactions of the ASME
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SSC55/SDC6:4 showed a very good electrochemical property of
0.30 cm
2
at 600C and a low TEC value of 12.310
6
/ K at
600C, as shown in Table 2. These characteristics were clearly
reected in the thermal cycling performance. The composite cath-
ode series of the Sm base, such as SSC55/SDC9:15:5, on the
SDC electrolyte are very attractive materials for SOFC, although
further verication of reliability for long-term performance re-
mains.
Acknowledgment
This work was supported by the Best Lab program by Ministry
of Commerce, Industry and Energy MOCIE, and the Brain Ko-
rea 21 BK21 program by the Ministry of Education and Human
Resources Development MOE. The author appreciates their -
nancial support.
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Table 2 Electrochemical and thermal properties of Sm-based
cathodes at 600C
Classication Composition
ASR
cm
2

E
a
eV
TEC
10
6
/ K
Perovskite
SSC55 0.87 1.16 19.6
SSCF5537 1.11 1.06 17.3
SSCF5555 4.40 1.09 19.6
SSCF5573 1.98 1.12 20.4
SSF55 2.00 1.24 16.0
Spinel
SSCN5555 So high 1.49 15.6
SSN55 So high 1.53 13.3
Composite
SSC55/SDC9:1 0.17 1.00 17.4
SSC55/SDC8:2 0.16 0.88 16.8
SSC55/SDC7:3 0.28 0.94 15.9
SSC55/SDC6:4 0.30 0.90 12.3
SSC55/SDC5:5 0.54 0.94 12.0
Electrolyte SDC - - 11.9
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