Solid State Ionics 177 (2006) 149 – 157

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(La0.75Sr0.25)(Cr0.5Mn0.5)O3/YSZ composite anodes for methane oxidation

reaction in solid oxide fuel cells
S.P. Jiang *, X.J. Chen, S.H. Chan, J.T. Kwok, K.A. Khor
School of Mechanical and Aerospace Engineering, Nanyang Technological University, Singapore 639798, Singapore

Received 19 April 2005; received in revised form 10 August 2005; accepted 7 September 2005

Abstract

The synthesis and performance of (La0.75Sr0.25)(Cr0.5Mn0.5)O3/Y2O3 – ZrO2 (LSCM/YSZ) composites are investigated as alternative anodes for
the direct utilization of methane (i.e., natural gas) in solid oxide fuel cells. Addition of YSZ phase greatly improves the adhesion and reduces the
electrode polarization resistance of the LSCM/YSZ composite anodes. LSCM/YSZ composite anodes show reasonably good performance for the
methane oxidation reaction in wet CH4 and the best electrode performance was achieved for the composite with LSCM contents of 50 – 60 wt.%
with polarization resistances of 2 – 3 V cm2 in 97% CH4/3% H2O at 850 -C. The electrode impedance for the methane oxidation in wet CH4 on the
LSCM/YSZ composite anodes was characterized by three separable arcs and the electrode behavior could be explained based on the ALS model
for the reaction on the MIEC electrode. The results indicate that electrocatalytic activity of the LSCM/YSZ composite anodes for the methane
oxidation is likely limited by the oxygen vacancy diffusion in the substituted lanthanum chromite-based materials.
D 2005 Elsevier B.V. All rights reserved.

PACS: 84.60.D
Keywords: Alternative anodes; LSCM/YSZ composite; Methane oxidation; Solid oxide fuel cells

