Structure and electrochemical properties of Sm

0.5
Sr
0.5
Co
1 x
Fe
x
O
3
cathodes for solid oxide fuel cells
Hong Lv

, Yu-ji Wu, Bo Huang, Bin-yuan Zhao, Ke-ao Hu
State Key Laboratory of Metal Matrix Composites, Shanghai Jiaotong University, Shanghai 200030, P. R. China
Received 23 October 2005; received in revised form 14 January 2006; accepted 21 January 2006
Abstract
Crystal structure, thermal expansion coefficient, electrical conductivity and cathodic polarization of compositions in the system Sm
0.5
Sr
0.5
Co
1 x
Fe
x
O
3
with 0x0.9 were studied as function of Co/ Fe ratio and temperature, in air. Two phases, including an Orthorhombic symmetry
for 0x0.4 and a cubic symmetry for 0.5x0.9, were observed in samples of Sm
0.5
Sr
0.5
Co
1 x
Fe
x
O
3
at room temperature. The adjustment
of thermal expansion coefficient (TEC) to electrolyte, which is one of the main problems of SSC, could be achieved to lower TEC values with
more Fe substitution. High electrical conductivity above 100S/cm at 800C was obtained for all specimens, so they could be good conductors as
cathodes of IT-SOFC. The polarization behavior of SSCF as a function of Fe content was evaluated by means of AC impedance using LSGM
electrolyte. It was discovered that the Area Specific Resistance (ASR) of SSCF increased as the amount of substitution of Fe for Co increased.
When the amount of Fe reached to 0.4, the highest ASR was obtained and then the resistance started decreasing above that. The electrode with a
composition of Sm
0.5
Sr
0.5
Co
0.2
Fe
0.8
O
3
showed high catalytic activity for oxygen reduction operating at temperature ranging from 700 to
800C.
2006 Elsevier B.V. All rights reserved.
Keywords: Solid oxide fuel cell; Cathode; Iron-doped Sm
0.5
Sr
0.5
CoO
3
; Polarization resistance
1. Introduction
Solid oxide fuel cell (SOFC) is an all solid device that
converts the chemical energy of gaseous such as hydrogen and
natural gas to electricity through electrochemical processes.
SOFC, being an electrochemical device, has unique advantages
over the traditional power generation technologies. SOFCs
combine the benefits of environmentally benign power
generation with fuel flexibility. However, the necessity for
high operating temperatures (9001000C) results in high costs
and materials compatibility challenges [1]. As a consequence,
significant effort has been devoted to the development of
intermediate-temperature (500800C) SOFCs. A key obstacle
to reduced-temperature operation of SOFCs is the poor activity
of traditional cathode materials for electrochemical reduction of
oxygen in this temperature regime.
Currently, Sr-doped LaMnO
3
is commonly used as the
cathode material for the SOFCs operating at high temperatures
(900 1000 C) because of its high catalytic activity for oxygen
reduction and thermal and chemical compatibility with the YSZ
electrolyte at SOFCs operating temperatures [2]. While LSM
has shown promising performance for SOFCs operating at
temperature above 800C, its performance decreases rapidly as
the operating temperature decreases, for example, the LSM
overpotential at 1000C is 1 cm
2
but increases to 2000
cm
2
at 500C [3]. Sm
0.5
Sr
0.5
CoO
3
(SSC) is regarded as one of
the most promising cathode materials for IT-SOFCs because
SSC has shown a higher ionic conductivity than that of LSM,
similar performance to La
0.6
Sr
0.4
Co
0.2
Fe
0.8
O
3
, exchange para-
meters higher than LSC and LSM [4,5], and to be particularly
compatible with GDC and LSGM [6]. However, the thermal
expansion coefficient (TEC) values are very larger than 20
(10
6
C
1
), which could produce stress at the interface
during thermal cycling [11]. Further investigations should be
done to improve the compatibility with the electrolyte. S.
Balagopal et al. have pointed out that doping in B-site
(replacing Co) could decrease the TEC [7]. It is found that the
electronic conductivity of LSCF can exceed 300S/cm at 750C
[8] and has more compatible TEC than LSC [9,10]. Doping with
Solid State Ionics 177 (2006) 901906
www.elsevier.com/locate/ssi

Corresponding author. Tel.: +86 21 62933751; fax: +86 21 62822012.

