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Recent Progress in the Development of Anode Materials
REVIEW
for Solid Oxide Fuel Cells
Peter I. Cowin, Christophe T. G. Petit, Rong Lan, John T. S. Irvine, and Shanwen Tao*
The field of research into solid oxide fuel cell (SOFC) anode materials has
been rapidly moving forward. In the four years since the last in-depth review
significant advancements have been made in the reduction of the operating
temperature and improvement of the performance of SOFCs. This progress
report examines the developments in the field and looks to draw conclusions
and inspiration from this research. A brief introduction is given to the field,
followed by an overview of the principal previous materials. A detailed anal-
ysis of the developments of the last 4 years is given using a selection of the
available literature, concentrating on metal-fluorite cermets and perovskite-
based materials. This is followed by a consideration of alternate fuels for use
in SOFCs and their associated problems and a short discussion on the effect
of synthesis method on anode performance. The concluding remarks compile
the significant developments in the field along with a consideration of the
promise of future research. The recent progress in the development of anode
materials for SOFCs based on oxygen ion conducting electrolytes is reviewed.
1. Introduction
Interest in low carbon and renewable power generation has
grown massively in the last 20 years after the acceptance of the
idea that greenhouse gases are causing significant damage to the
environment. Combustion of fossil fuels, by an overwhelming
degree the most utilised power generation method in use today,
is less efficient and causes significant environmental pollution.
While flue gas scrubbing and catalytic conversion may reduce
harmful emissions, they do not sufficiently eliminate them.
Various alternative technologies with minimal to non-existent
carbon emissions have been put forward as viable alternatives to
fossil fuel use, however many of these still suffer from high ini-
tial costs and reliance on prevailing environmental conditions.
Fuel cells, devices which convert chemical energy to electrical
energy with a higher efficiency than heat based power genera-
tors, are considered to be a promising technology.
P. I. Cowin, C. T. G. Petit, Dr. R. Lan, Prof. S. W. Tao
Department of Chemical and Process Engineering
University of Strathclyde
Glasgow G1 1XJ, UK
E-mail: shanwen.tao@strath.ac.uk
Prof. J. T. S. Irvine
School of Chemistry
University of St Andrews
St Andrews, Fife KY16 9ST, UK
DOI: 10.1002/aenm.201100108
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Fuel cells are produced in a variety of
different guises, from low temperature
polymer electrolyte membrane fuel cells
(PEMFCs) to high temperature solid oxide
fuel cells (SOFCs). The basic design con-
sists of an electronically insulating, ion-
conducting membrane separating two
electrodes, connected through an external
circuit. For an oxygen-ion conducting FC,
the oxygen from the air is dissociated and
ionised at the cathode, the oxygen ions are
transported through the electrolyte; these
then react at the anode with the fuel gas,
producing electrons which are transported
round an external circuit to the cathode,
generating electricity. For a hydrogen-
ion conducting FC the process is sim-
ilar, however the fuel is dissociated into
hydrogen ions and electrons at the anode
and reacted at the cathode with oxygen
from the air. The first working example of
a solid oxide fuel cell was demonstrated in 1937 by Baur and
Preis.[1] SOFCs are mostly constructed from ceramic mate-
rials and function optimally at high temperatures, dictated by
the operating temperature range of the electrolyte. Operation
at these temperatures causes significant thermal stresses and
this rules out some efficient SOFC materials, e.g. some metallic
interconnects, on the basis of their thermal stability[2] Due to
drawbacks of high temperature operation, research over the last
10 years has focused on reduction of the operating temperature
through development of novel SOFC materials.
In this paper, we begin by examining the various require-
ments of SOFC anode materials, reviewing each requirement
briefly. We then summarise significant previous work in this
field, followed by an in depth analysis of progress in this area
between 2007 and the present day. A short discussion on the
use of alternative fuels and the effect on the fabrication method
and microstructure on anode performance follows. This is com-
pleted by an overview of the direction of current research, a dis-
cussion on progress has been made and a look at future work
and considerations. It is not possible to cover all the recent
research work on SOFC anode materials in a short review but
we manage to include the important ones.
2. Anode Requirements
To allow for reduction from current SOFC operating temper-
atures, all SOFC components must demonstrate similar or
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improved performance at intermediate temperatures, 500 °C to

REVIEW
700 °C. Design of novel anode materials for operation at these Shanwen Tao received his PhD
temperatures requires careful consideration of anode require- from University of Science &
ments and the effect of improved anode performance on fuel Technology of China in 1998.
cell performance. He worked at Risø National
Ideal fuel cell performance can be theoretically calculated Laboratory of Denmark in
using the Nernst equation, although actual cell performance 1999. During 2000–2007, he
is affected by losses from various electrochemical processes, as worked at University of St An-
demonstrated in Equation 1. drews as Research Associate,
EastCHEM Fellow/Lecturer.
V = E 0 − IR − 0 cathods − 0 anods (1) He moved to Heriot-Watt
University to take a Reader-
where E0 is the Nernst potential of the reactants, I is the current ship in 2007. In 2010, he
through the cell, R is the ohmic resistance of the cell and ηcathode was appointed as Professor
and ηanode are the cathodic and anodic polarisation losses. in Nanotechnology for Energy Solutions at University of
The I–V curve can be broken down into various resistances Strathclyde. His research interests include nano-materials,
caused by activation polarisation, ohmic polarisation and new ionic/electronic conducting materials for electrochemi-
concentration polarisation. Activation polarisation includes cal devices, particularly fuel cells.
both the anodic and cathodic reactions and is a combina-
tion of the reaction rate and the electron/ion transfer. Ohmic
polarisation is a combination of resistances to electron and Peter I. Cowin is currently study-
ion transport throughout the fuel cell while concentration ing for his PhD at the University
polarisation is caused by difficulties with the transport of of Strathclyde under Professor
the fuel and waste gases to and from the anode-electrolyte Shanwen Tao. He obtained his
interface. Bachelor of Science from the
If anode materials are to function efficiently then there are a University of Southampton in
number of criteria which must be met: 2007. Peter’s current area of
interest is the development
1. High electronic conductivity of novel anode materials for
2. Catalytic activity for fuel oxidation/combustion intermediate temperature solid
3. High ionic conductivity oxide fuel cells, concentrating
4. Stability on successive reducing and oxidizing (redox) cycles on the synthesis and characteri-
5. Thermal stability sation of cermet alternatives.
6. Chemical stability to contacting components
7. Matched thermal expansion coefficient (TEC) to contacting
Christophe T.G. Petit
components
graduated in France from
the University Institute of
Formation of a material with all of these properties has Technology of the University
proved difficult, however the formation of composite or of Strasbourg, having com-
ceramic-metal (cermet) anodes can produce a combination of pleted his University Degree
all these properties. in Technology in Chemistry in
High electronic conductivity is essential for SOFC anode 2006. Enrolled in Heriot-Watt
materials for smooth transfer of electrons on the anode. It is University, UK, he completed
generally considered that conductivities of 1 Scm−1 are suf- his BSc in Chemistry (2008)
ficient for certain FC configurations however conductivities and his MSc in Forensic Mate-
of higher than 10 Scm−1 are desirable. For example, anode- rials (2009). In October 2009,
supported SOFCs require higher electronic conductivity as he joined Professor Tao’s fuel
they have greater distance for conduction to the current cell group as a PhD student within the EPRSC Supergen
collector. Fuel Cell Consortium and focuses on the development of
Catalytic activity for the anodic reaction is another main con- new materials for IT-SOFCs.
tributor to fuel cell efficiency. The fuel reaction at the anode
occurs through oxidation of the fuel at the catalytically active
site, demonstrated in Equation 2 and 3:

H2 + O 2 → H2 O + 2e − (2) Increased catalytic activity can be observed on the I–V curve

as a reduction of the activation polarisation. In high temperature
Cn H2n+2 + (3n + 1)O 2− SOFCs activation polarisation is often not observed on the I–V
curve as reaction kinetics proceed quickly, despite this reaction
→ nC O2 + (n + 1)H2 O + (6n + 2)e − (3) kinetics still have a significant impact on fuel cell performance.