1. Introduction endothermic nature of the steam reforming reaction can also

It is well known that Ni/Y2O3 –ZrO2 (Ni/YSZ) cermet
anodes of solid oxide fuel cells (SOFC) have excellent
catalytic properties and stability for the H2 oxidation of
hydrogen fuel at SOFC operation conditions [1,2]. However,
Ni/YSZ-based anode suffers a number of drawbacks in
systems where hydrocarbon fuel is used such as sulfur
poisoning and carbon deposition [2]. Carbon deposition covers
the active sites of the anode, resulting in the loss of the cell
performance [3]. Under high carbon activity environment, Ni
metal could be corroded by a process known as metal dusting
[4]. As Ni is a good catalyst for hydrocarbon cracking reaction,
Ni/YSZ cermet anodes can only be directly used in hydrocar-
bon fuels if excess steam is present to ensure the complete fuel
reforming and to suppress the carbon deposition. High steam/
carbon ratio is not attractive for fuel cells as it lowers the
electrical efficiency of the fuel cells by diluting the fuel. The
* Corresponding author. Fax: +65 6791 1859.
E-mail address: mspjiang@ntu.edu.sg (S.P. Jiang).
0167-2738/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.ssi.2005.09.010
cause local cooling and steep thermal gradients potentially
capable of mechanically damaging the cell stack [5]. Thus,
development of structurally stable anodes with high electro-
catalytic activity for hydrocarbon fuel oxidation is vital for the
natural gas fuel-based SOFC.
Replacing Ni/YSZ cermet anodes by Ni-free oxides such as
ceria, titanate and lanthanum chromite-based oxides has
attracted a great attention recently. Doped LaCrO3-based
materials have been extensively investigated as interconnect
material in SOFC [6]. LaCrO3-based oxide such as (LaSr)CrO3
was shown to have very low activity towards carbon deposition
[7]. Catalytic activity of LaCrO3 for methane oxidation can also
be substantially enhanced by partial substitution at A- and B-
sites. Sfeir et al. [8,9] studied the thermodynamic stability and
the catalytic activity of (LaA)(CrB)O3 system (A= Ca, Sr and
B = Mg, Mn, Fe, Co, Ni) as alternative anode materials under
simulated SOFC operation conditions. Thermodynamically, Sr
and Mn substitution maintains the stability of the perovskite
while other substitutes destabilize the system. However,
transition metal substituted LaCrO3 did not decompose easily
under reducing conditions, indicating that the decomposition of
150 S.P. Jiang et al. / Solid State Ionics 177 (2006) 149 – 157
the substituted LaCrO3 would be hindered kinetically. Ca and Sr
substitution at the A-site improves the catalytic activity and for
B-site substitution, Co and Mg show an inhibiting effect while
Mn, Fe and Ni improve the activity.
Recently, Tao and Irvine [10,11] reported promising results
of La0.75Sr0.25Cr0.5Mn0.5O3 (LSCM) as anode for SOFC.
LSCM is a p-type conductor with conductivity of ¨ 38 S
cm
1 in air and 1.5 S cm
1 in 5% H2 at 900 -C. The electrode
polarization resistance for the oxidation reactions in wet CH4
and H2 at 900 -C was 0.85 V cm2 and 0.26 V cm2,
respectively. The performances are considered to be compatible
to the Ni/YSZ cermet anodes. Addition of the ionic conducting
phase such YSZ allows delocalization of the reaction in the
entire electrode volume, increasing the reaction sites and
enhancing the performance of the electrode. Thus, it would
be interesting to investigate the performance of LSCM/YSZ
composite anodes. In this report, the fabrication and perfor-
mance of LSCM/YSZ composite anodes were investigated to
assess their feasibility as alternative anodes for methane
oxidation reactions for SOFC. The process and reaction
mechanism of the CH4 oxidation reaction in wet CH4 (3%
H2O) are discussed.
2. Experimental
YSZ electrolyte substrates were prepared from 8 mol%
yttria-stabilized zirconia (YSZ, Tosoh, Japan) powders by die
pressing and sintered at 1550 -C for 4 h. The diameter and
thickness of the YSZ electrolyte were ¨ 20 mm and ¨ 1 mm,
respectively. The surface of YSZ discs was ground using
sandpapers to increase the roughness of the surface and the
contact between the electrode and the YSZ electrolyte.
The composition of LSCM was chosen as La0.75Sr0.25
Cr0.5Mn0.5O3 (LSCM) [10,11]. LSCM was prepared from
La2O3, SrCO3, Cr2O3 and MnCO3 (all from Aldrich) by
solid-state reaction. La2O3 was heat-treated at 1000 -C to get
rid of the moisture. The powders were mixed and ball-milled
for 4 h with propanol. The mixture was then heated at 1200
-C for 20 h in air. LSCM/YSZ composites with various
weight ratios were made by ball milling for 1 h. The mixture
of LSCM and YSZ was again mixed thoroughly with addition
of PG400 in mortar for another 30 min to form slurry. Carbon
(5 wt.%) was added to the composite slurry as pore-former.
LSCM and LSCM/YSZ composite electrodes were applied to
the electrolyte disk by slurry painting. To study the sintering
temperature, LSCM (50 wt.%)/YSZ (50 wt.%) composite
anodes were sintered at 1100, 1200 and 1300 -C in air,
respectively, for 2 h.
The thermal expansion coefficients of the LSCM and LSCM
(50%)/YSZ (50%) composites were measured by a Perkin
Helmer Dynamic Mechanical Analyzer. The samples were
pressed into cylinder with a diameter of 10 mm and a length of
5 mm. After sintering at 1200 -C for 2 h, the diameter of the
cylinders shrank to ¨ 8 mm. Temperature was raised from 30
-C to 900 -C with heating rate of 10 -C min
1. Data were
recorded and thermal expansion coefficient (TEC) was
calculated from the slope of the curve.
Platinum paste was painted onto the center of the other side
of the electrolyte substrate as the counter electrode and the
reference electrode was painted as a ring at the edge of the
electrolyte substrate. Pt mesh was used as current collector for
both anode and counter electrode. Different to the experimental
settings reported by Tao and Irvine [11], no additional Pt or Au
paste was applied to the coating surface of the anode. The
distance between the counter and ring reference electrodes was
¨ 4 mm. Methane humidified at room temperature (97% CH4/
3% H2O) was used as fuel and air was used as oxidant. The
fuel flow rate was controlled at 100 sccm. Electrochemical
impedance spectroscopy was carried out using a Solartron 1255
frequency response analyzer coupled to a Solartron 1287
electrochemical interface. The impedance spectra of the
electrochemical cell were recorded at open circuit voltage
(OCV) with amplitude of 10 mV over the frequency range 0.01
Hz to 1 MHz. The ohmic resistance of the electrolyte and the
anode (R V) was estimated from the high frequency intercept of
the impedance curves and the overall electrode polarization
(interface) resistance (R E) was directly measured from the
differences between the low and high frequency intercepts on
the impedance curves. The impedance responses were analyzed
using an equivalent circuit method. The measurement was
carried out in the temperature range of 800 to 950 -C.
Microstructure of the anodes after the performance testing
was inspected by scanning electron microscopy (SEM, Leica
360, Germany).
3. Results and discussions
3.1. The phase and thermal expansion coefficient
Fig. 1 is the X-ray diffraction (XRD) pattern of a LSCM
powder sintered at 1200 -C. The patterns are identical to the
La0.75Sr0.25Cr0.5Mn0.5O3 obtained at 1400 -C [11], indicating
the formation of the perovskite phase of the LSCM powder.
Fig. 2 shows the thermal expansion of pure LSCM and LSCM
(50%)/YSZ (50%) composite. The linear thermal expansion
coefficient (TEC) of LSCM is 9.2  10
6 K
1 in the
Fig. 1. XRD pattern of La0.75Sr0.25Cr0.5Mn0.5O3 (LSCM) powder sintered at
1200 -C for 20 h.
 S.P. Jiang et al. / Solid State Ionics 177 (2006) 149 – 157 151