E-mail address: leosjtu@yahoo.com.cn (H. Lv).
0167-2738/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ssi.2006.01.038
Fe into Co-site in SSC maybe lower the TEC, without resulting
in a great decrease in electrochemical properties and there is
little published information relating the structural, thermal and
electrical properties of Sm
0.5
Sr
0.5
Co
1 x
Fe
x
O
3
(0x0.9)
(SSCF).
In this paper, we investigated the effects of Fe doping of
Sm
0.5
Sr
0.5
CoO
3
(0x0.9). Their crystal structure, thermal
expansion coefficient, electrical conductivity and cathodic
polarization were studied from the viewpoint of intermediate
temperature SOFCs.
2. Experimental
Sm
0.5
Sr
0.5
Co
1 x
Fe
x
O
3
(x=0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6,
0.7, 0.8, 0.9) were prepared using traditional solid-state reaction
method. The precursors were Sm
2
O
3
(N99.99%), SrCO
3
(N99.9%), Co
3
O
4
(N99%), and Fe
2
O
3
(N99%). They were
calcined in air for 2h at 800C and 300C, respectively, to
remove the absorbed moisture. The powders were mixed in
absolute alcohol by ball mill for 24h, then calcined at 1000C
for 10h followed by repeated grinding and calcining until
complete reaction and uniform composition were achieved. The
products were ground, pressed into pellets and sintered in air at
1200C for 5h. The phases were identified using X-ray
diffraction (XRD, D8 Discover GADDS), diffractometer
using monochromated CuK radiation at the scanning speed
of 0.5/min. Structural parameters were refined from XRD data
using least-squares procedure.
La
0.8
Sr
0.2
Ga
0.8
Mg
0.2
O
3
(LSGM) using as the electrolyte was
prepared by traditional solid-state reaction method. Stoichio-
metric amounts of La
2
O
3
(N99.99% purity), SrCO
3
(N99.9%
purity), Ga
2
O
3
(N99.99% purity) and MgO (N99.99% purity)
were intimately mixed in an agate mortar with the aid of
absolute alcohol for 24h and then calcined at 950C for 10h.
The calcined powders were crushed using agate mortar and
pestle and ball milled in absolute alcohol for another 24h. The
resulting fine powder was dried and uniaxially pressed into
pellet under 100MPa. After being sintered at 1500C for 5h, the
pellets were obtained with diameter of 20mm and thickness of
0.60.1mm. The polarization resistance of SSCF cathode was
measured in the two-electrode symmetric cell configuration
under air [16]. Electrolyte-supported symmetric cells for
impedance studies were prepared by screen printing. The slurry
of SSCF, which was ground and mixed with isopropyl alcohol,
was printed onto both sides of an LSGM electrolyte disk,
followed by calcination at 1150C for 2h under stagnant air.
After being sintered, the resulting electrode areas are 1 cm
2
. Pt
mesh (80 meshes) was attached to the electrode surfaces using
Pt paste as the current collector. The scheme of electrolyte-
supported symmetric cell was shown in Fig. 1. The electro-
chemical activities of the SSCF cathodes were characterized by
the electrochemical impedance spectroscopy (EIS), using a
solartron 1260 frequency response analyzer at open circuit. The
applied frequency was in the range of 10mHz to 100KHz at five
points per frequency decade with the signal amplitude of 20mV.
The EIS was measured in the temperature range from 500 to
800C increments of 50C in the air. The impedance spectra
were analyzed by the equivalent circuit of the program Zview.
Cross-section of the cathode was observed by scanning electron
microscopy (SEM, PHLIPS 515).
The electrical conductivity of the Sm
0.5
Sr
0.5
Co
1 x
Fe
x
O
3
materials was measured using the standard four-probe DC meth-
od. Rods of SSCF were sintered at 1200C for 5h in air. Rec-
tangular bars with approximate dimensions of 5520mm
3
were obtained from the sintered rods. Pt lead was attached to the
rod with Pt paste and fired at 1000C for 30min to obtain a firm
bonding and good electrical contact between the Pt leads and the
sample. Measurements were performed from room temperature
to 900C with a heating rate of 5C/min.
