i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 3 9 8 9 e3 9 9 6

Available at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/he

Investigation on thermal, electrical, and electrochemical

properties of scandium-doped Pr0.6Sr0.4(Co0.2Fe0.8)(1Lx)ScxO3Ld
as cathode for IT-SOFC

Yi-Mei Yin a, Ming-Wen Xiong a, Nai-Tao Yang a, Ze Tong a, Ya-Qin Guo a, Zi-Feng Ma a,*,
Ellen Sun b, Jean Yamanis b, Bu-Yun Jing b
a
Department of Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, PR China
b
United Technologies Research Center, 411 Silver Lane, East Hartford, CT 06108, USA

article info abstract

Article history: A systematic study and evaluation were performed on the effect of scandium doping
Received 17 September 2010 at the B site of Pr0.6Sr0.4Co0.2Fe0.8O3
d (PSCF) on key material properties as cathode for
Received in revised form intermediate temperature solid oxide fuel cells (IT-SOFC). The doped products
20 December 2010 Pr0.6Sr0.4(Co0.2Fe0.8)(1
x)ScxO3
d (PSCFSx, x¼0.0e0.2) retained perovskite structure confirmed
Accepted 23 December 2010 by X-ray diffraction, and their particles were smaller than the non-doped materials as
Available online 26 January 2011 evidenced by TEM. The electrical conductivity (EC) of PSCFSx decreased with increasing
Sc3þ content, but EC values were still larger than 100 S cm
1 in temperature range of
Keywords: 300e800  C as x  0.1. The thermal expansion coefficients (TEC) of PSCFSx were observed to
Scandium generally decrease with increasing x especially at lower temperature range of 50e600  C. In
Perovskite addition, the AC impedance revealed better electrochemical performance of PSCFSx
Cathode cathode as x  0.1 than that of the undoped sample PSCF. Therefore, PSCFSx (x  0.1) shows
Pr0.6Sr0.4Co0.2Fe0.8O3
d some potential as cathode electrode for IT-SOFC. The function of Sc3þ dopant was tenta-
SOFC tively elucidated and discussed.
Copyright ª 2010, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction oxygen reduction [2]. Considerable effort has been devoted to

Decreasing the operating temperature of a solid oxide fuel cell
(SOFC) to a low or intermediate temperature of 500e800  C will
facilitate commercialization of SOFC technology, since such
a reduction would provide solutions for many problems in
conventional SOFC operating at high temperature (i.e.
800e1000  C), such as improving the long-term performance
stability, broadening the material selection, enabling the use of
low-cost metallic interconnects and reducing the sealing
problem [1]. However, lowering the operation temperature will
result in rapid increase of over-potential at electrodes, espe-
cially at cathode because of the high activation energy of
decrease polarization resistance of electrode at low and inter-
mediate temperature, with the key approaches having been
focused on developing new electrode materials [3] and
improving electrode and cell structures [4]. Cobalteiron based
perovskite oxides, Ln1
xSrxCo1
yFeyO3
d (LnSCF, Ln ¼ La, Pr,
Sm, Gd), are promising candidates as cathode materials for
application in intermediate temperature SOFC (IT-SOFC),
because of their high electroniceionic mixed conductivity and
good catalytic activity for the cathodic reaction. But LnSCFs still
suffer uncompatible thermal expansion coefficient with most
electrolytes [5], reaction with zirconia based electrolyte (for
example, YSZ) and insufficient low polarization resistance [6].

* Corresponding author. Tel.: þ86 21 54742894; fax: þ86 21 54747717.