Fig. 4. Impedance curves of the reaction on LSCM (50 wt.%)/YSZ (50 wt.%)
composite anodes sintered at different temperatures. The EIS was measured at
850 -C in wet CH4.
Fig. 2. The TEC of La0.75Sr0.25Cr0.5Mn0.5O3 (LSCM) and LSCM (50%)/YSZ
(50%) at high temperatures in air.
temperatures in 97% CH4/3% H2O (wet CH4), as shown in Fig.
3. In the figure, the solid lines are the theoretical open circuit
temperature range of 34 – 135 -C and 13.7  10
6 K
1
potentials based on the equilibrium of the 97% CH4/3% H2O
between 161 -C and 900 -C. There is a slope change at
fuel and air as oxidant (the theoretical calculation for H2O –
135 –161 -C. The average TEC between 30 -C and 900 -C is
CH4/air system is given in Appendix A). In comparison, the
11.4  10
6 K
1, which is higher than 9.3  10
6 K
1
theoretical OCP and the measured OCP on a LSCM (50 wt.%)/
reported by Tao and Irvine [11] for the same oxide.
YSZ (50 wt.%) composite anode sintered at 1200 -C in 97%
Addition of YSZ phase reduces the thermal expansion of the
H2/3% H2O is also given in the figure. For the LSCM (50
composite. In the case of LSCM (50%)/YSZ (50%) compo-
wt.%)/YSZ (50 wt.%) composite anodes in wet CH4, the OCP
sites, the TEC is 8.4  10
6 K
1 and 12.2  10
6 K
1 in the
was typically in the range 0.91 to 0.93V at 850 -C and
temperature range of 30– 243 -C and 291– 900 -C, respective-
decreased slightly with the increase in the sintering temperature
ly. The slope change occurred between 243 and 291 -C. The
of the anodes. The OCP in wet CH4 decreases with the
average TEC between 30 and 900 -C is 10.3  10
6 K
1,
decrease in temperature and shows the same trend as the
identical to that of the YSZ electrolyte. This indicates that
calculated OCP based on the thermodynamic equilibrium in the
matching of the TEC of the LSCM/YSZ composites with YSZ
97% CH4/3% H2O fuel. However, the theoretical OCP at 97%
electrolyte can be achieved.
CH4/3% H2O is 1.246 V at 850 -C, much higher than that
measured on the LSCM/YSZ composite anodes. The very low
3.2. Open circuit potential (OCP) behavior
observed OCP as compared to the theoretical OCP is most
likely due to the low conversion of methane on the substituted
The open circuit potential (OCP) of the LSCM (50 wt.%)/
lanthanum chromites [8]. This is also supported by the
YSZ (50 wt.%) composite anodes was recorded at different
observation that addition of small amount of Ni (¨ 5 wt.%)