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REVIEW
DPB
TPB
Cathode Cathode
Electrolyte
Figure 1. Graphical representation of the specific spatial positions where
HOR and ORR take place (left) and an ideal double phase boundary DPB
(right)
One essential problem with reduction of the operating temper-
ature is a significant reduction in the efficiency of these cata-
lytic reactions, thus a significant increase in catalytic activity
is required for a relatively small reduction of the operating
temperature.
While ionic conduction itself is not essential to the anode
reaction, maximisation of the triple phase boundary (TPB),
where the fuel, oxygen ions and a catalytic reaction site coin-
cide (exhibited in Figure 1), can significantly increase anodic
efficiency and decrease anode polarisation resistance. Ionic
conductivity in anode materials can be induced through the use
of a single phase mixed ionic-electronic conductor (MIEC) or
through the combination of separate electronic and ionic con-
ducting phases in a composite or cermet material.
Anode materials must also have the capacity to withstand
SOFC operating conditions. This requires materials which do
not degrade or significantly alter at high temperatures (thermal
stability), which do not form non-conductive phases at elec-
trode-electrolyte or electrode-interconnect interfaces (chemical
stability) and which do not degrade upon successive reduction
and oxidation cycles (redox stability). Of these three require-
ments redox stability is the most elusive, with many compounds
exhibiting structural changes, degradation or changes in volume
or TEC upon reduction.[3,4] Additionally, chemical stability to
fuel contaminants is necessary as the formation of sulphurous
impurities, for H2S, or phosphorous impurities, for PH3, can
cause significant degradation of fuel cell performance.[5,6]
Matching of the thermal expansion coefficient of contacting
components has been found to be essential to long term fuel
cell performance, with most fuel cell electrolytes having TECs
of 11–13 × 10−6 K−1.[7] For mismatched materials, stresses
can build up at the interface and can cause delamination or
cracking. A deviation of electrode TEC of 7 × 10−6 K−1 from the
electrolyte TEC has been found to cause a noticeable reduction
in fuel cell performance, attributed to electrode delamination.[8]
One further consideration must be the microstructure of the
anode, which will affect the transport of gases to and from the
TPB, and thus is responsible for the concentration polarisa-
tion. The anodic microstructure is dependent on the fabrication
process used and significant improvements in anode perform-
ance can be achieved through microstructural modification.
Design of anode materials must consider the electrolyte with
which the material will operate as the operating temperature,
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Figure 2. Comparison of the ionic conductivities of various oxide ion
conducting electrolytes. Reproduced with permission.[9] Copyright 2004,
Elsevier.
TEC and chemical reactivity are electrolyte dependent. There
are a variety of different materials which can be utilised, a com-
parison of which is exhibited in Figure 2, taken from the review
by V. V. Kharton et al in 2004.[9]
The most common electrolyte was previously yttrium sta-
bilised zirconia (YSZ) due to its high ionic conductivity and
low electronic conductivity,[10] however other materials such as
gadolinium-doped ceria (GDC) and lanthanum strontium gal-
lium magnesium oxide (LSGM) are becoming more popular
due to their higher ionic conductivity at lower temperatures
(500 °C–700 °C).[11–13] Bismuth oxide-based materials[14,15] and
metal doped bismuth vanadium oxides[16] have high ionic con-
ductivities at low temperatures but suffer from high chemical
reactivity, low mechanical strength and instability in reducing
environments.[17–19] Apatite materials, of the general formula
Ln10Si6O27–where Ln is a rare earth metal-, are also under
investigation although the high reactivity of silicates could be a
potential problem.[20–22]
3. Previous Research into Anode Materials
To judge the recent research and the progression in this area,
a benchmark is required from previous work, detailed in this
section.
As should now be apparent, there are a plethora of different
factors to take into consideration when designing an SOFC
anode material. As the main consideration is electronic conduc-
tion under SOFC operating conditions, much of the research
has been focused on production of highly conducting, redox
stable materials. In the previous decade a number of substan-
tial reviews have been published in this area, notably those by
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Atkinson and Irvine et al (2004),[23] Tao and Irvine (2004)[24]
and Sun and Stimming (2007),[25] and much of the information
in this section has been condensed from a collation of these
works.
3.1. Metal-Fluorite Cermets
Primarily, in SOFCs, metals were used as both anode and
cathode, however as these materials were optimised, the use
of a support was introduced, generally a metal oxide. As dis-
cussed in the preceding section, the introduction of a metal
oxide can be used to propagate the TPB and increase anode
efficiency, whilst alleviating other numerous problems asso-
ciated with pure metal anodes. Much of the research into
fluorite structured materials has focused on the development
of cermets, especially transition metal and ceria/zirconia anode
materials.[26,27]
A cermet consisting of Ni and YSZ has many of the proper-
ties required for an efficient anode material. It has high elec-
tronic conductivity, reasonable ionic conductivity and high
catalytic activity for hydrogen oxidation. This cermet, however,
has multiple problems to effective implementation. Ni/YSZ is
prone to carbon deposition, or coking, when using hydrocarbon
fuels,[28] sulphur poisoning,[29] nickel agglomeration upon pro-
longed usage[30] and is not redox stable.[31]
Reduction of coking and sulphur poisoning was achieved
by transition metal substitution for nickel, however this
was coupled with a significant reduction in the anodic effi-
ciency[32,33]. Redox instability was found to occur upon anodic
re-oxidation and was a result of the expansion of Ni to NiO
which produced stresses at the anode-electrolyte interface.[34,35]
This has been found to be partially alleviated by modification of
the microstructure and distribution of the Ni and YSZ phases
in the cermet[36,37]. No satisfactory solution to either of these
problems has been proposed, however due to a lack of alterna-
tive high performance anodes, Ni/YSZ remains a benchmark
material in this field.
Many materials based on CeO2 demonstrate mixed ionic
and electronic conductivity in reducing atmospheres due to
the mixed valence of cerium, Ce3+ and Ce4+ under these con-
ditions. Doping with lanthanoids was found to significantly
increase the ionic conductivity, especially for Gd (forming
GDC) and Sm (forming SDC).[38] Cermets of GDC or SDC
with nickel were found to have increased performance com-
pared to Ni/YSZ when methane was used as a fuel.[27] Pure
and doped ceria have also been found to promote catalytic
activity for hydrocarbon oxidation reactions without coking.[39]
Formation of a cermet consisting of ceria coupled with both
a transition metal and a noble metal was found to be espe-
cially effective for anodic hydrocarbon reforming.[27] The use
of doped ceria in cermets does provide a significant advan-
tage in terms of higher catalytic activity with hydrocarbon
fuels and lower temperature conductivity over typical YSZ
cermets.[40] Doped or undoped ceria, while improving the
cermet properties, still requires nickel or nickel-copper alloys
to provide the electronic conductivity within the cermet and,
as with Ni/YSZ, still suffer from nickel agglomeration and
redox instability.
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3.2. Perovskites-Based Anode Materials
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Much of the research into cermet-alternatives for both anodic
and cathodic application has focused on the production of
perovskite-type compounds.[41–43] The perovskite structure con-
sists of a network of corner-sharing BO6 octahedra with a larger
A-site atom in the resultant 12-coordinate position. Perovskites
are widely researched due to their ease of production, flexibility
and sheer variety of properties.
The first example of an efficient and fully redox stable
anode material, (La0.75Sr0.25)Cr0.5Mn0.5O3 (LSCM), was devel-
oped in 2003,[42] building on previous research into intercon-
nect, LaCrO3, and cathode, La1-xSrxMnO3, materials.[44] LSCM
is a p-type semiconductor with a conductivity of approximately
38 S cm−1 in air and 1.5 S cm−1 at 900 °C in 5% H2/Ar, with
similar performance in humidified methane.[45] Due to the con-
ductivity in both oxidising and reducing atmospheres, LSCM
can be utilised as both an anode and cathode in a symmetrical
SOFC.[46] The material also shows a high resistance to coking
when using hydrocarbon fuels, although LSCM has been found
to form MnS, La2O2S and α-MnOS upon exposure to 10%
H2S but the stability at lower H2S concenteration has not been
reported yet.[5] Whilst the material is stable and has a suitable
TEC, the electronic conductivity and catalytic activity is insuf-
ficient for efficient use as an SOFC anode material at interme-
diate temperatures.
Another material which has been under extensive investiga-
tion is strontium titanium oxide, SrTiO3 (STO). In 1997, Irvine
et al. first proposed and investigated to use SrTiO3 based mate-
rials as potential anode for SOFCs.[47] These materials have
shown a high sulphur tolerance, resistance to coking and have
good chemical and redox stability.[48] The main difficulty with
the use of pure STO is low electronic conductivity in a reducing
atmosphere.[49] Petric et al.[50] reported high conductivity of Nb-
and Y- co-doped SrTiO3 with a conductivity of 340 S/cm in a
reducing atmosphere but dropped to less than 10 S/cm when
firing in air. A-site doping of either yttrium or lanthanum signif-
icantly increased the electronic conductivity without adversely
affecting the compound stability.[41,51] Lanthanum doped STO,
LST, has higher conductivity but is coupled with negligible
catalytic activity for hydrogen oxidation. Doping with yttrium,
forming YST, provides both reasonable electronic conductivity
and catalytic activity. As these compounds also have little to no
ionic conductivity they must be either modified or utilized as
part of a composite anode.
Double perovskite materials were first of interest due to
reasonable ionic conductivity but early materials such as
SrFeNbO6–δ and Sr2MnNbO6–δ mostly had negligible electronic
conductivity.[52−54] Both Sr2MgMoO6 and Sr2MnMoO6 came of
interest upon exhibition of electronic conductivity of ∼10 Scm−1
at 800 °C in addition to redox stability and stability to sul-
phurous impurities.[43,55] Acceptable fuel cell performance was
found for fuel cells with Sr2MgMoO6 or Sr2MnMoO6 anodes,
albeit whilst using platinum as an anode current collector[43]
but in fact platinum is not an inert current collector.[56] In a
recent report, it was found that the catalytic activity of SrMoO3
anode is not ideal for SOFC anode.[57] Further research into
Sr2MgMoO6 determined that degradation of the compound
occurred at 900 °C in a reducing atmosphere.[54] Doping with
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La was found to improve the fuel cell performance, although
REVIEW
subsequent research noted compound degradation upon
reoxidation.[58,59]
3.3. Other Anode Materials
Both pyrochlore and tungsten bronze structured compounds
were the focus of investigations into suitability for utilisation
as an anode material. Tungsten bronze structured compound
were investigated in 1999 with limited success, producing
electronic conducting materials of the order of ∼ 5 Scm−1 at
930 ° C.[60,61] Gadolinium titanate-based pyrochlores were first
of interest as electrolyte materials but were further developed
into mixed electronic-ionic conductor materials through B-site
doping.[62,63] Despite initial promising results, further inves-
tigation uncovered various deficiencies, such as interfacial
reactivity with YSZ for the most promising tungsten bronze,
Sr0.2Ba0.4Ti0.2Nb0.8O3,[64] and low electronic conductivity and
redox instability for pyrochlores such as Pr2Sn2O7.[65] SrVO3
from reduction of SrVO4 was also investigated as potential
SOFC anode.[66]
4. Recent Developments in SOFC Anode Materials
In the three years since the last significant review of anode
materials, over 200 papers have been published in this area.
A small selection of review papers have briefly covered anode
materials,[67–69] however none of these papers specifically
address the progress in anode materials development, mainly
dwelling on previously covered materials, i.e. Ni/YSZ, STO and
LSCM. This section covers recent developments in this area
in both written and tabulated form, using a selection from the
available literature.
4.1. Metal-Fluorites Cermets
Researches on cermets anodes are still active despite a number
of known complications with their application. The most
common electrolytes in SOFCs are based on the fluorite struc-
ture, either as doped zirconia or doped ceria, thus many new
anode materials are developed using these structures as a base.
In the study of Qiao et al.[70] using Ni/YSZ and Ni-CeO2/YSZ
as anodes, it was demonstrated that at least 25 wt% of Ni was
needed to ensure low ohmic resistance and that, despite being
doped with ceria, the nickel and ceria phases co-existed sepa-
rately with a decrease in cell polarisation resistance observed
with increases in ceria doping, thus enhancing performance.
However, performance was linked directly to the presence of
nano-sized nickel oxide formed during the impregnation syn-
thesis and therefore better dispersion of nickel particles onto
YSZ played a more important role than the doping with ceria.
When applied to other fuels, the same system produced some
interesting performance: Ma et al.[71] showed that humidi-
fied ammonia gave the same performance than humidified
hydrogen despite the fact that the ammonia cell having a larger
interfacial polarisation resulting from a two-stage process
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namely the cracking of ammonia and the oxidation of hydrogen
into water requires a much greater catalytic activity; and
Kurokawa et al.[72] found that the impregnation of Ni-YSZ with
nanoparticles of ceria rendered this former much more stable
to sulphur-containing hydrogen as the initial cell voltage could
almost be fully recovered by exposing the cell back to sulphur-
free hydrogen after 500 h of operation under poisonous con-
ditions. Again, this behaviour is an indirect effect from ceria
by allowing a better dispersion of the nickel anode onto the
YSZ electrolyte rather than directly through doping of ceria. If
doped with titanium, YSZ exhibits an increased electronic con-
ductivity with a smaller ionic conductivity in reduced atmos-
phere[73] and compounds with high yttrium content and low
titanium content are better conductors than YSZ both in air and
hydrogen.[74] However, Pd/ceria impregnated ceria-doped YSZ
and LST-YSZ have less ionic conductivity than YSZ alone when
impregnated with ceria, which is mainly a consequence of the
presence of titanium.[75] Concerning the use of other metals,
Venancio et al.[76] and Cimenti et al.[77] reported new advances
on carbon deposition issues when dealing with alcohol fuels.
Using a copper cermet, the former applied a cell to ethanol and
found no degradation after 200 h with no carbon deposition at
all; while using a copper/cobalt catalyst on zirconium-doped
ceria, the latter established that even if the performance of the
cell in either methanol or ethanol was slightly below the one in
wet hydrogen, the coke deposition was limited after 24 h and
re-exposure to hydrogen allowed the performance to be recov-
ered indicating that the anode was not deactivated by coking.
Not only copper, recently Linic et al.[78] demonstrate that sup-
ported Sn/Ni alloy catalyst is more resistant to deactivation via
carbon deposition than supported monometallic Ni catalyst
in steam reforming of isooctane at moderate steam to carbon
ratios. The reasons for the enhanced carbon-tolerance of Sn/
Ni compared to monometallic Ni are high propensity of Sn/
Ni to oxidize carbon and lower driving force to form carbon
deposits on low-coordinated metal sites.[79] A striking point
however in Venancio’s study is the difference of performance
observed between ethanol and hydrogen fuels. While under
both fuels the performance increases with increasing tempera-
ture, the lower the temperature the nearer both performances
are. Moreover, only a maximum performance of 168 mW.cm−2
is obtained for ethanol at 950 ºC, which approaches the limiting
value of operation for a copper based anode.
Considering SDC-based systems, Chen et al.[80] showed that
synthesised through the urea-combustion sintering method,
a volume percent of 50 to 60% of nickel was required for the
cermet to meet requirements for anode materials based on
electrical conductivity data and TEC. It was also shown that
despite a lack of chemical reactivity between Ni and SDC, the
porosity and bending strength of the materials were highly
dependent on Ni content. If other metals are used or if cata-
lysts are added, results obtained are not always predictable,
calling for further investigations to be carried out when SDC-
based anodes/electrolytes are used. Wang et al.[81] showed that
adding a SDC-Ru catalyst layer on top of a nickel-SDC cermet
had no influence on the cell efficiency both in wet hydrogen
and wet methane whereas work done on copper-nickel com-
posite cermets obtained significantly different results,[82] which
is probably related to the already high catalytic activity of nickel
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Table 1. Conductivity of selected metal- fluorite cermet anode materials.