E-mail address: zfma@sjtu.edu.cn (Z.-F. Ma).
0360-3199/$ e see front matter Copyright ª 2010, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2010.12.113
3990 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 3 9 8 9 e3 9 9 6
Doping strategies are frequently used to exploit new
materials and improve the properties of known materials. B
site cations play more important role in deciding the catalytic
properties of perovskite materials, therefore, are often
substituted. Scandium is in the first transitional metal series
with stable þ3 valence and large ionic radius (74.5 pm),
therefore, may lessen the thermal expansion of cobalt-based
perovskite oxides as replacing cobalt cations at B site or
improve the catalytic properties by changing the crystal
structure of these oxides. Small amount of scandium dopant
at the B site has been reported to improve the cathode
performance of perovskite oxides by optimizing the crystal
structure of SrCoO3
d from rhombohedral to cubic structure
[7] or by suppressing the segregation of SrO to surface and
optimizing the concentration of surface oxygen vacancies for
La0.8Sr0.2MnO3
d (LSM) [8].
In this study, we selected Pr0.6Sr0.4Co0.2Fe0.8O3
d (PSCF) as
candidate and systematically evaluated the effect of scandium
doping on its performance as cathode material for IT-SOFCs
with a GDC10 electrolyte. The crystal phases, chemical reac-
tivity with GDC, morphology of cathode particles, thermal
expansion properties, electrical conductivities, electroche-
mical properties and H2 temperature-programmed reduction
(H2-TPR) of Pr0.6Sr0.4(Co0.2Fe0.8)(1
x)ScxO3
d (x ¼ 0.0e0.2)
(PSCFSx) oxides were studied.
2. Material and methods
2.1. Preparation of PSCFSx powders
PSCFSx (x ¼ 0.0e0.2) were synthesized via an EDTAecirtric acid
sol-gel combustion method. Metal nitrates Pr(NO3)3$6H2O,
Sr(NO3)2, Co(NO3)2$6H2O, Fe(NO3)3$9H2O and Sc(NO3)3 were
used as starting materials. The stoichiometric nitrates were
first dissolved in deionized water, EDTA and citric acid were
then added to the mixture in sequence. A certain amount of
NH3NO3 was added as combustion assistant reagent. The pH
of the solution was adjusted to w7 via addition of NH3$H2O.
After evaporating the water from the mixture via heating at
90  C, a transparent purple gel formed. The gel was transferred
to a quartz container and heated on a hot plate to ignite. Black
powders were collected after combustion and subsequently
calcined at 1000  C for 2 h under an air atmosphere to yield the
final desired products denoted as PSCFSx. The powders of
electrolyte Gd0.1Ce0.9O2
d (GDC) were also synthesized using
the sol-gel method and calcined at 600  C for 5 h.
2.2. Characterization on phase structure, morphology
and chemical reactivity toward electrolyte
The phase and crystallinity of the powders were investigated
by X-ray diffraction using a Rigaku D/max-2200/PC X-ray
diffractometer at a 2q range from 15 to 80 .
The morphology and crystallite size of PSCFSx (x ¼ 0.0e0.2)
powders were investigated using JEM-2010/INCA Oxford
Analytical Transmission Electron Microscope. The powders
used here were calcined at 600  C for 5 h and denoted as
PSCFSx-600. The reason for using PSCFSx-600 is that perov-
skite phase has formed at 600  C except minor impurity
phase of SrCO3, yet coarsening of particles has not signifi-
cantly occurred, thus uniform particles can be easily obs-
erved and compared. Whereas coarsening of particles is
obvious with increasing temperature above 600  C, nonuni-
form size and shape of PSCFSx particles made the comparison
difficult. Therefore, PSCFSx-600 was used to verify the effect
of scandium dopant on the size and morphology of powder
grains.
The chemical reaction between PSCFS0.10 and GDC were
investigated by XRD as an example of chemical stability of
PSCFSx with electrolyte. The mixture of PSCFS0.10 and GDC
with weight proportion 1:1 was ground thoroughly in agate
mortar, pressed into pellet, then sintered at 1250  C for 5 h.
The pellets were ground into powers again and examined
using XRD.
2.3. Thermal expansion coefficients (TEC) and electronic
conductivity measurements
The calcined powders were pelletized in the form of rectan-
gular bars with dimensions of 4 mm  4 mm  15 mm under
a uniaxial pressure of 4 MPa, and then fired at 1250  C for 10 h
for both the measurements of thermal expansion coefficient
(TEC) and electrical conductivity. All samples used for the
measurements had densities >90% of the theoretical values.
Electrical conductivities were measured via four-terminal DC
technique. The current and voltage were collected at an
interval of 50  C over a temperature range of 100e800  C under
an air atmosphere. TECs were measured using a horizontal
pushrod Netzsch DIL 402 PC dilatometer from room temper-
ature to 1000  C with alumina (Al2O3) as reference.
2.4. Electrochemical characterization
Electrolyte supported symmetrical PSCFSx/GDC/PSCFSx
(x ¼ 0.0e0.2) cells were fabricated. The GDC powders were
pressed into pellets and sintered at 1500  C for 10 h in air.
EthanolePVB based PSCFSx (x ¼ 0.0e0.2) cathode slurry was
sprayed on each side of the GDC pellets and then sintered at
1250  C in air for 2 h. The electrode performance was inves-
tigated via AC impedance method using Zahner IM6eX elec-
trochemical workstation. The applied frequency range was
from 0.01 Hz to 1  106 Hz, and the signal amplitude was 10 mV
under open circuit voltage (OCV) conditions.
2.5. H2 temperature-programmed reduction (H2-TPR)
and X-ray photoelectron spectroscopy (XPS) measurements
H2-TPR tests were performed on Finesorb 3010 (Finete, China)