Fig. 3. Open circuit potentials (OCP) of the LSCM (50 wt.%)/YSZ (50 wt.%)
composite anodes at different temperatures in wet CH4. The composite anodes
were sintered at different temperatures. The solid lines are the theoretical OCP
for the systems of 97% CH4/3% H2O and 97% H2/3% H2O fuels and air as
oxidant.
Fig. 5. Electrode polarization resistance, R E, of the reaction on LSCM (50
wt.%)/YSZ (50 wt.%) composite anodes as a function of anode sintering
temperature. EIS was measured at open circuit in wet CH4 at different
temperatures.
152 S.P. Jiang et al. / Solid State Ionics 177 (2006) 149 – 157
(a) 1100°C
(b) 1200°C
(c) 1300°C
2 µm
Fig. 6. SEM micrographs of the surface of the LSCM (50 wt.%)/YSZ (50 wt.%)
composite anodes sintered at different temperatures after testing.
to the LSCM/YSZ composite anodes significantly increased
the OCP values for the reaction in wet CH4. For example, for
the reaction on a 5 wt.% Ni added LSCM (50 wt.%)/YSZ (50
wt.%) composite anode in wet CH4, the OCP increased to
¨ 1.19 V at 850 -C, which is much higher than ¨ 0.92 V
observed on the same composite anodes without Ni addition at
the same temperature. However, we found no significant
improvement of the electrochemical performance of the Ni
added LSCM/YSZ composite anodes for the methane oxidation
reaction. In wet H2, as would be expected, the OCP for the H2
oxidation reaction on LSCM/YSZ composite anode increases
with the decrease in temperature and is close to that calculated
for the 97% H2/3% H2O system. This indicates that the lower
OCP observed on LSCM/YSZ composite anodes in wet CH4 as
compared to the calculated one is not due to the leakage of the
system.
3.3. Effect of composite anode sintering temperature
The electrolyte and electrode ohmic resistance, R V, varied
significantly with the anode sintering temperatures. For
example, for the LSCM (50 wt.%)/YSZ (50 wt.%) composite
anodes sintered at 1100 -C, R V was 3.0– 3.5 V cm2 at 900
-C. When the sintering temperature increased to 1200 -C, R V
at 900 -C decreased significantly to 1.3 –1.6 V cm2. Further
increase in the anode sintering temperature only slightly
increased the R V values to ¨ 2.0 V cm2. At 900 -C, the
conductivity for the Tosoh YSZ powder was reported as
0.109 S cm
1 [12]. Thus, the ohmic contribution of the YSZ
electrolyte with thickness of 1 mm would be 0.92 V cm2 at
900 -C. The higher resistance of the cell with the LSCM/YSZ
composite anodes as compared to the electrolyte resistance
indicates the ohmic resistance of the LSCM/YSZ composite is
not negligible and this is probably due to the low conductivity
of the LSCM material in reducing environment [11].
Nevertheless, the significant variation of the R V with the
sintering temperature shows the cell resistance of LSCM/YSZ
anode also depends on the anode sintering temperatures.
Fig. 4 is the impedance curves of the methane oxidation
reaction on LSCM (50 wt.%)/YSZ (50 wt.%) composite
anodes sintered at different temperatures. For the purpose of
comparison, the high frequency intercept of the impedance
responses was adjusted to zero. For the methane oxidation at
850 -C, the electrode polarization resistance was 11.5, 2.3 and
12.7 V cm2 for the LSCM/YSZ composite anodes sintered at
1100, 1200 and 1300 -C, respectively. Clearly, the composite
anode sintered at 1200 -C has the lowest electrode
polarization resistance (R E). It is interesting to note that the
sintering temperature has significant effect on the impedance
responses at low frequencies. This is also the case for the
electrode polarization resistance measured at other tempera-
tures. Minimum R E was obtained for the composite anodes
sintered at 1200 -C, as shown in Fig. 5. The electrode
performance for the LSCM/YSZ composite anode in the
present study is lower than that reported for the graded LSCM
anodes (R E is ¨ 0.8 V cm2 in wet CH4 at 900 -C [11]). This
is probably due to the fact that we did not use Pt or Au paste
on the anode coating and have not attempted to optimize the
electrode structure and structure of the composite anodes
using functional graded electrode approaches. As shown
recently, the resistance and polarization performance of the
fuel cell depends significantly on the contact area between the
electrode coating and the current collector and the mechanical
Fig. 7. Impedance curves of the LSCM (30 wt.%)/YSZ (70 wt.%), LSCM (50
wt.%)/YSZ (50 wt.%) and LSCM (70 wt.%)/YSZ (30 wt.%) composite anodes
in wet CH4 at 900 -C.
 S.P. Jiang et al. / Solid State Ionics 177 (2006) 149 – 157 153

load [13,14]. Thus, the use of Pt or Au paste [11] could partly

Fig. 8. Plots of the electrode polarization resistance (R E) for the reaction in wet
CH4 as a function of the LSCM/YSZ composite composition, measured at
different temperatures.
lead to the improvement in the electrode performance through
the increased contact areas between the LSCM anode and
current collector.
Fig. 6 shows the SEM micrographs of the surface of the
LSCM (50 wt.%)/YSZ (50 wt.%) composite anodes sintered
at different temperatures after testing. For the anode sintered
at 1100 -C, the microstructure of the LSCM/YSZ composite
anode is characterized by relatively large LSCM grains
covered by fine YSZ particles. However, it appears that the
contact between the LSCM and YSZ particles is poor as there
is little necking formation between the particles. This may
imply the poor interface between the LSCM/YSZ composite
anode and YSZ electrolyte. The poor interface contact
between the LSCM and YSZ electrolyte is indirectly
indicated by the high cell resistance (R V = 3.0– 3.5 V cm2)
and relatively high electrode polarization resistance for the
anodes sintered at 1100 -C (Fig. 5). As the sintering

(a)
(b)

2 µm 2 µm

(c) (d)

2 µm 2 µm

(e) (f)

2 µm 5 µm

Fig. 9. SEM micrographs of the surface of (a) LSCM (30 wt.%)/YSZ (70 wt.%), (b) LSCM (50 wt.%)/YSZ (50 wt.%), (c) LSCM (60 wt.%)/YSZ (40 wt.%), (d)
LSCM (70 wt.%)/YSZ (30 wt.%) and (e) pure LSCM anodes. The cross-section of LSCM (50 wt.%)/YSZ (50 wt.%) composite anode is given in (f).
154 S.P. Jiang et al. / Solid State Ionics 177 (2006) 149 – 157