REVIEW
Anode Composition Anode Performance Reference
Electronic Conductivity (Scm−1) Ionic Conductivity (Scm−1) Temperature (ºC) Fuel
70 vol% Ni-SDC ∼4000 - 800 40% H2-N2 [80]
60 vol% Ni-SDC ∼2950 - 800 40% H2-N2 [80]
50 vol% Ni-SDC ∼2140 - 800 40% H2-N2 [80]
40 vol% Ni-Y0.1Ce0.8Ti0.1O1.95 1480 - 800 4% H2-Ar [74]
40 vol% Ni-Y0.2Ce0.8O1.9 1320 - 800 4% H2-Ar [74]
40 vol% Ni-SDC ∼1260 - 800 40% H2-N2 [74]
xAg-Ce0.8Gd0.2O1.9 (x>45 wt%) 1260 - 650 CO [86]
45 wt% Ag-Ce0.8Sm0.2O1.9 1254 - 650 CO [83]
Ni-Sc0.1Ce0.01Zr0.89O1.95 837 - 600 3% H2O-H2 [213]
Cu/Ni/SDC 633 - 600 dry CH4 [82]
30 vol% Ni-SDC ∼630 - 800 40% H2-N2 [80]
Ni0.95Cu0.05/SDC 417 - 600 dry CH4 [82]
Ni/SDC 405 - 600 dry CH4 [82]