at atmospheric pressure in a continuous flow reactor charged
with 25 mg sample powders. 10% H2 in pure N2 at a flow rate of
20 ml min
1 was used and samples were heated from room
temperature to 1000  C at a heating rate of 6  C min
1.
XPS experiments were carried out on a RBD upgraded PHI-
5000C ESCA system (Perkin Elmer) with Mg Ka radiation
(hn ¼ 1253.6 eV) or Al Ka radiation (hn ¼ 1486.6 eV). Binding
energies were calibrated by using the containment carbon
(C1s ¼ 284.6 eV). The data analysis was carried out by using the
RBD AugerScan 3.21 software provided by RBD Enterprises.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 3 9 8 9 e3 9 9 6
3. Results and discussion
3.1. Phase structure, morphology and reaction with GDC
The X-ray diffraction patterns of PSCFSx (0.0  x  0.2),
acquired at room temperature are presented in Fig. 1. The
PSCF oxides possess a pseudo-cubic perovskite phase struc-
ture, and the main peaks are well indexed and the same as
those of Sr(Co0.5Fe0.5)O3 (PDF card no. 46-0335). As the
concentration of scandium (x) increases, the main diffraction
peaks of the PSCFSx oxides gradually shift to lower values of
2q, indicating the expansion of the perovskite lattice. The
expansion of lattice suggests that the scandium cations (Sc3þ)
were successfully introduced into the lattice of PSCF, since the
ionic radius of Sc3þ cation (74.5 pm) is larger than the ionic
radii of the most of other B site cations such as Fe3þ (64.5 pm),
Fe4þ (58.5 pm), and Co3þ (61 pm). Consequently, the pseudo-
cubic perovskite structure for PSCF changes to hexagonal
structure for PSCFS0.2. Based on an empirical rule that cations
normally adopt ionic radius larger than 51 pm at B site and
larger than 90 pm at A site in perovskite structure, it is
reasonable to propose that the Sc3þ cations may predomi-
nately replace the lattice position of B site cations such as
Co2þ/Co3þ and Fe3þ/Fe4þ. Nevertheless, as x > 0.10, a peak with
trace intensity at 25 e26 2q appeared which was indexed as
PrFeO3, indicating that the higher amount substitution of
Fig. 1 e (a) X-ray diffraction patterns of PSCFSx
(x [ 0.0e0.2). (b) Magnified XRD patterns for 31 £2q £ 35 .
3991
scandium (x  0.10) for Fe result in the separation out of
PrFeO3 impurity phase.
The morphology and particle size of PSCFSx-600
(x ¼ 0.0e0.2) powders investigated via TEM were presented in
Fig. 2. It can be seen that the PSCFSx-600 grains are mainly
rounded and wormlike. The particle size of PSCF-600 is of the
order of 50e60 nm, whereas the grain size of PSCFSx-600
(x  0.05) is about 20e30 nm, obviously smaller than that of
PSCF-600. This indicated that the scandium dopant facilitated
PSCFSx-600 to form smaller particles. The effect of scandium
dopant on morphology and particle size of perovskite oxides
has not been reported previously. As well known, smaller
particle size is beneficial to cathode performance by
increasing the special surface area of grains. However, the
effect of particle size of PSCFSx-600 on cathode performance
needs further investigation, because the final powders coars-
ened after calcined at 1000  C.
The high temperature phase reaction between PSCFSx and
GDC were examined by mixing powders thoroughly in a 50:50
weight ratio, followed by calcinations at various tempera-
tures. The XRD patterns of PSCFS0.1 and GDC calcined at
1250  C were shown in Fig. 3. It can be seen that no new peaks
can be found from the curve (c) for the mixture, indicating that
no obvious reaction occurred between GDC and PSCFS0.1 in the
condition as processed. Similar results were obtained for
other PSCFSx and GDC.
3.2. Thermal expansion
Proper TECs of cathode electrode layers matching well with
electrolyte are of importance to ensure long-term SOFC
operational stability. Cobalt-based perovskite materials are
known to have high TECs. This property may be attributed to
lattice expansion resulting from instability of high oxidation
states of Co and Fe (e.g. Co3þ, Fe4þ, Fe3þ) with the increase of
temperature, which may change to their lower oxidation
states (e.g. Co2þ, Fe3þ, Fe2þ) and induce the release of molec-
ular oxygen because of charge compensation. Consequently,
the crystal lattice expands due to larger coordination poly-
hedron of low oxidation states than that of high oxidation
states. Fig. 4 shows the thermal expansion curves for the
PSCFSx (x ¼ 0.0e0.2) oxides. The average TECs for different
temperature ranges are listed in Table 1.
For all the samples, the slope of the thermal expansion curves
increases with temperature which can be explained by a loss of
oxygen at elevated temperatures. The TEC values in Table 1
depended upon both the addition of Sc3þ amount (x) and the
selected temperature range. The TECs generally slightly decrease
with increasing the concentration of Sc3þ in temperature range of
50e800  C, this trend is more obvious in the 50e600  C temper-
ature range which is the temperature scope of the thermal
reduction process of Co3þ/Fe4þ to Co2þ/Fe3þ [9,10]. This suggests
that the replacement of Sc3þ with B site cations partly suppresses
the lattice expansion of PSCF induced by the reduction of Co3þ/
Fe4þ. At higher temperature range of 600e800  C, the thermally
activated chemical reduction was accelerated which was
supposed to attribute to a transfer from low spin-state transition
ion to a high one. Low Sc3þ substitution (x  0.1) not only seems
unable to balance the acceleration of expansion, but also might
facilitate the lattice expansion, as a result, PSCFSx (x ¼ 0.05, 0.1)
3992 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 3 9 8 9 e3 9 9 6