temperature increases, there is significant grain growth of
LSCM and in particular YSZ in the composite anodes. The
particle size of YSZ was ¨ 0.5 Am, significantly larger than
¨ 0.2 Am for the anode sintered at 1100 -C. Moreover, there
is clearly necking formation between the YSZ and LSCM
particles (Fig. 6b). The necking formation leads to the
intimate contact between the LSCM-to-LSCM, YSZ-to-YSZ
and YSZ-to-LSCM particles in the composite, resulting in the
formation of the continuous network of both ionic and
electronic conduction [15]. This also indicates the good
interfacial contact between the LSCM/YSZ anode and YSZ
electrolyte. Thus, the low R V and low electrode polarization
resistance for the LSCM/YSZ composite anodes sintered at
1200 -C are most likely due to the significant enhancement
of the interface contact between the LSCM and YSZ phases.
Further increasing the sintering temperature would simply
cause the grain growth with no additional benefit to the
interface contact between the LSCM and YSZ. However, the
rather rapid increase of the electrode polarization resistance
indicates that sintering at 1300 -C has significant detrimental
effect on the electrode electrocatalytic activity for the
methane oxidation reaction probably due to the resistive
layer formation at the LSCM and YSZ interface. The
formation of the resistive phase such lanthanum zirconate at
the LSCM and YSZ interface may be similar to that between
the A-site stoichiometry Sr-doped LaMnO3 and YSZ [16,17].
Thus in the following sections, all LSCM/YSZ composite
anodes were sintered at 1200 -C without specification.
3.4. Effect of LSCM/YSZ composite composition
microstructure of the LSCM/YSZ composite anodes depends
on the composition. For LSCM (30 wt.%)/YSZ (70 wt.%)
composite anode, the microstructure is characterized by the
large LSCM particles completely embedded in the fine YSZ
particles. Pores were in the range of 0.3 –0.8 Am and were
uniformly distributed. The porosity appears to be small (Fig.
9a). As the LSCM content in the composite increases, there is
gradually an increase in the porosity and the number of large
pores. In the case of LSCM (50 wt.%)/YSZ (50 wt.%), the
distribution of LSCM large particles and YSZ fine particles is
clearly visible and there is a formation of small and large pores
(Fig. 9b). A good interface contact between the LSCM/YSZ
composite anode and YSZ electrolyte is formed (Fig. 9f). The
porosity increased significantly as compared to that of the
LSCM (30 wt.%)/YSZ (70 wt.%) composite anode. Despite the
open structure of the LSCM/YSZ composite anode, it appears
that LSCM and YSZ particles are networked to form
continuous LSCM-to-LSCM and YSZ-to-YSZ contact. Such
open structure with good distribution of fine and coarse pores is
consistent with the low electrode polarization resistance
measured for the methane oxidation. Increasing the LSCM
content to 70 wt.% resulted in the reduction in porosity (Fig.
9d). This may be caused by the significant grain growth of the
LSCM phase due to the reduced inhibiting effect of YSZ
phases in the composite. For pure LSCM anodes, the particles
were in the range of 1 –2 Am and porosity is very small (Fig.
9e). In some part of the pure LSCM electrode coating, nano-
sized fiber-like deposits were also found, indicating the poor
conversion of methane on the LSCM. This explains the high
R E values for the reaction for the pure LSCM and LSCM/YSZ

The LSCM/YSZ composite anodes with LSCM contents

in the range of 30– 100 wt.% were studied. In this case, no
significant variation of the cell resistance, R V, with the
composition of the LSCM/YSZ composite was found. Fig. 7
shows typically the impedance responses of the LSCM (30
wt.%)/YSZ (70 wt.%), LSCM (50 wt.%)/YSZ (50 wt.%),
and LSCM (70 wt.%)/YSZ (30 wt.%) composite anodes in
wet CH4 at 900 -C. The electrode polarization performance
clearly depends on the LSCM/YSZ composition. For the
CH4 oxidation reaction on the LSCM/YSZ composite
anodes, the electrode polarization resistance is low for the
anodes with LSCM content close to 50 wt.%. As shown in
the figure, the LSCM content in the composite anode
primarily affects the low frequency impedance responses.
Fig. 8 shows the plots of the electrode polarization re-
sistance for the reaction in wet CH4 as a function of the
LSCM/YSZ composite composition, measured at different
temperatures. Electrode polarization resistance (R E) of pure
LSCM anodes is high and decreases significantly with the
increase of LSCM contents in the composite. In the case of
pure LSCM, delamination of the anode was also observed.
The results indicate that the best performance of the LSCM/
YSZ composite is the composite anode with 50– 60 wt.%
LSCM. Fig. 10. Impedance curves for the oxidation reaction in wet CH4 at different
SEM micrographs of the LSCM/YSZ composite anodes temperatures on a LSCM (50 wt.%)/YSZ (50 wt.%) composite anode. Symbols
with various compositions are presented in Fig. 9. The are experimental data and lines are fitted results. Numbers are frequency in Hz.
 S.P. Jiang et al. / Solid State Ionics 177 (2006) 149 – 157 155

Fig. 11. The equivalent circuit used for the fitting of the collected impedance data of LSCM (50%)/YSZ (50%) composite anodes. In the figure, L is the inductance,
R S the electrolyte resistance, R 1 and Q 1 the electrode polarization resistance and constant phase element (CPE) of the high frequency arc, R 2 and Q 2 the electrode
polarization resistance and constant phase element (CPE) of the medium frequency arc, and R 3 and Q 3 the electrode polarization resistance and constant phase
element (CPE) of the low frequency arc.