metal, intrinsically reduced in the copper-nickel composite
as an overall. The latter study demonstrated that while losing
60% of power density after 7 h of operation in dry methane
with pure Ni, only 7% or 2% losses were obtained after 12 h
when copper was doped into the cermet or added as an inter-
layer respectively, which is a direct result of nickel agglomera-
tion and carbon deposition in the pure nickel cermet. When
looking at relative area of carbon deposition after the tests, the
same conclusion was drawn with only 5% for Cu/Ni/SDC com-
pare to 49% for Ni/SDC anodes. A study with silver[83] was also
conducted and results included a high electrical conductivity in
pure CO, no carbon deposition during fuel cell testing, a high
porosity and generally a better performance than the copper-
ceria/SDC anode. However, the nature of the electrode itself is
a major obstacle to its commercialisation as silver is onerous
and difficult to mass-produce for industrial usage. The conduc-
tivities of selected metal-fluorite cermets are listed in Table 1.
GDC has also been applied with some success. A Ni-Cu alloy
with GDC on a GDC supported electrolyte was tested by Sin
et al.[84] and showed suitable performance for the 1300 h of
testing in dry methane with compositional changes negligible
and carbon deposition not affecting the performance while
being minimisable by using wet methane. A similar effect was
noted for a Fe-Ni alloy with GDC, although the test period was
only 50 h.[85] When used with silver, using CO as a gas, a con-
version above 96% can be achieved over a period of 50 h and
carbon deposition is unchanged with temperature rendering
this latter negligible on Ag-GDC anodes;[86] however, again, cost
would be an issue. Introduction of Ir to GDC caused a hun-
dredfold increase in the CH4 conversion rate without observed
carbon deposition.[87] The main problem with GDC remains
that the doping of ceria with gadolinium decreases the conduc-
tivity in either metallic or bi-metallic compounds[88] making
GDC unlikely to be used with current cermet anodes or with
any future materials based on the same properties as metals.
Concerning systems using ScSZ, Huang et al.[88] showed that
using Fe-Ni alloys with ScSZ as cermet, carbon formation could
be suppressed compare to Ni, unfortunately stability over time
was an issue. If copper is used with ceria as anode however, oper-
ability up to 250 h without degradation was observed.[89] This
latter behaviour was also observed even with a Ni-ScSZ system
given that a layer of copper-ceria was present.[90] Even so the pres-
ence of copper with nickel can suppress most effects of degrada-
tion, a study by Asamoto et al.[91] showed that Ni incorporated
with alkaline-earth oxides (in particular calcium oxide) were
more stable in metal/SDC systems with ScSZ as electrolyte than
Ni alone in similar systems independently of the proportions
(even if an excess of oxide did increases the ohmic resistance).
More recently, Huang et al.[92] investigated Ni/ScSZ systems with
catalytic layers of LSCM and despite the chemical impossibility
of carbon deposition when using LSCM/ceria, the critical long
term exposure with Ni performance was not carried out.
Finally, cermet anodes are also used in combination with
the perovskite-type electrolyte LSGM, however as shown by
Hwang[93] and Bozza,[94] inter-diffusion between anode/electro-
lyte components are subject to the synthesis procedure used
(APS vs. EPD). Moreover, if Ni-Pd alloys or interlayers are used
in conjunction with a mixed LSC-SDC anode[95] or if Cu-Pd
is added to lanthanum-doped ceria (LCO) anode,[96] results
obtained show respectively that the methane oxidation over
Pd-Ni involves non-electrochemical formation of hydrogen and
carbon monoxide from methane and water and that if impreg-
nated with Cu-Pd, a better performance for LCO is obtained
than when using pure copper as well as less carbon deposition
than when using pure palladium. Therefore, LSGM has yet to
be associated in the right anode/cathode system in order to give
the same promising results it exhibits as an electrolyte than
as a whole. The typical fuel cell performances based on metal-
fluorite cermet anode are listed in Table 2.
4.2. Perovskites-Based Anode Materials
Perovskite materials have been the main focus of alternative
SOFC anode research over the last 20 years. This trend has not
diminished in the previous 3 years and much, if not most, of

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Table 2. Fuel cell performance of selected metal- fluorite cermet anode materials.
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Anode Composition Fuel Cell Performance Reference

Electrolyte/ Temperature Fuel Maximum Power Test Period
Cathode (ºC) Density (mWcm−2) (hours)
Co0.5Fe0.5-Sm0.2Ce0.8O1.9/Sm0.2Ce0.8O1.9 LSGM/SCF 800 3% H2O-H2/O2 1200 40 [217]
Ni-Sc0.1Ce0.01Zr0.89O1.95 ScCSZ/GDC/LSCF-GDC 600 3% H2O-H2 1100 - [213]
Ni-Sm0.2Ce0.8O1.9 YSZ/LSM-YSZ 800 H2O saturated H2 980 - [218]
Fe0.1Ni0.9/YSZ YSZ/LSM-YSZ 800 3% H2O-H2 ∼960 - [219]
NiO-Gd0.1Ce0.9O1.95 GDC/LSCF-GDC 650 3% H2O-H2 909 - [220]
1 wt% Pd-5 wt% CeO2-La0.4Ce0.6O2-δ LSGM/SCF 800 dry H2/O2 dry CH4/O2 ∼870 345 80 [96]
7wt% SDC-Ru/NiO-SDC SDC/BSCF 650 3% H2O-H2/O2 3% 850 462 - [81]
H2O-CH4/O2
NiO-La0.4Ce0.6O2-x LSGM/LSCF 700 H2 780 - [94]
1 wt% Cu-5 wt% CeO2-La0.4Ce0.6O2-δ LSGM/SCF 800 dry H2/O2 dry CH4/O2 ∼610 66 80 [96]
Cu-CeO2-YSZ/Ni-ScSZ ScSZ/PCM 800 H2/O2 50% 604 438 - [90]
H2O-C2H5OH/O2
2 wt% Gd0.2Ce0.8O2-Ni-ScSZ ScSZ/PCM 800 3% H2O-H2/O2 602 - [221]
10% Cu- 90% Ce0.8Zr0.2O2/Ni-CeO2/ ScSZ/PCM 800 H2/O2 50% 601 519 250 [89]
Ni-YSZ H2O-C2H5OH/O2
3:1 wt LSCM-CeO2:Ni-ScSZ ScSZ/PCM 800 3% H2O-H2/O2 50% 582 422 - [92]
H2O-C2H5OH/O2
Ni-Sm2O3 SDC/SSC-SDC 600 3% H2O-H2 550 - [222]
Ni-CeOx GDC/SSC 600 3% H2O-H2 545 - [223]
25 wt% Ni- 10wt% CeO2 – 65 wt% YSZ YSZ/Pt 800 3% H2O-H2 530 - [70]
Ni-YSZ 8YSZ/LSM-8YSZ 850 3% H2O-NH3 3% 526 530 - [71]
H2O-H2
10% Cu- 90% CeO2/Ni-YSZ ScSZ/PCM 800 H2/O2 50% ∼520 ∼410 - [94]
H2O-C2H5OH/O2
Ni/La0.8Sr0.2CrO3-Ce0.8Sm0.2O1.9 LSGM/LSC 800 dry H2/O2-He dry CH4/ 520 20 - [95]
O2-He
NiO-YSZ 8YSZ/LSM-8YSZ 800 3% H2O-H2 500 - [224]
Cu-Co (Ru)/Zr0.35Ce0.65O2-δ YSZ/LSM 800 3% H2O-H2/O2 C2H5/ 496 440 444 24 [77]
O2 CH4/O2
Ni-GDC (98 μm electrolyte) GDC/LSCF-GDC 700 3% H2O-H2 412 - [225]
Ni-GDC (19 μm electolyte) 650 492
Ni0.5-Pd0.5/La0.8Sr0.2CrO3-Ce0.8Sm0.2O1.9 LSGM/LSC 800 dry H2/O2-He dry CH4/ 480 150 - [95]
O2-He
Ni-ScSZ ScSZ/PCM 800 3% H2O-H2/O2 466 - [221]
Ni-Sm0.2Ce0.8O1.9 SDC/SSC-SDC 600 3% H2O-H2 460 - [222]
25% Cu- 75% CeO2/Ni-YSZ ScSZ/PCM 800 H2/O2 50% ∼450 ∼ 380 - [89]
H2O-C2H5OH/O2
Pd/La0.8Sr0.2CrO3-Ce0.8Sm0.2O1.9 LSGM/LSC 800 dry H2/O2-He dry CH4/ 440 70 - [93]
O2-He
45 wt% Ag-Ce0.8Sm0.2O1.9 SDC/LSCF-SDC 700 CO 439 100 [83]
Ni-Sm0.2Ce0.8O1.9 SDC/LSCF 600 H2 400 - [212]
CuO-SDC-CeO2 YSZ/LSM-YSZ 800 H2 C3H7OH 350 220 - [226]
Ni-CeO2/Ni-SDC SDC/SSC-SDC 600 3% H2O-H2 CH4 340 300 - [227]
Ni0.95Cu0.05/SDC SDC/SSC-SDC 600 Dry CH4 338 - [82]
Cu0.5Ni0.5-GDC GDC/LSCF 800 Dry CH4 320 - [84]
Ni-GdOx GDC/SSC 600 3% H2O-H2 314 - [223]