Fig. 2 e TEM images of (a) PSCF, (b) PSCFS0.05, (c) PSCFS0.1 and (d) PSCFS0.2 powders calcined at 600  C for 5 h.

exhibit higher TEC value than that of PSCF. As the concentration current collection [11]. Thus, the effect of Sc3þ dopant on the
of Sc3þ (x) reached 0.2, the suppression effect seemed over- electrical conductivity (EC) of the PSCFSx (x ¼ 0.0e0.2) oxides
whelming the expansion effect, causing the decrease of TEC of was investigated and the temperature dependence of EC is
PSCFS0.2 in this temperature range. presented in Fig. 5. The EC value of all oxides initially increases
linearly with temperature up to a transition temperature (Ts)
3.3. Electrical conductivity between 600  C and 700  C, then the conductivity decreases
slightly for temperatures exceeding Ts, which may be due to
The electrical conductivity of a cathode material is normally the thermal reduction of Co3þ/Fe4þ to Co2þ/Fe3þ [8]. The latter
required to be not less than 100 S cm
1 to ensure efficient
0.0125
∇
PSCF
Relative Intensity / CPS

PSCFS0.10+GDC
♦
∇ ∇ ∇ 0.0100 x=0.05
c ♦ ♦ ♦ ♦∇ ♦∇ ∇♦∇ x=0.1
x=0.2
0.0075

♦ PSCFS
b 0.10 0.0050

0.0025

∇ GDC
a
20 30 40 50 60 70 80 100 200 300 400 500 600 700 800

Fig. 3 e X-ray diffraction patterns of (a) 7GDC, (b) Fig. 4 e Linear thermal expansion curves for PSCFSx
APSCFS0.1 and (c) GDC D PSCFS0.1. (x [ 0.0e0.2) under an air atmosphere.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 3 9 8 9 e3 9 9 6 3993

