Solid State Ionics 177 (2006) 2005 – 2008

www.elsevier.com/locate/ssi

Electronic transport in the novel SOFC anode material

La1
xSrxCr0.5Mn0.5O3±δ
Steven M. Plint, Paul A. Connor, Shanwen Tao, John T.S. Irvine ⁎
School of Chemistry, University of St. Andrews, St Andrews, FIFE, KY16 9ST, UK
Received 29 August 2005; received in revised form 19 February 2006; accepted 22 February 2006

Abstract

Electronic conductivity in the potential SOFC anode material La1
xSrxCr0.5Mn0.5O3±δ has been investigated in the range 0.2 < x < 0.3. log(σT )
U
vs. 1/T plots indicate conduction via thermally activated polaron hopping. At 900°C, conductivity in air increases with Sr2+ via an increase in [BB]
holes (B—transition metal). X-ray absorption spectroscopy (XAS) studies indicate that compensation for A-site Sr substitution and oxygen
vacancy formation is via the Mn cation only; Cr maintains a 3+ oxidation state and 6-fold oxygen coordination. Electronic transport occurs by
percolation between Mn cations in a disordered B-site sub-lattice. Conductivity decreases with p(O2), which is indicative of p-type conduction
behaviour, but the relationship cannot be explained by a simple redox equilibrium involving Mn3+, Mn4+ and oxygen, possibly due to co-existence
of Mn2+, Mn3+ and Mn4+ via disproportionation as with La1
xSrxMnO3±δ.
© 2006 Elsevier B.V. All rights reserved.