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Table 3. Conductivity of selected SrTiO3-based anode materials.
Anode Composition
Electronic Conductivity (Scm−1) Ionic Conductivity (Scm−1)
La0.3Sr0.7TiO3 ∼220 - 800
Y0.08Sr0.92Ti0.92Nb0.08O3 ∼200 - 600
(La0.3Sr0.7)0.93TiO3 145 0.01
(Y0.08Sr0.92)0.95TiO3 ∼80 ∼0.014
Y0.09Sr0.91TiO3 73.7 0∗
La0.3Sr0.7Sc0.1Ti0.9O3 49 0.01
La0.3Sr0.7Ti0.93Co0.07O3 ∼45 ∼0.011
Y0.08Sr0.92Ti0.97O3 ∼35 ∼0.015
Sr0.86Y0.08TiO3 ∼23 - 800
Y0.08Sr0.92Ti0.96Co0.04O3 20 0.0007
the new materials developed for anode applications have this
structure. Contemporary research in this area has taken off in
three main directions:
1. doping of known anode materials
2. use of known anode materials to form a cermet
3. development of novel anode materials
Due to the wealth of research already on compounds with
this structure, much of the research has focused on the devel-
opment of the properties of previous materials such as LST,
YST and LSCM. Due to the previously determined characteris-
tics of these materials much of the recent work has focused on
improvement of the ionic conductivity and catalytic activity of
these materials.
Improvement of the ionic conductivity is generally
approached in one of two ways; either doping of the com-
pound to produce oxygen vacancies or combination of the
compound with an ionic conductor. Li et al.[97] used DFT to
determine the optimum B-site dopant to increase ionic con-
ductivity, through modelling of the oxygen migration energy
in various Sr(TM)O3 compounds, where TM is a transition
metal. As scandium was determined to have the lowest oxygen
migration energy, La0.3Sr0.7Sc0.1Ti0.9O3 was synthesised and
exhibited a good balance of electronic and ionic conductivi-
ties, 49 Scm−1 and 0.01 Scm−1 respectively at 800 °C. Doping
with cobalt met with similar success, with a small decrease in
electronic conductivity and a corresponding increase in ionic
conductivity compared to the scandium doped analogue.[98]
The corresponding Co-doped YST material exhibited compar-
atively lower electronic and ionic conductivities, likely owing
to the reduced conductivity of the parent compound.[99] These
results were confirmed in a blanket study of B-site doped
LST, with the Sc-doped compound exhibiting the highest con-
ductivity and lowest anodic overpotential.[100] The evidence
here suggests that this method of balancing the electronic
and ionic conductivities is certainly a feasible method for fuel
cell anode formation. A-site doping has proved a less efficient
method of improving anode properties, with recent studies
showing that strontium substitution with barium signifi-
cantly reduces fuel cell performance.[101]
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Anode Performance Reference
Temperature (°C) Fuel
H2(<5.8%)/N2 [98]
Humidified H2 [121]
800 H2(<5.8%)/N2 [103]
800 5%H2/Ar [104]
800 H2(<5.8%)/N2 [51] *[105]
800 H2(<5.8%)/N2 [97]
800 H2(<5.8%)/N2 [98]
800 H2(<5.8%)/N2 [105]
50% H2/N2 [228]
800 H2(<5.8%)/N2 [99]
Creation of oxygen vacancies can also be achieved through
charge balance compensation from the introduction of cation
deficiencies, as demonstrated previously on doped STO.[102]
Introduction of A-site deficiency (ASD) for both LST[103] and
YST[104] was discovered to be more efficient at retaining the
electronic conductivity than introduction of B-site deficiency
(BSD).[105] Li et al.[103] found that ASD-LST retained an elec-
tronic conductivity of 145 Scm−1 at 800°C while improving
the ionic conductivity to 0.01 Scm−1, significantly higher elec-
tronic conductivity than was observed for ASD-YST,[104] likely
due to the higher initial electronic conductivity of LST. Work
on the stability of the deficient YST materials determined that
sintering temperature or reduction has limited effects on the
conductivity of the ASD compound; however, the conductivity
of the BSD compound is dictated by those same factors.[106]
A-site deficient LST and YST have both been found to retain
greater electronic conductivity whilst gaining similar ionic con-
ductivities to the B-site doped compounds, without, as yet, any
observed drawbacks, which would make these compounds ideal
for SOFC anode applications. The conductivities of selected
SrTiO3 -based anode materials are listed in Table 3.
Improvement of anode performance through promotion of
catalytic activity and thus reduction of the activation polarisation
has primarily involved the incorporation of various noble and
transition metals, as well as ceria, to porous ceramic anodes.
It was found that impregnation of ∼ 20% gadolinia-doped ceria
and copper in La0.2Sr0.7TiO3 anode can significantly improve
the fuel cell performance and a power density of 0.5 W cm−2
at 750 °C has been achieved when hydrogen was used as the
fuel.[107]
The use of a small amount, typically < 5–10%, of nickel as
an anode catalyst has been found to significantly increase fuel
cell performance, with a five times increase in the maximum
power density observed with a LST-GDC anode.[108] The method
of catalyst incorporation into an anode can also have a signifi-
cant effect on the fuel cell performance. It was found that the
local point defects in a perovskite can affect the catalytic prop-
erty thus anode performance. Introduction of both gallium
and manganese in LST, e.g., La4Sr8Ti11Mn0.5Ga0.5O37.5, forms
an excellent SOFC anode material.[109] At relative lower tem-
perature, infiltration of the metal into a porous framework was
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found to be more effective than mixing into the ceramic during
REVIEW
synthesis, reducing the polarisation resistance by an order of
magnitude for a Ni-YST-YSZ composite.[110]
Increasing the catalytic activity will not, however, cover for
other deficiencies, as formation of anodes comprised of LST
or YST and ceria in a 1:1 ratio demonstrated.[111,112] Despite an
improvement of the anodic microstructure, universally poor
performance of these materials was observed, < 200mWcm−2 at
900 °C, which can be attributed to the low ionic conductivity
of the anodes. Manipulation of the LST:YSZ ratio was found
to be effective to increasing anode performance which, along-
side incorporation of palladium and ceria, caused a threefold
increase the fuel cell performance.[75]
The use of recently developed materials, such as ASD-LST,
has proved equally successful in the production of efficient
anodes. A composite anode with ASD-LST and GDC, with
copper infiltration used to increase the catalytic activity, demon-
strated similar fuel cell performance at lower temperatures than
was observed for LST-YSZ composites.[113] It must be noted that
the catalytic activity of copper is less than is found for other
metal catalysts, thus this performance could be improved by
replacement of the copper with other, more catalytically active,
metals.
While nickel has been found to have the highest activity for
hydrogen oxidation, thought to be due to the ideal strength of
the oxygen-metal bond,[114] other metals have been found to
exhibit sufficient catalytic activity, without coking or sulphur
poisoning, to supplant nickel in cermets. The use of palladium
as an anode catalyst has met with definitive success, doubling
the fuel cell performance of a LST-La0.4Ce0.6O2 composite,
reaching over 1 Wcm−2 at 850 °C with no observed degradation
upon exposure to H2S.[115] Ruthenium has also been found to
be an effective replacement for nickel, causing a reduction in
polarisation resistance from 2.6 Ωcm−2 to 0.8 Ωcm−2 at 800 °C
for a YST-YSZ composite, further reduced to 0.5 Ωcm−2 with
addition of ceria.[116] The cost of these alternative metal catalysts
has, however, meant that only small amounts of these metals
can be used, although, as can be seen from the above studies,
this is usually sufficient to cause significant improvements in
anode performance.
Table 4. Fuel cell performance of selected SrTiO3-based anode materials.
Anode Composition
Electrolyte/ Temperature
Cathode (°C)
1.5wt% Pd-Sr0.88Y0.08TiO3- LSGM/SSC 850 800
La0.4Ce0.6O1.8
5% CeO2–0.5% Pd–45% YSZ/LSF-YSZ 800
La0.3Sr0.7TiO3–65% Y0.08Zr0.92O2
1wt% Pd–3wt% CeO2–60% YSZ/LSCF-YSZ 800
SrTi0.99Nb0.01O3–40% Y0.08Zr0.92O2
1wt% Pd–10wt% CeO2–75% YSZ/LSCF-YSZ 800
La0.3Sr0.7TiO3–25% Y0.08Zr0.92O2
Cu- Gd0.2Ce0.8O2 – La0.2Sr0.7TiO3 YSZ/LSM-YSZ 750
Ru-CeO2–50% Sr0.88Y0.08TiO3–50% YSZ/LSM-YSZ 800
Y0.08Zr0.92O2
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The effect of catalyst addition to fuel cell performance cannot
be overstated, as aptly demonstrated by Lee et al.[117] who
increased the fuel cell performance of a LST infiltrated YSZ
anode from less than 20 mWcm−2 to 780 mWcm−2 through the
addition of palladium and ceria. This study also ably demon-
strated the effect that anodic microstructure has on the fuel cell
performance as an increase of the sintering temperature caused
a significant drop in fuel cell performance, due to an increase in
the anode porosity and sintering of the LST in the YSZ pores.
Not all contemporary research into strontium titanates has
been limited solely to improvement of the ionic conductivity
and catalytic activity. Blennow et al.[118] determined that a
combination of niobium doping of STO and sintering at high
temperature in reducing atmosphere gave electronic conduc-
tivity similar to LST and YST, up to 200 Scm−1 at 800 °C. The
increased conductivity was proven to be a consequence of the
sintering conditions and this was nullified after oxidation at
1200 °C.[119] A further increase in conductivity was observed
to occur upon sintering in ammonia gas, however the conduc-
tivity enhancement was negated at much lower temperatures,
∼600 °C, reducing the applicability of the material.[120] Despite
the problems associated with high temperature sintering, a
composite Nb-doped STO–YSZ anode, infiltrated with palla-
dium and ceria, proved to be an efficient anode material when
combined with a YSZ electrolyte.[119] Replacement of niobium
with tantalum reduced the electronic conductivity without any
observable improvement in anode properties, although forma-
tion of a CeO2, Pd impregnated composite anode with YSZ
did give a low area specific resistance (ASR) of 0.4 Ωcm−2 at
700 °C.[121] The typical fuel cell performances based on selected
SrTiO3-based anode are listed in Table 4.
Similar compositional manipulations to those used for stron-
tium titanates can also be applied to LSCM, although as the
compound is already doped on both A-site and B-site the effect
cannot be easily predicted. As with LST and YST, introduction
of A-site deficiency to LSCM causes a predictable increase in the
ionic conductivity and a resultant decrease in electronic conduc-
tivity, however the conductivity changes are not as dramatic as
found for the doped strontium titanates, with ionic conductivity
peaking at ∼3 × 10−4 Scm−1 at 950 °C.[122]
Fuel Cell Performance Reference
Fuel Maximum Power Density Test Period
(mWcm−2) (Hrs)
Dry H2 1066 577 - [116]
Humidified H2 780 - [118]
Humidified H2 640 - [85]
Humidified H2 570 - [113]
Humidified H2 550 - [114]
Humidified H2 Humidified H2 510 470 - [117]
with 10ppm H2S
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Table 5. Conductivity of selected La0.75Sr0.25Cr0.5Mn0.5O3-based anode materials.
Anode Composition
Electronic Conductivity (Scm−1)
Ni–CeO2–La0.7Sr0.3Cr1-xNixO3 5.03
La0.75Sr0.25Cr0.5Mn0.44Ni0.06O3 2.4
La0.65Ce0.1Sr0.25Cr0.5Mn0.5O3 ∼0.4
Pr0.75Sr0.25Cr0.5Mn0.5O3 0.14
A-site substitution for LSCM met with greater success than
was found for strontium titanates. Partial substitution of lan-
thanum with cerium successfully increased the catalytic activity
of the anode, reducing the polarisation resistance by one order
of magnitude, from 2.3 Ωcm−2 to 0.2 Ωcm−2 at 800 °C.[123] The
Rp of Ce-substituted LSCM was similar to that found for elec-
trolyte-graded LSCM anodes[45] but less than for praseodymium
substituted LSCM, which is more suited for cathodic applica-
tions.[124] Building on research into cathodic materials[125],
La0.8Sr0.2Sc0.2Mn0.8O3 (LSSM) was investigated as an anode
material for symmetric SOFCs.[126] Scandium was previously
calculated to be the most effective dopant to increase the oxygen
ion conductivity in strontium based perovskites,[97] however for
LSSM an improvement in total conductivity in reducing atmos-
pheres was observed. Despite the improvement in conductivity,
symmetrical fuel cell performance was not an improvement on
that found for symmetrical LSCM-based FCs.[46]
Substitution of cobalt for manganese in LSCM was deter-
mined to elicit the highest conductivity of the tested transition
metals.[127] The catalytic activity of the compounds was deter-
mined by temperature programmed reduction (TPR) and was
a reasonable indicator of fuel cell performance, with the iron
analogue exhibiting the highest performance. The high cata-
lytic activity of the iron-substituted compound was echoed in
the results of fuel cell operation in CO/CO2 mixtures.[128] The
iron doped sample was observed to partially degrade into the
spinel phase upon exposure to a highly reducing atmosphere at
900 °C, although this was reversible upon re-oxidation.[129]
Introduction of nickel or ruthenium for manganese, forming
LSCRu and LSCNi, was found to increase the catalytic activity
of the anode[130] due to the formation of metal nano-particles
upon reduction. The formation of these nanoparticles has previ-
ously been found to reduce anode polarisation resistance, albeit
with greater efficacy for ruthenium.[131,132] The resultant fuel
cell performance of both of these anodes was <300 mWcm−2
at 800 °C and both anodes required >96 h before stable opera-
tion at these outputs was observed. A solid state combination
of LSCRu with GDC was found to give steady fuel cell perform-
ances between 400 and 500 mWcm−2 at 800 °C without notice-
able ruthenium nanoparticles coarsening over 1000 h of opera-
tion.[131,132] Despite the reasonable performance of LSCRu, wet
chemical infiltration of the respective metals into a LSCM-
electrolyte composite may be a more effective, and controllable,
method for increasing anode performance.
The nickel substituted material, LSCNi, was additionally
considered for symmetrical fuel cells as a result of high con-
version of CH4 at 800 °C and slightly improved conductivity
over LSCM.[133,134] Despite an observed ASR of 1.3 Ωcm−2 at
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REVIEW
Anode Performance Reference
Ionic Conductivity (Scm−1) Temperature (°C) Fuel
- 800 Humidified H2 [56]
- 800 5% H2/Ar [135]
- 700 Humidified H2 [45]
- 900 5% H2/Ar [125]
800 °C the long term stability of these materials is in doubt
over observed coarsening of the surface nickel nanoparticles
upon extended use.[130] Building on the work by Lay et al.[123]
and Kobsiriphat et al.[130], Bao et al.[135] formed (La0.7Sr0.3)0.4
Ce0.6Cr0.4Ni0.6O3 which increased the conductivity upon reduc-
tion but degraded into CeO2, Ni and LSCNi and thus exhibited
poor fuel cell performance. The conductivity of selected La0.75
Sr0.25 Cr0.5 Mn0.5 O3-based anode are listed in Table 5.
The formation of composite materials, with the aim of col-
lating desirable properties, has already proven successful for
strontium titanates and the same trends are noted for LSCM
anodes. The use of palladium was previously found to cause
a significant increase in fuel cell performance for strontium
titanate composite anodes and a LSCM infiltrated YSZ scaffold
also demonstrated a substantial increase in fuel cell perform-
ance upon impregnation with palladium, with further increases
noted upon ceria infiltration.[56] Substitution of 0.5% rhodium
or 1% nickel in place of 0.5% of palladium gave similar fuel cell
performances, suggesting that the electrocatalytic activity and
mechanism of reaction of these metals is not dissimilar.
Impregnation of an ionic conducting support with an elec-
tronic conducting phase was expected to be especially effec-
tive in forming efficient anode materials. Impregnation with
LSCM into YSZ formed catalytically active and stable anodes,
with little difference in fuel cell performance between hydrogen
and methane fuels.[136] Additional impregnation of nickel and
silver doubled fuel cell performance in hydrogen and caused a
50% increase in performance in methane with no observable
anode degradation. Despite the increased catalytic activity of
GDC over YSZ,[137] replacement of YSZ with GDC was found
to reduce fuel cell performance, although this could be due to
impregnation of the electronically conducting phase with the
electrolyte and not vice-versa.[138] The method of impregnation
also has an effect on the anode performance, with co-impregna-
tion of LSCM and nickel proving more effective than sequen-
tial impregnation of LSCM then nickel, likely due to micro-
structural and distributional differences.[139] Despite the high
loading of the LSCM-nickel composite onto YSZ, stable opera-
tion was observed for 6 hours without coking or noticeable per-
formance degradation and acceptable fuel cell performance was
noted in both hydrogen and methane. Similar performance in
both hydrogen and methane was noted for a nickel, SDC and
La0.75Sr0.25Cr0.5Fe0.5O3 impregnated YSZ anode, with reasonable
performance in ethanol also observed at 800 ° C.[140]
In some cases the use of graded anodes has been found to
enhance both fuel cell performance and stability. A solid state
synthesised composite of copper, LSCM and YSZ, utilised as
part of a graded anode with two anode functional layers Ni/YSZ
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and Ni/ScSZ, was found to treble fuel cell power density over degradation was observed upon operation for 50 hours for the
REVIEW