Thermal expansion measurement was performed on rectan-
gular specimens (5520mm
3
) from room temperature to
900C with a heating rate of 5C/min using quartz as a
reference. Measurements of YSZ and LSGM were also carried
out for comparisons.
Fig. 1. The scheme of a symmetric two-electrode measurement cell.
Table 1
The cell parameters of Sm
0.5
Sr
0.5
Co
1 x
FexO
3
ceramics at room temperature
SSCF Crystal structure a/ b/ c/ Cell volume/
3
x=0 Orthorhombic 5.35910.0093 5.39270.0053 7.57660.0107 218.96
x=0.1 Orthorhombic 5.37220.0090 5.38850.0093 7.58870.0096 219.68
x=0.2 Orthorhombic 5.39720.0003 5.39810.0003 7.62830.0003 222.25
x=0.3 Orthorhombic 5.41120.0024 5.40260.0025 7.65360.0026 223.75
x=0.4 Orthorhombic 5.41030.0039 5.41130.0041 7.64530.0042 223.83
x=0.5 Cubic 3.82670.0008 56.04
x=0.6 Cubic 3.85540.0023 57.26
x=0.7 Cubic 3.85390.0004 57.24
x=0.8 Cubic 3.85470.0006 57.28
x=0.9 Cubic 3.87390.0009 58.14
902 H. Lv et al. / Solid State Ionics 177 (2006) 901906
3. Results and discussion
3.1. Crystal structure and the cell parameters
The lattice parameters for Sm
0.5
Sr
0.5
Co
1 x
Fe
x
O
3
(0
x0.9, sintered in air at 1200C for 5h) are summarized in
Table 1. Sm
0.5
Sr
0.5
CoO
3
has been studied by Tu et al. [11] the
parameters of Sm
0.5
Sr
0.5
CoO
3
(a=5.367, b=5.406, c=7.588)
they reported are the same as our results. Two phases are ob-
served in sample of Sm
0.5
Sr
0.5
Co
1 x
Fe
x
O
3
at room temper-
ature, the perovskite phase of SSCF has an Orthorhombic
symmetry for 0x0.4 and a cubic symmetry for 0.5x0.9.
It also can be observed that the initial volume of both phases
increases at room temperature with increasing iron content, as
may result from the relative values of ionic radii of iron and
cobalt cations in octahedral coordination. The ion size of Co
3+
(r =0.61 ) is somewhat smaller than that of Fe
3+
(r =0.645 ).
In this paper, detailed crystal information has not been obtained,
but the characteristics pertaining to use as an electrode for
SOFC are the main focus.
3.2. Thermal expansion coefficient
Thermal expansion curves in Fig. 2 show gradual increases
in the high temperature region for most compositions, but they
deviate from linearity as indicated by the plots of YSZ and
LSGM. The observed abnormal expansion in samples at high
temperatures is due to the loss of lattice oxygen [12]. Thermal
expansion coefficients (TEC's) calculated from these curves in
Fig. 2 are plotted as function of Fe content in Fig. 3. The TEC
for compositions has been found to decrease with increasing Fe
content. The adjustment of thermal expansion rate to electro-
lyte, which is one of the main problems of SSC, could be
achieved to lower TEC values with more Fe substitution. At
x=00.3 composition, the TEC does not show remarkable
decrease and it displays decreasing obviously from 0.4 to 0.9.
Thermal compatibility with the electrolytes has been improved
at x0.8 evidently. The same phenomena have been observed
in La
0.8
Sr
0.2
Co
1 y
Fe
y
O
3
and Nd
0.7
Sr
0.3
Co
1 y
Fe
y
O
3
as Fe
solution content increases [12,14].
L.-W. Tai et al. explained that the lattice expansion associated
with the formation of oxygen vacancies: (1) the repulsion force
arising between those mutually exposed cation when oxygen
ions are extracted from the lattice; (2) the increase in cation size
due to the reduction of the Fe and Co ions from higher to lower
valences, which must occur concurrently with the creation of
oxygen vacancies in order to maintain electrical neutrality.