Keywords: SOFC; Anode; Perovskite; Conductivity; EXAFS; XANES

1. Introduction currently utilised in SOFCs as cathode and interconnect

The SOFC anode provides sites for the electrochemical
oxidation of fuel, but good electronic conductivity is also
required to provide transfer of generated charge, especially in
the absence of an additional anode current collector material.
Some oxygen ion conductivity is also desirable so that
electrochemical oxidation of fuel is not restricted to the triple
phase boundary. The anode material must also be chemically
and structurally stable in the high temperature/low p(O2) SOFC
anode operating conditions, and resistant to cyclic p(O2)
changes.
La1
xAxBO3±δ (A—alkaline earth metal; B—transition
metal) materials are being considered as anode materials to
address limitations of the standard nickel/YSZ cermet, which
include low sulphur tolerance, carbon deposition with hydro-
carbon fuel, poor redox cycling and detrimental sinter activity
of the nickel phase. La1
xAxMnO3±δ, and La1
xAxCrO3±δ are
⁎ Corresponding author.
E-mail address: jtsi@st-andrews.ac.uk (J.T.S. Irvine).
0167-2738/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ssi.2006.02.025
materials respectively [1].
La1
xSrxCrO3±δ is stable in the low p(O2) of the anode
environment but as an anode exhibits an unacceptably high
polarisation resistance. La1
xSrxMnO3±δ might be expected to
be a good catalyst for fuel oxidation but is thermodynamically
unstable under anode conditions. The composition La1
xSrx
Cr0.5Mn0.5O3±δ offers a good compromise of low anode
polarisation resistance and stability in fuel [2]. Decreased
polarisation is attributed to the catalytic effect of Mn on the
anode oxidation reaction. Further, this composition appears
not to suffer carbon deposition with hydrocarbon fuels [2].
The ideal oxide perovskite structure ABO3 consists of a
cubic array of corner sharing BO6 octahedra with the A-
cation at the body centre position, but non-ideal A and B
ionic radii create distortions to the cubic lattice (often
orthorhombic or rhombohedral). The series LaxSr1
xCr0.5
Mn0.5O3±δ is isostructural with La1
xSrxCrO3±δ and La1
xSrx
MnO3±δ; for x = 0.25 at room temperature x = 0.25 all show
rhombohedral distortion with space group R-3c [2–4].
Cation radius ratio and valence rules would predict no B-
site cationic order in the former [5].
2006 S.M. Plint et al. / Solid State Ionics 177 (2006) 2005–2008
In La1
xAxBO3±δ materials, electronic conductivity is
enhanced by A-site substitution with a divalent ion such as
Sr2+. The decreased A-site charge is compensated by hole
formation in the transition metal d band. The holes are generally
localised by lattice distortion as small polarons which afford
electronic transport by thermally activated hopping.
The effect of decreasing p(O2) is described most simply by
the following equilibria:
½SrLa  ¼ 2½VUU U
=
O  þ ½BB 
½SrLa  þ ½BB  ¼ 2½VUU
= =
O
p- and n-type behaviour should prevail in conditions (1) and
(2) respectively; conductivity should be proportional to [BB/]
U
and [BB] and be minimum where the oxidation state of B is
3.0+.
La1
xSrxCrO3±δ and La1
xSrxMnO3±δ exhibit p-type polaro-
nic behaviour over the range of SOFC anode operation
conditions, but La1
xSrxMnO3±δ is limited by its decomposition
in fuel p(O2)s. Electronic conductivity decreases and ionic
conductivity increases on reduction. In SOFC anode conditions
the mean valence of the Cr in La1
xSrxCrO3±δ is >3+ and
electroneutrality is maintained via relation (1) [6]. La1
xSrx
MnO3±δ remains p-type over the p(O2) stability range, but the
p(O2)–conductivity relation cannot be explained by relations
(1) and (2) and require defect models incorporating co-existent
Mn2+, Mn3+ and Mn4+ states [7,8]. The Seebeck coefficient of
La0.75Sr0.25MnO3±δ is very small compared to other 3d
transition-metal perovskite oxides and varies little with p(O2)
implying a metallic state despite thermal activation [9,10].
The electronic transport properties of (La,Sr)Cr1
xMnxO3±δ
have been explained by multiple trapping and percolation
models [11,12]. LaCr1
xMnxO3±δ exhibits a conductivity
minimum at ∼x = 0.05 several orders of magnitude lower than
that of LaCrO3. This has been attributed to trapping of carriers
at Mn B-sites with much lower small polaron site energy than at
Cr sites. As the Mn concentration is increased above x = 0.31
(site percolation threshold in a cubic lattice [13]) direct transport
among Mn sites becomes possible and the conductivity
increases. Incorporation of Sr increases the depth and Mn
concentration of the conductivity minimum. Here we have
investigated the transport properties and electronic structure of
Sr-substituted lanthanum chromo-manganite perovskites.
2. Experimental
La1
xSrxCr0.5Mn0.5O3±δ (x = 0.2, 0.25, 0.3) and LaCrO3±δ
compositions were synthesised via solid-state reaction of
appropriate amounts of La2O3 (Alfa 99.99%), SrCO3 (Aldrich,
99.9%), Cr2O3 (Alfa, 99%) and MnO2 (Aldrich 99+%). The
powders were ground under acetone, pressed into pellets then
fired at 1450–1500°C in air with intermediate grindings and
annealed at 900 °C.
Reduction cycles were undertaken in wet 5% H2/Ar at
900 °C (p(O2) of 10
16.4 atm.) for XRD and TGA studies, and
unhumidified 5% H2/Ar at 900 °C (p(O2) of ∼ 10
20 atm) for
XAS studies. Phase purity and crystal parameters were assessed
by X-ray diffraction (XRD) analysis of powders on a Stoe Stadi-
P diffractometer. Thermogravimetric analysis was undertaken
using a Rheometric Scientific TG1000M Plus instrument. Pre-
reduced samples were heated in flowing air at 5°C/min. to
900 °C, held for 3 h and then cooled at 5 °C/min. DC
Conductivity was measured via a four-terminal method using
a Keithley 220 current source and a Schlumberger Solartron
7150 digital multimeter. p(O2) was controlled using air, Ar and
ð1Þ wet 5%H2/Ar gases. Intermediate p(O2) conditions were
established using MnOx buffers.
X-ray absorption spectra were collected using the Synchro-
ð2Þ
tron radiation source at Daresbury laboratories on station 9.3,
which used a Double crystal harmonic rejecting Si220
monochromator. Standard ion chambers filled with Ar; (20%
absorbing Io) and (80% absorbing It), backfilled to 1000mbar
with He were used for detection of incident and transmitted
flux. Samples were prepared by milling with graphite 15:100 wt
ratio and pressing into pellets.
3. Results and discussion
3.1. Structure
Table 1 presents crystallographic refinement data for the
La1
xSrxCr0.5Mn0.5O3±δ samples fired at 1500°C/12 h in air and
then reduced in 5%H2/Ar at 900 °C/72 h. Before reduction, all
samples had Rhombohedral structure (R-3c). Unit cell volume
decreased with increasing Sr but increased on reduction. These
changes are associated with changes in B-site cationic charge
and ionic radii. Before reduction, the increase in Sr level results
in an increase in B-site oxidation state, a decrease ionic radii,
and smaller metal oxygen bondlengths. On reduction, oxygen
vacancy formation is compensated by a decrease in B-site
cationic charge and expansion of metal oxygen bondlengths. An
increased in symmetry is observed on reduction at higher Sr
levels, and at x = 0.3 the structure is cubic. At 0.25 the structure
refined most easily as orthorhombic, however, x = 0.2 did not
undergo a symmetry change with relatively small volume
change on reduction in wet 5% H2, indicating good stability in
fuel cell conditions.
3.2. XAS/manganese oxidation state
Fig. 1 presents Mn and Cr K XANES spectra for La1
xSrx
Cr0.5Mn0.5O3±δ. The Cr K edges do not deviate with Sr level or
reduction cycle (dry 5% H2/Argon—900 °C) and are coincident
Table 1
XRD data for La1
xSrxCr0.5Mn0.5O3±δ
Sr = x Fired 1500°C/12h→Wet 5% H2–900°C/72h ΔV (%)
0.2 Rhombohedral R-3c Rhombohedral R-3c 0.36
Vol. = 350.56 (5) Z = 6 Vol. = 351.83 (10) Z = 6
0.25 Rhombohedral R-3c Orthorhombic Pnma 0.79
Vol. 348.73(8) Z = 6 Vol. = 234.32 (10) Z = 4
0.3 Rhombohedral R-3c Cubic Pm3m 0.97
Vol. = 347.25 (14) Z = 6 Vol. = 58.443(5) Z = 1
 S.M. Plint et al. / Solid State Ionics 177 (2006) 2005–2008 2007