the parent Cu/LSCM/ScSZ anodes.[141] While graded anodes do
have the capacity to increase fuel cell performance, the prac-
ticality of these materials undermines their usage and compa-
rable performances can be achieved using alternative, more
efficient methods.
While ionic conduction throughout the anode is desir-
able, it is not strictly necessary to achieve good fuel cell per-
formance. Impregnation of nickel and ceria to an LSCM sup-
port increased the fuel cell performance six-fold, reaching
948 mWcm−2 at 800 °C.[142] Similar performance was observed
in a LSCM anode infiltrated with high levels of copper and palla-
dium, 20 wt% and 1.5 wt% respectively, although a lanthanum-
doped ceria interlayer was required to prevent interfacial
reactions between LSGM and LSCM.[143] When using methane
as a fuel, impregnation of palladium into the anode causes a sig-
nificant increase in power density, not observed when hydrogen
is utilised as the fuel, suggesting that palladium might catalyse
methane cracking at the anode.[144] A reduction in the electrode
polarisation resistance is also noted for palladium impregnated
anodes when using methane or ethanol as the fuel, enhancing
the performance of a LSCM/YSZ composite.[145] Typical fuel cell
performances based on selected La0.75Sr0.25Cr0.5Mn0.5O3-based
anode materials are listed in Table 6.
The appropriation of cathode materials for anode appli-
cations is not unknown but the most of existing cathode are
expected unstable under anode operating conditions.[126] As
La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) was found to have reasonable
catalytic activity for methane,[146] propane and syn-gas[147] oxi-
dation, it was investigated as a component in an anode com-
posite with GDC. Reasonable fuel cell performance was noted
with hydrogen fuel[146] and, after nickel impregnation, similar
performance was noted with propane fuel.[148] No anodic
LSCF-GDC composite, although after 100 hours partial degra-
dation into La2NiO4 and SrCo1-xFexO3 was seen for the nickel
impregnated LSCF-GDC anode.[149]
The chemical and redox stability of SMMO has been ques-
tioned recently with reports of interfacial reactions with YSZ
and LSGM electrolytes[150] and the formation of Ruddlesden-
Poppler phases upon reduction at 900°C.[51] The reported
redox instability was successfully refuted by Marrero-López
et al.,[151,141] being ascribed to the high temperature synthesis
method, however interfacial reactivity with common electrolytes
does occur and requires the use of either a GDC electrolyte or
interlayer for long term stability.
Magnesium substitution in SMMO was found to increase the
total conductivity, in the order Mg < Co < Ni, yet fuel cell per-
formance for the cobalt analogue was determined to be superior
to that of the nickel, likely due to higher catalytic activity for fuel
oxidation.[142,152] Increased conductivity over SMMO was fur-
ther compounded by high temperature annealing in a reducing
atmosphere, increasing the conductivity of Sr2NiMoO6 from
∼5 Scm−1 to 50 Scm−1 at 800 °C.[153] Increased catalytic perform-
ance for methane combustion was also noted with partial sub-
stitution of manganese, although with a subsequent reduction
in the compound stability.[154] Introduction of iron for magne-
sium achieved a slight increase in fuel cell performance com-
pared to the nickel analogue, with no improvement observed
upon increased iron doping.[155,156] Stable operation of the iron
substituted SMMO in city gas was observed over 20 h with a
reduction of ∼ 100 mWcm−2 at 850 °C compared with pure
hydrogen, also hinting that these compounds may be stable
to detrimental impurities such as H2S, ammonia and naph-
thalene. The stability of the series of transition metal doped
SMMO compounds was called into question by Vasala et al.[157]