Therefore, the loss of lattice oxygen decreased with increasing
Fe content, which leads to the decrease of TEC [12,13].
3.3. Electrical conductivity
Fig. 4 shows the electrical conductivity plots (log) versus
inverse temperature measured from room temperature to
Fig. 2. Linear thermal expansion curves for Sm
0.5
Sr
0.5
Co
1 x
Fe
x
O
3
.
Fig. 3. Thermal expansion coefficient of Sm
0.5
Sr
0.5
Co
1 x
Fe
x
O
3
.
Fig. 4. Temperature dependence of the electrical conductivity for Sm
0.5
Sr
0.5
Co
1 x
Fe
x
O
3
.
903 H. Lv et al. / Solid State Ionics 177 (2006) 901906
900C, the electrical conductivities of SSCF decrease as the Fe
content increases from x=0 to x=0.9 (except x=0.6). In
Sm
0.5
Sr
0.5
Co
1 x
Fe
x
O
3
systems, most of the samples show
the semi-conducting behavior and the electrical conductivity of
each composition increases with temperature through a
maximum, then decreases. The same phenomena have been
observed in La
0.8
Sr
0.2
Co
1 y
Fe
y
O
3
, the p-type electrical con-
ductivity of LSCF decreases with Fe content because oxygen
vacancies formed in these oxides at high temperatures resulted
in a reduction in the concentration of electronic charge carriers
[12]. The observed unique temperature dependence of electrical
conductivity was attributed to several factors including: charge
disproportionation of Co ions, ionic compensation by the for-
mation of oxygen vacancies at higher temperatures, and pre-
ferential electronic compensation to form Fe
4+
rather than Co
4+
.
The composition dependence of electrical conductivity at
800C is shown in Fig. 5. High electrical conductivity has been
obtained for all specimens. Although conductivity decreases
with the enhancement of Fe content from the order value of
3 (=10
3
S/cm, x=0) to 2(=10
2
S/cm, x=0.9), all the values
are higher than LSM. So they can be better conductors as
cathodes of IT-SOFC than LSM.
3.4. AC impedance measurement
The microstructure of SSC/LSGM has been shown in Fig. 6.
SSC sintered in 1150C for 2h shows a structure with a
reasonable porosity and well-necked particles. LSGM sintered
in 1500C for 5h shows a densified structure. The interface
combines well between electrode and electrolyte. Electrode
thickness was determined from SEM micrograph; the average
thickness of SSC is 151.5m. The electrode thickness of
SSCF with different Fe content is also the same with SSC.
The typical impedance spectroscopies for SSCF cathode at
various temperatures (at 550, 650, 750, 800C) are shown in
Fig. 7, the impedance spectra are evaluated by fitting impedance
data with the equivalent circuit shown in Fig. 8, where R
s
is the
overall ohmic resistances including the electrolyte resistance,
electrode ohmic resistance, lead resistance and contact resis-
tance between cell and Pt mesh. L is the inductance, which
could be due to the platinum current/voltage probes or the high
frequency phase shift of electrochemical equipment. At the low
frequency phase, L has little effect on impedance spectra. In the
temperature range over 400C, electrolyte impedance that
appeared in high-frequency domain could not be observed with
the exception of resistor part, so the difference between real-
axes intercepts of the impedance plot is considered to be the
electrode polarization resistance (R
p
).
Because the electrical conductivity of SSCF shows high val-
ues (100S/cm) and the electrode average thickness is 15
1.5m, the electrode ohmic resistances are so small as to be
omitted. In Fig. 7, the real-axes value which meets the left side of
semi-circle corresponds to R
s
of the equivalent circuit in Fig. 8.