composite anodes with LSCM content higher than 70 wt.%
(Fig. 8).
3.5. Oxidation reaction in wet CH4
Fig. 10 is the impedance curves for the CH4 oxidation
reaction on a LSCM (50 wt.%)/YSZ (50 wt.%) composite
anode in wet CH4 at different temperatures under open circuit
condition. Symbols are the experimental data and lines are
the fitted results. The equivalent circuit for the fitting is
shown in Fig. 11. Table 1 gives the fitted results for the
reaction at different temperatures. Good fitting between the
equivalent circuit and the observed data is observed. Most
interesting, as the operation temperature increases, the
impedance responses particularly at low frequencies decrease
significantly. Three impedance arcs are clearly separated at
high, medium and low frequencies. This indicates that the
electrochemical oxidation of CH4 on LSCM/YSZ composite
anodes is limited by at least three electrode steps. For the
reaction at 800 -C, the characteristic frequencies for the high,
medium and low frequency arcs are 501, 3.16 and 0.02 Hz,
respectively (Fig. 10b).
Fig. 12 is the activation energy plots of the electrode
polarization resistance for the oxidation reaction in wet CH4
on the LSCM (50 wt.%)/YSZ (50 wt.%) composite anodes.
For the methane oxidation, the activation energies are 159,
168 and 150 kJ mol
1 for the electrode process at high,
medium and low frequency arcs. The activation energy of the
overall electrode resistance for the methane oxidation reaction
is 160 kJ mol
1. High activation energy of 160– 200 kJ
mol
1 was also reported by Primdahl et al. [18] for the H2
oxidation reaction on La0.8Sr0.2Cr0.97V0.03O3 anode. In the
temperature range studied, it is clear that the oxidation
reaction in wet CH4 is dominated by the low frequency
impedance process. For the H2 oxidation reaction on Ni/YSZ
cermet anodes, the reaction is generally considered to be
limited by two electrode steps, namely, hydrogen dissociative
adsorption and diffusion on the Ni surface or hydrogen gas
diffusion inside the porous anode, and the charge transfer
reaction at the electrode and electrolyte interface [19]. The
electrode process associated hydrogen dissociative adsorption
has much lower activation energy (0 –50 kJ mol
1) as
compared to the charge transfer process [19,20]. The three
phase boundary areas between the Ni electrode, YSZ
electrolyte and H2 reactant gas play a very important role
in the reaction kinetics of the H2 oxidation reaction in the Ni
and Ni/YSZ cermet anodes [15,21]. The high activation
energy, 150 kJ mol
1, of the electrode process associated
with low frequency arc on the LSCM/YSZ composite anodes
indicates that the low frequency impedance is not dominated
by the gas phase diffusion inside the porous LSCM/YSZ
composite anodes. Such high energetic process also implies
that the low impedance response for the CH4 oxidation
reaction on the LSCM/YSZ composite anodes could not be
the gas diffusion impedance due to the stagnant gas outside
the porous anode, as reported by Primdahl and Mogensen for
the H2 oxidation reaction on porous Ni/YSZ cermet anodes
[22].
According to the Adler – Lane – Steele (ALS) model
[23,24] on the oxygen reduction on the mixed ionic and
electronic conducting (MIEC) oxides, the electrode imped-
ance is consisted of charge transfer and noncharge transfer
processes
ZE ¼ Zelectronic þ Zionic þ Zchem ð1Þ
where Z electronic is the impedance of electron transfer process
occurring at the current collector/electrode interface, and
Z ionic is the impedance of the ionic transfer process at the
electrode/electrolyte interface. Z chem is the convoluted con-
tribution of noncharge transfer processes including oxygen
surface exchange, solid-state diffusion, and gas-phase diffu-
sion inside and outside the electrode. Tao and Irvine [25]
studied the H2 oxidation reaction on the mixed conducting
oxide Sc0.15Y0.05Zr0.62Ti0.18O1.9 (ScYZT) in 5% H2. The
impedance responses were characterized by three separated
arcs. The characteristic frequency of the low frequency arc at
900 -C is 0.025 Hz, similar to that for the methane oxidation
reaction on the LSCM/YSZ composite anodes in the present

Table 1
Impedance fitting results for the methane oxidation on the LSCM (50 wt.%)/YSZ (50 wt.%) composite anode in wet CH4
Temperature (-C) R s (V cm2) High frequency arc Medium frequency arc Low frequency arc
2 2 n 2 2 n
R 1 (V cm ) Q 1 (V cm s ) n1 R 2 (V cm ) Q 2 (V cm s ) n2 R 3 (V cm2) Q 3 (V cm2 sn ) n3