Table 6. Fuel cell performance of selected La0.75Sr0.25Cr0.5Mn0.5O3-based anode materials.

Anode Composition Fuel Cell Performance Reference

Electrolyte/ Temperature Fuel Maximum Power Test Period
Cathode (°C) Density (mWcm−2) (Hrs)
2wt% Ag–6wt% Ni–32% La0.75Sr0.25Cr0.5Mn0.5O3–60% YSZ/LSM 850 Dry H2 Dry CH4 1302 769 - [137]
Y0.08Zr0.92O2
37wt% (NiO-La0.75Sr0.25Cr0.5Mn0.5O3)–63wt% Y0.08Zr0.92O2 YSZ/LSM 800 Dry H2 Dry CH4 1151 704 6 hrs [140]
Ni -Sm0.2Ce0.8O2–La0.75Sr0.25Cr0.5Fe0.5O3–Y0.08Zr0.92O2 YSZ/LSM-SDC 800 Dry H2 Dry CH4 960 744 406 - [141]
Dry C2H5OH
8.9wt% Ni–5.8%wt CeO2–La0.75Sr0.25Cr0.5Mn0.5O3 YSZ/LSM 800 Dry H2 Dry CH4 948 197 7 hrs [143]
20wt% Cu–1.5wt% Pd–La0.75Sr0.25Cr0.5Mn0.5O3 LDC/LSGM/SCF 850 Dry H2 Dry CH4 890 600 - [145]
35% La0.75Sr0.25Cr0.5Mn0.5O3–65% Y0.08Zr0.92O2 YSZ/LSM 850 Dry H2 Dry CH4 567 561 - [137]

Cu–La0.7Sr0.3Cr0.5Mn0.5O3–Y0.08Zr0.92O2 Ni-YSZ/Ni-ScSZ/ScSZ/PCM 800 H2 2:1 mixture 534 384 20 hrs 120 hrs [142]
CH3CH2OH-H2O
50% La0.8Sr0.2Cr0.82Ru0.18O3–50% Gd0.1Ce0.9O2 LSGM/LSCF-GDC 800 Humidified H2 530 - [132]
0.5% Pd–5% CeO2–45% YSZ/LSF-YSZ 700 Humidified H2 520 - [136]
La0.75Sr0.25Cr0.5Mn0.5O3–Y0.08Zr0.92O2
50% La0.8Sr0.2Cr0.82Ru0.18O3–50% Gd0.1Ce0.9O2 LSGM/LSCF-GDC 750 Humidified H2 458 - [131]
La0.75Sr0.25Cr0.5Mn0.5O3 – Gd0.2Ce0.8O2 YSZ/LSM-YSZ 800 Humidified H2 419 158 24 hrs [139]
Humidified CH4