Table 2
Cr K Estimated Mn oxidation states before and after reduction cycle from TGA data

X=0.25 LaCrO 3 La1
xSrxMn0.5Cr0.5O3±δ (%) wt. O- Mean Mn oxidation

pre-reduction gain on formula state
post-reduction reoxidation unit
As- Post-
change
prepared reduction
δ
x = 0.2 0.35 0.05 +3.4 +3.2
Absorption (arbitrary units)

x = 025 0.7 0.1 +3.5 +3.1

x = 0.3 0.8 0.125 +3.6 +3.1

5995 6000 6005 6010 6015 cell volume change. Mean Mn oxidation states are estimated
from δ assuming that Sr2+ compensation in as-prepared
Mn K samples is via the Mn ion only.

3.3. Conductivity

Fig. 2 plots log(σT) vs. 1/T for La1
xSrxCr0.5Mn0.5O3±δ

X=0.3
Post –
X=0.25
reduction
X=0.2
6540 6545 6550
Energy (eV)
Fig. 1. Cr and Mn K XANES spectra for La1
xSrxCr0.5Mn0.5O3±δ.
with that of LaCrO3, clearly indicating that Cr is in the 3+
oxidation state for all La1
xSrxCr0.5Mn0.5O3±δ samples. For
as-prepared samples, the Mn K threshold energy increases
with Sr content indicating compensation at the Mn ion. The
trend is reversed for the reduced samples. Mn K EXAFS
indicate a change in the short-range order relating to a
decrease in oxygen coordination. Mn K edges are wider in
reduced samples and the width increases with the Sr level.
The edges show no inflections, but the widths may indicate
localised states. Theoretically modelled Mn K edge XANES
spectra for La1
xCaxMnO3±δ [14] based on weighted
averages for CaMnO3 and LaMnO3 (representing localised
Mn3+ and Mn4+ ions) show no inflections but are wider
than the component spectra. Actual La1
xCaxMnO3±δ Mn K
edge widths are similar to those of LaMnO3 and CaMnO3,
indicating fractional oxidation states which correlate with
metallic conduction behaviour. The Mn K edge width for
X=0.3 (x = 0.2, 0.3). These are linear over a wide temperature range,
Pre –
X=0.25 reduction
indicating thermally activated polaron hopping. The
X=0.2
activation energy from the Arrhenius equation is derived
from the gradient of log (σT) vs. 1000/T. In air activation
energies are ∼ 0.18eV compared to ∼ 0.11 eV for La1
xSrx
CrO3±δ (0.2 < x < 0.3) [6].
6555 6560
Conductivity for La1
xSrxMnO3±δ (0.2 < x < 0.3), however,
is only slightly thermally activated and can show metallic
character, depending upon oxygen stoichiometry [9,10]. The
relatively high activation energy of La1
xSrxCr0.5Mn0.5O3±δ
may be the result of reduced hopping frequency due to
restriction of available B-sites. Conduction activation
energies in wet 5%H2/Ar, are ∼0.28 eV for x = 0.2 and
∼0.4eV for x = 0.3. This higher activation energy in the
latter may be due to a phase change and associated increase
in unit cell volume.
The plots of σ vs. log p(O2) for La1
xSrxCr0.5Mn0.5O3±δ
(Fig. 3) show two regimes.
(i) p(O2) > 10
8, in which σ changes little with decrease in
p(O2)
(ii) p(O2) 10
8–10
16 in which the slope of σ vs. log p(O2)
increases and conductivity, dependencies converge.
12
10 Air:
X=0.3
Ln (σT)/Scm-1K)