3
800 4.01 0.63 1.10  10 0.9 1.70 0.17 0.7 9.94 0.69 1
850 2.9 0.18 9.70  10
3 0.8 0.80 0.15 0.7 4.08 0.68 0.9
900 2.0 0.12 6.22  10
4 1 0.43 0.18 0.7 2.07 0.58 0.8
156 S.P. Jiang et al. / Solid State Ionics 177 (2006) 149 – 157
Fig. 12. Activation energy plots for the oxidation reaction in wet CH4 on the
LSCM (50 wt.%)/YSZ (50 wt.%) composite anodes.
study. Tao and Irvine also observed the increase of the high
frequency impedance with the increased polarization poten-
tial. This appears to be consistent with the reduced electronic
conductivity of the ScYZT at low partial pressure of O2 due
to the increased overpotential. For O2 reduction on MIEC
cathodes such as (La,Sr)(Co,Fe)O3 and GDC-impregnated
(La,Sr)MnO3, the electrode impedance is generally charac-
terized by two impedance arcs [26,27]. The disappearance of
the electrode impedance associated with the electronic
transfer process could be explained by the high electronic
conductivity of the LSCF and GDC-impregnated LSM
materials.
LSCM is a p-type conductor and shows limited mixed ionic
and electronic conductivity under SOFC operation conditions
[11]. The substitution of Sr into the A-site of the LSCM
perovskite results in a charge-compensating transition of Cr3+/
Mn3+ to Cr4+/Mn4+ and at low partial pressure of oxygen, the
compensation is achieved by the formation of oxygen
vacancies. The concentration of oxygen vacancies would
increase under reducing conditions. Thus, similar to the H2
oxidation on the ScYZT anodes [25], the electrode impedance
for the methane oxidation on the LSCM/YSZ composite
anodes can be in principle represented by the impedances of
the electrode processes at the current collector/anode interface,
the anode/electrolyte interface and the chemical processes
according to Eq. (1). This is supported by the observation of
the distinctive three impedance arcs for the methane oxidation
on the LSCM/YSZ composite anodes (see Fig. 10). The high
and medium frequency impedance responses are likely related
to the electronic current exchange and ionic exchange
processes, respectively, while the low frequency impedance
to the noncharge processes including oxygen surface exchange
and diffusion reactions. The chemical nature of the electrode
process at low frequencies is also indicated by the high value
of the constant phase element or the pseudo capacitant, Q 3 (see
Table 1). Sakai et al. [28] studied the oxygen transport
properties of La0.8Ca0.2CrO3 and the activation energy is 160
and 167 kJ mol
1 for the bulk and grain boundary diffusion,
respectively, which are close to the high activation energies
Table 2
Concentration of each component in the H2O – CH4 system before and after the
system reaches equilibrium condition
CH4 H2O CO CO2 O2 H2
Initial concentration a b 0 0 0 0
Equilibrium concentration a – x 1 – x 2 b – x 1 – 2x 2 – 2x 3 x 1 x2 x3 x4
observed for the electrode polarization resistance at high,
medium and low frequency arcs for the methane oxidation on
the LSCM/YSZ composite anodes. This indicates that the
methane oxidation reaction on the LSCM/YSZ composite
anodes could be essentially controlled by the high energetic
process of the oxygen vacancy diffusion in the LSCM
perovskites. The dominance of the electrode process associated
with low frequency arc may indicate that the noncharge
process may be limited by the oxygen exchange rate at the
surface of the LSCM/YSZ composite electrodes. Nevertheless,
the methane oxidation is a complex process and more work
will be needed in order to fundamentally understand the
reaction mechanism and kinetics of this importance reaction in
SOFC.
4. Conclusions
The La0.75Sr0.25Cr0.5Mn0.5O3 (LSCM)/YSZ composites
have been synthesized and studied as the alternative anode
materials for the direct utilization of methane in SOFCs.
Electrochemical performance of pure stoichiometric LSCM
was low probably due to the poor conversion of methane, low
porosity and poor adhesion between LSCM electrode and YSZ
electrolyte. Addition of YSZ phase greatly improved the
adhesion and reduced the electrode polarization resistance.
LSCM/YSZ composite anodes show relatively good perfor-
mance for the methane oxidation reaction in wet CH4 and the
best electrode performance was achieved for the composite
with LSCM contents of 50 – 60 wt.% with polarization
resistances of 2– 3 V cm2 in wet CH4 at 850 -C without using
of Pt or Au paste. The impedance for the methane oxidation on
Fig. 13. Calculated OCP for the cell with H2O – CH4 fuel and air at different
temperatures.
 S.P. Jiang et al. / Solid State Ionics 177 (2006) 149 – 157 157

the LSCM/YSZ composite anodes is characterized by three
separable arcs and could be explained based on the ALS model
for the reaction on the MIEC electrode. The high activation
energies of the methane oxidation reaction imply that electro-
catalytic activity of the LSCM/YSZ composite anodes may be
limited by the oxygen ion conductivity. This could be enhanced
by impregnation of high oxygen ion conducting phase such as
Gd-doped ceria into the composite [27].
Fig. 13 is the theoretical OCP for the cell with H2O –CH4
fuel and air at different temperatures. Sfeir et al. [8] calculated
the thermodynamic equilibrium concentration in the 56% CH/
41% Ar/3% H2O/air system and the theoretical OCP is 1.205 V
at 800 -C. This is close to 1.228 V for the 3% H2O – 97% CH4/
air at the same temperature in the present study.
References