Fig. 7 shows the difference of the R
s
at the same temperature,
which mainly attributes to the different thickness of electrolyte
disk, the different length of the lead and the different contact
resistance between cell and Pt mesh. From Fig. 7, it can be
known that the polarization resistance decreases between the
electrolyte and electrode as the temperature increases. Fig. 9
shows the Area Specific Resistance (ASR) at 800C according
to the change of Fe doping mole fraction. R
p
of Sm
0.5
Sr
0.5
Co
1 x
Fe
x
O
3
is the fitting result of equivalent circuit by
Zview software from EIS (Fig. 7). ASR is one half of the
polarization resistance and corrected for area since the imped-
ance is measured on symmetric cells [15]. As the amount of
substitution of Fe for Co increases, the ASR increases. When
the amount of Fe reaches to 0.4, the highest ASR is obtained and
then the resistance starts decreasing above that. This tendency
exists at various temperatures, which can be shown in Fig. 10.
Higher ASRs are found due to the lower catalytic activity for
oxygen reduction. LSCF systems indicate that cobalt makes an
important contribution to the electrochemical reaction with
cathode. The substitution of Fe on the Co-site makes the
overpotential increase in the composition range from 0 to 1 in
Fig. 6. SEM photograph of cross-section of SSC/LSGM.
Fig. 5. Composition dependence of the electrical conductivity for Sm
0.5
Sr
0.5
Co
1 x
Fe
x
O
3
at 800C.
904 H. Lv et al. / Solid State Ionics 177 (2006) 901906
Ln
1 x
Sr
x
Co
1 y
Fe
y
O
3
(Ln=Pr, Nd, Gd; x=0.2, 0.3) [14],
which is different from the result of our investigation. Ln
1 x
Sr
x
Co
1 y
Fe
y
O
3
have a single-phase Orthorhombic perov-
skite structure as Fe solution content increase, but two phases
Fig. 8. Equivalent circuit of the solid oxide with Fe doping mole fraction at
800C. Fig. 9. Area specific resistance of SSCF/LSGM electrolyte/electrode system.
Fig. 7. Impedance spectroscopy for Sm
0.5
Sr
0.5
Co
1 x
Fe
x
O
3
(x=0, 0.2, 0.6, 0.8) cathode in the air at various temperature.
905 H. Lv et al. / Solid State Ionics 177 (2006) 901906
are observed in sample of Sm
0.5
Sr
0.5
Co
1 x
Fe
x
O
3
at room
temperature, the perovskite phase of SSCF has an Orthorhom-
bic symmetry for 0x 0.4 and a cubic symmetry for
0.5x0.9. The change of crystal structure in SSCF systems
may lead to the difference, which catalytic activity changes as
substitution of Fe on the Co-site increases, between SSCF and
LSCF. Meanwhile, the sintering activity of the materials is not
the same when the composition is different, and has a strong
influence on the electrode microstructure, which also influences
the performance of the cathode. However, these causes are still
not well understood and further study is necessary.
4. Conclusion
Sm
0.5
Sr
0.5
Co
1 x
Fe
x
O
3
(0x0.9) (SSCF) were studied
for their crystal structure, thermal expansion rate, electrical
conductivity and cathodic polarization. Two phases were
observed in sample of Sm
0.5
Sr
0.5
Co
1 x
Fe
x
O
3
at room
temperature, the perovskite phase of SSCF has an Orthorhom-
bic symmetry for 0x 0.4 and a cubic symmetry for
0.5x0.9. The adjustment of thermal expansion rate to
electrolyte, which is one of the main problems of SSC, could be
achieved to lower TEC values with more Fe substitution. High
electrical conductivity was obtained for all specimens and they
demonstrated above 100S/cm at 800C, so they could be good
conductors as cathodes of IT-SOFC. Polarization resistance of
SSCF was obtained by AC impedance. As the amount of
substitution of Fe for Co increased, the ASR increased. When
the amount of Fe reached to 0.4, the highest ASR was obtained
and then the resistance started decreasing above that. The
Sm
0.5
Sr
0.5
Co
0.2
Fe
0.8
O
3
electrode showed high catalytic
activity for oxygen reduction operating at temperature from
700 to 800C.
Acknowledgements
This work is supported by Instrumental analysis center of
Shanghai Jiaotong University.
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Fig. 10. Temperature dependence of the polarization for SSCF measured over a
temperature range of 500800C in air.
906 H. Lv et al. / Solid State Ionics 177 (2006) 901906