La1
xCaxMnO3±δ is ∼5–6 eV with a mean shift of ∼ 3 eV 8 X=0.2

for a valence change of +1 [15], compared to 8–9 eV for 6 Wet 5%H2/Ar:
the Mn K edges of the pre-reduced La1
xSrxCr0.5Mn0.5O3±δ, X=0.2
indicating more localised states. 4 X=0.3
Table 2 presents the thermogravimetric O2 gains at
2
900 °C on re-oxidation of samples previously reduced in wet
5%H2/Ar at 900 °C for 72 h. Oxygen formula unit changes 0
(δ) have been estimated, assuming that the stoichiometry 0 0.5 1 1.5 2 2.5 3 3.5 4
after reoxidation TGA is close to δ = 0 in La1
xSrxCr0.5 1000/T (K-1)
Mn0.5O3±δ. The level of reduction in fuel conditions
increases with Sr level, correlating with the trend in unit Fig. 2. Log(σT) vs. 1/T for La1
xSrxCr0.5Mn0.5O3±δ in air and 5% wet H2/Ar.
2008 S.M. Plint et al. / Solid State Ionics 177 (2006) 2005–2008

More detailed defect modelling of La1
xSrxCr0.5Mn0.5O3±δ is

1.6 required in order to fully understand the conductivity vs. p(O)2
relationship.
1.4

Log [σ (Scm-1)]
1/4
1.2 4. Conclusions
1/6
1/8
1 XAS has indicated defects controlling electronic transport in
X=0.2 La1
xSrxCr0.5Mn0.5O3±δ are associated with the Mn cation only.
X=0.25 0.8
X=0.3 This material shows thermally activated conduction behaviour
0.6 consistent with polaronic transport. In air at 900 °C there is
-18 -16 -14 -12 -10 -8 -6 -4 -2 0 reasonable correlation between Sr substitution and conductivity,
Log [p(O2)/atm] suggesting that charge carriers are associated with Mn4+ (Mn ),
U
U /
and [Mn ] = [Sr ]. La1
xSrxCr0.5Mn0.5O3±δ materials in this
Fig. 3. Log σ vs. log p(O2) for La1
xSrxCr0.5Mn0.5O3±δ. range show a decrease in conductivity below p(O)2 ∼ 10
8
characteristic of p-type behaviour but the σ vs. p(O2) relation is
U
inconsistent with simple defect equilibrium [h ] ∝ p(O2)1/4,
The defect equilibrium for oxidation of the Mn in the most probably due to the disproportion of Mn to Mn2+ and
3+

perovskite is most simply expressed as: Mn4+.

1=2O2 þ VUU X U
O þ 2MnMn ¼ 2MnMn þ OO
X
ð3Þ Acknowledgements
Equilibrium constant
We thank EPSRC, Rolls Royce, Carbon Trust and the EU

U 2
X 
MnMn OO RealSOFC IP for support. We also thank EPSRC and CCLRC
K¼
2

MnXMn VUU 1=2 for provision of Synchrotron time at Daresbury station 9.3 and
O pðO2 Þ Dr. Ian Harvey and Dr. Alistair Lennie for assistance and advice
UU
In region (i), [VO] is negligible and the neutrality condition
in running these experiments.
/
[SrLa
U UU
] = [MnMn] + 2[VO] is simplifed to [SrLa / U
] = [MnMn]. In
UU
region (ii) [VO] becomes significant. From the above equilib-
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