Table 1 e Linear TECs (310L6 KL1) of PSCFSx (x [ 0.0e0.2) a 16

oxides at various temperatures. PSCF
100Hz
Samples Average TEC on heating (10
6 K
1) x=0.05
12 x=0.10
50e800  C 50e600  C 600e800  C x=0.15
x=0.20
PSCF 15.8 14.4 19.8
8
x ¼ 0.05 15.8 14.2 20.3
x ¼ 0.10 15.8 13.3 22.5
x ¼ 0.20 14.5 12.8 18.8 100Hz
4
100Hz 100Hz
change would be expected to create additional oxygen vacan-
cies and thus result in decreased covalency of the (Co, Fe)eO 0
bonds. This, in turn, would decrease the concentration of 4 8 12 16 20 24 28
charge carriers and the covalent interaction, and may result in
the observed changes in conductivity. Across all values of x
examined, the conductivity decreases monotonically with
b 60
increasing the concentration of Sc3þ, an obvious reduction PSCF
50 x=0.05
occurred at x > 0.1. The replacement of partial variable valence
x=0.10
cations of Co3þ and Fe4þ by the constant valence state of Sc3þ
40 x=0.15
not only decreases the conduction through the BeOeB bonds, x=0.20
but also decrease the symmetry of phase structure of PSCF as 30
mentioned in Section 3.1. Both factors may contribute to the
decrease of the electrical conductivity of PSCFSx (x ¼ 0.05e0.2). 20
However, the EC values of PSCFSx (x  0.1) are still higher than
100 S cm
1 in the temperature range of 350e800  C, meeting the 10
requirement for EC of cathode of IT-SOFC.
0
3.4. Electrochemical performance 500 550 600 650 700 750 800

The electrochemical impedance measurements were carried

Fig. 6 e (a) EIS of symmetrical cells of PSCFSx/GDC/PSCFSx
out in air at temperature range of 500e800  C using symmet-
(x [ 0.0e0.2) at 600  C under OCV conditions. (b) Arrhenius
rical cell method. Nyquist plots at 600  C were shown in
plot of ASR of PSCFSx.
Fig. 6a, and Arrhenius plots of area-specific resistance (ASR) at
various temperatures were exhibited in Fig. 6b. The imped-
ance spectra at 600  C are composed of one or two depressed
arcs indicating that at least two different processes deter- oxygen molecule into oxygen ion (On
), and the incorporation
mined the oxygen reduction reaction (ORR) in PSCFSx. of oxygen ion into the electrolyte [12e14].
Generally, the ORR occurred within porous ioniceelectronic The measured impedance spectra can be divided into three
mixed-conducting cathode is complicated, including the gas parts by frequency region: high-frequency region (HFR,
diffusion near the cathode, the surface reaction related to the >104 Hz), medium-frequency region (MFR, 104e102 Hz), and low
adsorption of oxygen on the cathode, the dissociation of frequency region (LFR, 102e10
2 Hz). The HFR is related to the
grain boundary of the electrolyte [2,12]. The resistance/capac-
350 itance arcs at MFR may result from the impedance of dissoci-
PSCF ation of oxygen into the oxygen ion and charge transfer at the
x=0.05
280 interfaces [2,12]. Therefore, the resistance size of the MFR may
x=0.10
x=0.20 be related to kinetics of the reaction determined by the elec-
210 Ts trochemical activity of the cathode materials, electrical
conductivity of electrode/current collector, and ionic conduc-
140 tivity of electrode/electrolyte. The arc at LFR is characterized by
gas-phase diffusion, oxygen surface exchange at TPB, and
oxygen ion diffusion in the bulk of electrode [2,12]. The
70
behavior of the impedance spectra of PSCFSx changed not only
with Sc3þ concentration but also with temperatures. For PSCFSx
0
(x  0.1) on GDC at 550  C and above, only one resistance/
0 150 300 450 600 750 900 capacitance arc mainly at LFR can be observed. An additional
impedance arc across HFR and MFR has been observed for
PSCFSx (x  0.1) on GDC at lower temperatures (<550  C).
Fig. 5 e The temperature dependence of electrical Differently, for PSCFSx (x > 0.1), two resistance/capacitance
conductivity of PSCFSx (x [ 0.0e0.2) under an air arcs have been observed at 700  C and below, one arc at LFR can
atmosphere. only be observed at higher temperatures (750  C).
3994 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 3 9 8 9 e3 9 9 6