Appendix A. Calculated open circuit potential in [1] S.P. Jiang, S.H. Chan, Mater. Sci. Technol. 20 (2004) 1109.
H2O – CH4/air system [2] S.P. Jiang, S.H. Chan, J. Mater. Sci. 39 (2004) 4405.
[3] J.-H. Koh, Y.-S. Yoo, J.-W. Park, H.C. Lim, Solid State Ionics 149 (2002)
157.
The OCP in H2O–CH4/air system can be calculated from [4] C.M. Chun, J.D. Mumford, T. Ramanarayanan, J. Electrochem. Soc. 147
the thermodynamic equilibrium concentration of the mixture (2000) 3680.
gases, CH4, CO, O2, CO2, H2O and H2, according to the [5] P.V. Hendriksen, S.C. Singhal, H. Tagawa (Eds.), SOFC-V, vol. 97-40,
The Electrochem. Soc., Penington, NJ, 1997, p. 1319.
following four main chemical reactions:
[6] M. Mori, Y. Hier, J. Am. Ceram. Soc. 84 (2001) 2573.
CH4 þ 2O2 6CO2 þ 2H2 O ð2Þ [7] J. Vulliet, B. Morel, J. Laurencin, G. Gauthier, L. Bianchi, S. Giraud, J.-Y.
Henry, F. Lefebvre-Joud, S.C. Singhal, M. Dokiya (Eds.), SOFC-VIII,
vol. 2003-07, The Electrochem. Soc., Pennington, NJ, 2003, p. 803.
CH4 þ H2 O6CO þ 3H2 ð3Þ [8] J. Sfeir, P.A. Buffat, P. Möckli, N. Xanthopoulos, R. Vasquez, H.J.
Mathieu, J. Van herle, K.R. Thampi, J. Catal. 202 (2001) 229.
CH4 þ CO2 62CO þ 2H2 ð4Þ [9] J. Sfeir, J. Power Sources 118 (2003) 276.
[10] S. Tao, J.T.S. Irvine, Nat. Mater. 2 (2003) 320.
CO þ H2 O6CO2 þ H2 ð5Þ [11] S. Tao, J.T.S. Irvine, J. Electrochem. Soc. 151 (2004) A252.
[12] F.T. Ciacchi, K.M. Crane, S.P.S. Badwal, Solid State Ionics 73 (1994) 49.
The initial and equilibrium concentrations of each compo- [13] S.P. Jiang, J.G. Love, L. Apateanu, Solid State Ionics 160 (2003) 15.
nent are shown in Table 2. Defining that K 1, K 2, K 3 and K 4 are [14] S. Koch, P.V. Hendriksen, Solid State Ionics 168 (2004) 1.
[15] S.P. Jiang, J. Electrochem. Soc. 150 (2003) E548.
the equilibrium constants of the above four reactions, the four [16] A. Mitterdorfer, L.J. Gauckler, Solid State Ionics 111 (1998) 185.
unknown parameters, x 1, x 2, x 3 and x 4, can be obtained from [17] S.P. Jiang, J.-P. Zhang, K. Foger, J. Eur. Ceram. Soc. 23 (2003) 1865.
following equations. [18] S. Primdahl, J.R. Hansen, L. Grahl-Madsen, P.H. Larsen, J. Electrochem.
Soc. 148 (2001) A74.
x2 ðb
x1
2x2
2x3 Þ2 [19] S.P. Jiang, S.P.S. Badwal, Solid State Ionics 123 (1999) 209.
K1 ¼ ð6Þ [20] S.P. Jiang, W. Wang, Y.D. Zhen, J. Power Sources 147 (2005) 1.
ða
x1
x2 Þx23
[21] A. Bieberle, L.P. Meier, L.J. Gauckler, J. Electrochem. Soc. 148 (2001)
A646.
x1 x34 [22] S. Primdahl, M. Mogensen, J. Electrochem. Soc. 146 (1999) 2827.
K2 ¼ ð7Þ [23] S.B. Adler, J.A. Lane, B.C.B. Steele, J. Electrochem. Soc. 144 (1997)
ða
x1
x2 Þðb
x1
2x2
2x3 Þ
1884.
[24] S.B. Adler, Solid State Ionics 135 (2000) 603.
x1 x24 [25] S. Tao, J.T.S. Irvine, J. Electrochem. Soc. 151 (2004) A497.
K3 ¼ ð8Þ
ða
x1
x2 Þx2 [26] A. Esquirol, N.P. Brandon, J.A. Killer, M. Mogensen, J. Electrochem. Soc.
151 (2004) A1847.
x1 x4 [27] S.P. Jiang, W. Wang, J. Electrochem. Soc. 152 (2005) A1398.
K4 ¼ ð9Þ [28] N. Sakai, K. Yamaji, T. Horita, H. Yokokawa, T. Kawada, M. Dokiya, J.
x1 ðb
x1
2x2
2x3 Þ Electrochem. Soc. 147 (2000) 3178.
The above equations can be solved using nonlinear least
square method. As the concentration of the oxygen in air is 0.21
atm, the open circuit potential of the cell can be calculated as:
 
RT 0:21
OCP ¼ ln ð10Þ
4F x3