For all the PSCFSx, the resistance/capacitance across the
HFR and MFR is dominant at lower temperatures because it is
difficult to dissociate oxygen atom into the oxygen ion, as the
activation barrier is much greater than the thermal energy of
gas, moreover, the ionic conductivity of electrolyte and the
electronic conductivity of cathode are low at lower tempera-
tures. The resistance at the HFR and MFR decreased rapidly
with increasing temperature, and becomes no longer domi-
nant at higher temperatures, because the gas had sufficient
energy to overcome the activation barrier and the ionic/elec-
tronic conductivities of materials increased with temperature.
Oxygen transport in cathode becomes the rate-determining
step at higher temperatures.
HFR and MFR resistance/capacitance declined to incog-
nizable part in impedence spectra for x  0.1 at 550  C and
above, whereas for x > 0.1, similar transition occurred at
750  C and above. The fact indicated that the dissociation of
oxygen atom into the oxygen ion may be easier in PSCFSx
(x  0.1) than in PSCFSx (x > 0.1), revealing that the electro-
chemical activity of PSCFSx (x  0.1) is better than PSCFSx
(x  0.1). Moreover, the relative high electrical conductivity of
PSCFSx (x  0.1) may also be partly responsible for the decline
of HFR and MFR arcs. The LFR resistance dominates the total
impedance of PSCFSx (x  0.1) at most tested temperatures
(550e800  C) indicating that the transport of oxygen species in
the cathodes is the main limitation of their performance,
therefore, the optimization of electrode microstructure will
further improve the cathode performance. The ASR of
PSCFS0.05 and PSCFS0.1 at 600  C decreased by 19% and 22%,
respectively, compared with that of PSCF as shown in Fig. 6a.
These results revealed that the small amount of Sc3þ dopant
species and metal cations. TPR curves of PSCFSx (x ¼ 0.0e0.2)
were shown in Fig. 7. It can be seen that a peak at 258  C only
can be observed in the TPR profile for PSCFS0.05, it may be
attributed to the reduction of absorbed oxygen species which
was tested by XPS in the following paragraph. The peaks at
300e400  C were ascribed to the reduction of surface Co3þ to
Co2þ [15], the reduction temperature decreased monotonically
with increasing the concentration of scandium x, indicating
that Sc3þ dopant promoted the reduction of surface Co3þ to
Co2þ. The decrease of surface Co3þ may be helpful for the
increase of oxygen vacancy at the surface of cathode, which
may contribute to the improvement of cathode performance.
The successive two peaks at 650e950  C were attributed to the
reduction of lattice metal species such as Co2þ to Co0 and Fe3þ
to Fe0 successively. The reduction temperature of these B site
metal species decreased from 780  C/860  C for PSCF to the
lowest values of 753  C/818  C for PSCFS0.05, then increased
again with x to 762  C/826  C and 790  C/864  C respectively for
PSCFS0.1 and PSCFS0.2. This trend is agree well with ASR
change with Sc3þ concentration x as exhibited in Fig. 6b.
Therefore, it is reasonable to proposed that small amount of
Sc3þ (x  0.10) facilitated the reduction of lattice Co2þ and Fe3þ,
then obviously decreased their reduction temperatures. This
in turn promoted the formation of oxygen vacancy in the bulk
cathode and accelerated the transportation of oxygen species,
eventually improved the electrochemical performance of
a Active
[O] Lattice
Oxygen Oxygen
Intensity / a.u.

(x  0.1) can improve the oxygen transport in cathode. The

effect of Sc3þ dopant on the electrochemical performance of PSCFS0.05
PSCFSx (x  0.1) was further investigated by the H2 tempera-
ture-programmed reduction (H2-TPR) in the following
paragraph.

3.5. H2-TPR and XPS characterizations

PSCF
In order to reveal the reason of catalytic improvement of PSCF
doped with small amount of Sc3þ (x  0.10), H2-TPR was per- 536 534 532 530 528 526
formed to examine the reducibility of adsorbed oxygen Binding Eenergy / eV
b
[Sr] 3d
790
864
Relative Intensity

PSCFS0.20
Intensity / a.u.

310
762 PSCFS0.05
826
313 PSCFS0.10 753
818

258
320 780
PSCFS0.05
860
359 PSCF
PSCF

150 300 450 600 750 900 140 138 136 134 132 130 128 126
Binding Energy / eV
Fig. 7 e Hydrogen temperature-programmed reduction Fig. 8 e The XPS spectra of (a) O1s and (b) Sr3d for PSCF and
(TPR) curves of PSCFSx (x [ 0.0e0.2) oxides. PSCFS0.05 powders.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 3 9 8 9 e3 9 9 6
Table 2 e XPS results of O1s and Sr3d at the surface of
materials.
Cathode O1s Sr3d
materials (mol/%)
Binding Percent in
energy (eV) total oxygen (%)
PSCF 530.9 81.8
528.5 18.2
PSCFS0.05 531.3 63.9
528.7 36.1
PSCFSx (x ¼ 0.05e0.10) cathode. However, higher amount of
Sc3þ (x > 0.10) hindered the reduction of these metal species
resulting in the increase of the reduction temperature, and
finally deteriorated the catalytic ability of PSCFS0.2.
Based on XRD, electrical conductivity, EIS and TPR results,
the optimized Sc3þ doping level should be around 5e10 mol%.
At such a doping level, a balance between high electrical
conductivity and better cathode performance should be
reached. Although PSCFS0.20 exhibited the lowest TEC value,
its low conductivity (less than 50 S cm
1 at all tested
temperature range) and high ASR made it not ideal for cathode
material.
In order to further examine oxygen species and Sr cationic
oxidation in surface regions of PSCFS0.05 which may
contribute to the best electrochemical performance of
PSCFS0.05. XPS measurements were carried out for PSCF and
PSCFS0.05, XPS spectra for O and Sr were shown in Fig. 8.
The O1s peak at 528.7 eV of PSCF in Fig. 8a was attributed to
the surface lattice oxygen of the perovskite structure [16]. The
peak shifted toward a lower binding energy (BE) for PSCFS0.05
to 528.5 eV. These shift toward lower BE probably arises from
a difference in the molecular environment surrounding the O
atom. The peak at 531.3 eV for PSCF and 530.9 eV for PSCFS0.05
corresponded to chemisorbed oxygen in the forms of O2
2 and
O
. The absorbed oxygen in transition metal oxides was
related to the amount of oxygen deficiency (d). In other words,
the atomic percentages of oxygen-related sites in different
chemical states were expressed as area of one state of oxygen
peak to the total oxygen area indicated the concentration of
oxygen vacancy in the material for qualitative analysis. The
81.8% for attractive oxygen of PSCFS0.05 was higher than that
of PSCF with 63.9%. This indicated a higher concentration of
oxygen vacancy for PSCFS0.05. On the contrary, the molar
percentage of surface Sr3d of PSCFS0.05 was lower than that of
PSCF as shown in Fig. 8b and Table 2. The decrease of surface
SrO was benefit to the promotion of catalytic performance of
materials [8]. Therefore, the better performance of PSCFS0.05
relative to that of PSCF may have been contributed by the
absorbed oxygen species at the surface of material, the
decrease of surface SrO content and easy reduction of bulk
metal species.
4. Conclusion
A small amount of Sc3þ was doped into the B site of PSCF
forming new perovskite oxides denoted as PSCFSx
(x ¼ 0.05e0.2). Both PSCF and PSCFSx possessed perovskite
structure based on XRD results. TEM images showed that
3995
PSCFSx-600 (x ¼ 0.05e0.2) demonstrated smaller particles
compared to PSCF-600. The introduction of Sc3þ into the
oxides led to the decrease of electrical conductivity, but
PSCFSx (x  0.1) oxides still maintained electrical conductivity
high enough for application as IT-SOFC cathode. Among the
various PSCFSx oxides examined, PSCFS0.05 and PSCFS0.1
6.6 demonstrated smaller area-specific polarization resistance
than their parent oxide, which was might attribute to the
5.5 optimization of surface and bulk oxygen vacancies and
decrease of surface SrO content particle size, as revealed by
TPR and XPS. The general decrease of TEC values of doped
samples suggests that scandium doping is beneficial to
improve the thermal expansion properties of PSCF especially
at temperature ranges not more than 600  C. Considering all
tested items, it was concluded that PSCFSx at x  0.1 had
potential for application as cathode materials in IT-SOFCs. But
the present polarization resistance of these cathode materials
is still high, therefore, the optimization of microstructure of
the cathode layer is ongoing in our lab to further decrease the
polarization resistance of cathode electrode.
Acknowledgments
The authors are grateful for the financial support of this work
by United Technology Research Center, USA. It is also to be
thankful for the kindly support by the Natural Science Foun-
dation of China (20973111), 973 Program of China
(2007CB209705) and the Science and Technology Commission
of Shanghai Municipality (09ZR1413900, 10520708900 and
09XD1402400). Thanks were also given to the support of Nat-
ional Key Laboratory of Metallic Matrix Composite Material and
China Postdoctoral Science Foundation (20090450695).
references
[1] Brett DJL, Atkinson A, Brandon NP, Skinner SJ. Intermediate
temperature solid oxide fuel cells. Chem Soc Rev 2008;37:
1568.
[2] Adler SB. Factors governing oxygen reduction in solid oxide
fuel cell cathodes. Chem Rev 2004;104:4791.
[3] Zhu B. Solid oxide fuel cell (SOFC) technical challenges and
solutions from nano-aspects. Int J Energy Res 2009;33:1126.
[4] Suzuki T, Hasan Z, Funahashi Y, Yamaguchi T, Fujishiro Y,
Awano M. Impact of anode microstructure on solid oxide fuel
cells. Science 2009;325:852.
[5] Qiu L, Ichikawa T, Hirano A, Imanishi N, Takeda Y.
Ln1
xSrxCo1
yFeyO3
d (Ln ¼ Pr, Nd, Gd; x ¼ 0.2, 0.3) for the
electrodes of solid oxide fuel cells. Solid State Ionics 2003;
158:55.
[6] Kammer K. Studies of FeeCo based perovskite cathodes with
different A-site cations. Solid State Ionics 2006;177:1047.
[7] Zeng PY, Ran R, Chen ZH, Zhou W, Gu HX, Shao ZP, et al.
Efficient stabilization of cubic perovskite SrCoO3
d by B-site
low concentration scandium doping combined with sol-gel
synthesis. J Alloy Compd 2008;455:465.
[8] Gu HX, Zheng Y, Ran R, Shao ZP, Jin WQ, Xu NP, et al.
Synthesis and assessment of La0.8Sr0.2ScyMn1
yO3
d as
cathodes for solid-oxide fuel cells on scandium-stabilized
zirconia electrolyte. J Power Sources 2008;183:471.
3996 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 3 9 8 9 e3 9 9 6
[9] Zhou W, Ran R, Shao ZP, Jin WQ, Xu NP. Evaluation of A-site
cation-deficient (Ba0.5Sr0.5)1
xCo0.8Fe0.2O3
d (x > 0) perovskite
as a solid-oxide fuel cell cathode. J Power Sources 2008;182:24.
[10] Mai A, Tietz F, Stöver D. Partial reduction and re-oxidation of
iron-and cobalt-containing perovskites using catalyst
characterisation measurements. Solid State Ionics 2004;173:35.
[11] Steele BCH, Heinze A. Materials for fuel-cell technologies.
Nature 2001;414:345.
[12] Parka K, Leeb C, Baea J, Yooc Y. Structural and
electrochemical properties of Pr0.3Sr0.7Co0.3Fe0.7O3
d cathode
for IT-SOFC. Int J Hydrogen Energy 2009;34:6852.
[13] Adler SB. Mechanism and kinetics of oxygen reduction on
porous La1-xSrxCoO3
d electrodes. Solid State Ionics 1998;
111:125.
[14] Adler SB, Lane JA, Steele BCH. Electrode kinetics of porous
mixed-conducting oxygen electrodes. J Electrochem Soc
1996;143:3554.
[15] Pena MA, Fierro JLG. Chemical structure and performance of
perovskite oxides. Chem Rev 2001;101:1981.
[16] Van der heide PAW. Systematic x-ray photoelectron
spectroscopic study of La1
xSrx-based perovskite-type
oxides. Surf Interface Anal 2002;33:414.