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who concluded that only the Mg analogue was redox stable with
the cobalt, nickel and zinc containing compounds unstable to
reduction while the iron and manganese analogues unstable
to oxidation. This corroborates previous reports that the cobalt
and nickel analogues partially degrade upon reduction, forming
small amounts of metallic nickel and cobalt alongside SrO and
SrMoO4.[152] Reduction of the proportion of the molybdenum
for the iron containing sample has, however, been show to
improve the redox stability of the compound while retaining
reasonable conductivity.[158] The conductivity in both oxidizing
and reducing atmospheres allowed use as a symmetrical elec-
trode, achieving a fuel cell performance of ∼500 mWcm−2 at
800 °C, comparable to that of LSCM.[46]
Much of the research into SOFC anode materials is a deli-
cate balance between performance and stability. Substitution
of calcium for strontium in Sr2FeMoO6 significantly increased
the conductivity but was then observed to degrade at ∼400 °C
in nitrogen, with the opposite effect noted for the barium ana-
logue.[155] A similar effect was noted in SMMO, with niobium
and tungsten substitution for molybdenum increasing the sta-
bility of the compound to reduction whilst reducing the elec-
tronic conductivity.[159] As SMMO has been found to be redox
stable, the advantages of niobium doping are minimal, as
a small increase in the ionic conductivity should occur upon
increasing substitution, however doping of niobium into
the transition metal doped analogues would be of interest to
observe if this causes an increase in the redox stability of the
compounds.
The use of symmetrical electrodes in fuel cells would simul-
taneously simplify fuel cell manufacture and reduce fuel cell
costs.[160] While both anode and cathode share various require-
ments, the problem lies in the catalytic activity and the reten-
tion of properties in both oxidising and reducing environ-
ments. A composite electrode with a known cathode material
La0.7Ca0.3CrO3 and GDC exhibited acceptable conductivity
and TEC values in both oxidising and reducing atmospheres,
achieving similar performance to symmetrical LSCM electrodes
at high temperatures.[161] An alternative to true symmetrical
Table 7. Fuel cell performance of selected alternative perovskite anode materials.
Anode Composition
Electrolyte/Cathode Temperature (°C)
Sr2CoMoO6 LDC/LSGM/SCF 800
Sr1.6K0.4FeMoO6 LSGM/SKF 800
Sr2FeMoO6 SDC/LSGM/SmBaCo2O5 800 H2 Commercial City Gas
Sr2Fe1.5Mo0.5O6 LSGM/SFM 800
80% La0.7Ca0.3CrO3–20% LSGM/LCC-GDC20 900 H2 Commercial City Gas
Gd0.2Ce0.8O2
Sr2NiMoO6 LDC/LSGM/SCF 800
50% LaSr2Fe2CrO3–50% GDC/LSGM/LSCF 800
Gd0.1Ce0.9O2
Sr2MgMoO6 CGO/LSGM/LSCF 800
7wt% Ni–63wt% GDC/LSCF 800
La0.6Sr0.4Co0.2Fe0.8O3–
30wt% Gd0.2Ce0.8O2
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electrodes involves small compositional changes to tailor each
REVIEW
electrode to the specific operating conditions, whilst retaining
the desirable properties of the parent compound. A cathode of
Sr0.9K0.1FeO3-δ and an anode of Sr1.6K0.4FeMoO6-δ were combined
with LSGM to produce an efficient SOFC, with a maximum
power density of 766 mWcm−2 with H2 fuel at 800 ° C.[162] The
anode was later determined to be a composite of highly conduc-
tive SrMoO3 phase and a MIEC SrFe0.6Mo0.4O2.7 phase, with the
potassium thought to have sublimed from the structure during
high temperature synthesis. The effect of re-oxidation on the
anode has yet to be investigated, however, due to the nature of
the anode, problems associated with non-homogenous volume
expansion are to be expected. Typical fuel cell performances of
selected alternative anode materials are listed in Table 7.
Research into oxidation catalysts of hydrocarbons is a viable
field in its own right, however it can also be a fruitful area for
SOFC anode researchers to utilise. Vanadium oxides have been
previously investigated for their catalytic activity for hydro-
carbon and hydrogen sulphide oxidation.[163,164] A composite
anode of vanadium oxide, YSZ and LaCrO3 was expected to
provide the necessary anode properties, however carbon depo-
sition was observed upon extended use with syn-gas.[165] Soli-
tary use of La0.7Sr0.3VO3 as an anode, building on work by Hui
and Petric,[66] improved the fuel cell performance and the sta-
bility to coking yet anode coarsening caused severe perform-
ance degradation upon extended use.[166] Replacement of the
lanthanum with cerium caused a change in fuel utilisation, as
fuel cell performance was determined to be related to H2S con-
centration.[167] This did not prevent utilisation of a small per-
centage of the methane fuel and coking was observed after only
24 h operation. Replacement of vanadium with chromium in
Ce0.9Sr0.1VO3 increased both the conductivity in reducing atmos-
pheres and the redox stability of the compound, but despite the
formation of a composite anode with nickel and YSZ the fuel
cell performance was still predominantly related to the H2S
reaction for 0.5% H2S/CH4 fuel.[168] The poor fuel cell perform-
ance and coking upon use with hydrocarbon fuels observed for
these compounds renders them useless as stand-alone anode
Fuel Cell Performance Reference
Fuel Maximum Power Density (mWcm−2) Test Period (Hrs)
H2 Dry CH4 Wet CH4 1017 452 634 - [153]
H2 766 - [162]
584 476 - [81]
Humidified H2 ∼ 500 20 [158]
573 333 - [159]
H2 Dry CH4 Wet CH4 ∼490 ∼250 ∼125 50 cycles (H2) [229]
Humidified H2 365 48hrs [230]
Humidified H2 330 - [151]
Dry CH3CH2CH3 300 - [146]
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materials, however as part of a composite the introduction of
REVIEW
a small percentage of these materials may simultaneously pre-
vent H2S poisoning and increase anode performance.
Formation of a mixed vanadate-molybdate oxide,
CaV0.5Mo0.5O3, exhibited high electronic conductivity,
∼525 Scm−1 at 800 °C, although degradation of the compound
was observed above 600 °C,[169] which precludes the use of the
compound as an anode material. As calcium doping of a stron-
tium-based perovskite was previously found to increase the con-
ductivity while reducing the redox stability, due to the oxidation
states of the vanadium and molybdenum it is unlikely that this
compound will become redox stable.
Recently, Liu et al.[170] reported that a composite anode con-
taining mixed proton conducting oxide BaZr0.1Ce0.7Y0.1Yb0.1O3−δ
allows rapid transport of both protons and oxide ion vacancies.
It exhibits high ionic conductivity at relatively low tempera-
tures (500 to 700 °C). Its ability to resist deactivation by sulfur
and coking appears linked to the mixed conductor’s enhanced
catalytic activity for sulfur oxidation and hydrocarbon cracking
and reforming, as well as enhanced water adsorption capability.
This research may lead to a new direction to develop sulphur-
resistant and anti-coking anode for SOFCs based mixed proton
conducting oxides. The conductivities of selected alternative
perovskite anode materials are listed in Table 8.
4.3. Alternative Materials
Both tungsten bronze and pyrochlore structured materials
have previously been investigated as anode materials, without
much success. A redox stable pyrochlore Yb0.96Ca1.04TiNbO6.98
exhibited a conductivity of 9 Scm−1 at 800 °C, although high
temperature firing in reducing atmosphere was required, with
conductivity of 0.07 Scm−1 at 800 °C observed after low tem-
perature reduction.[171] Tungsten bronze structured samarium
molybdate, doped and undoped, was not found to react with a
YSZ electrolyte yet exhibited conductivities uniformly less than
0.2 Scm−1.[172] While the recently developed pyrochlore may
have some promise, the low electronic conductivity of the tung-
sten bronze compounds likely excludes them from application
as SOFC anode materials.
Rutile structured compound have previously come under
consideration as SOFC anode materials due to their short
Table 8. Conductivity of selected alternative perovskite anode materials.
Anode Composition
Electronic Conductivity (Scm−1) Ionic Conductivity (Scm−1)
Ca(V0.5Mo0.5)O3 525
Sr1.6K0.4FeMoO6 ∼450
Ce0.9Sr0.1VO3 ∼250
Sr2NiMoO6 ∼50 ∼5
La0.75Sr0.25Cr0.5Fe0.5O3 ∼7.5
Ce0.9Sr0.1Cr0.5V0.5O3 4.34
Sr2CoMoO6 ∼1
Sr2MgMoO6 0.8
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M-M distances, which promotes electronic conductivity.[173,174]
Building on previous work on rutile niobium titanates, Lash-
tabeg et al.[175] attempted to form a compound with a rutile
structure under oxidising and reducing atmospheres, by co-
doping rutile TiO2 with niobium and chromium. While a sig-
nificant increase in conductivity was observed, the reduction
kinetics of the compound were slow, with equilibrium not
reached after 50 h at 900 °C in 5% H2/Ar. Similarly structured
chromium niobate was not observed to suffer similarly slow
kinetics, although exhibited lesser conductivity, of ∼3.7 Scm−1,
than was observed for Ti1–2xCrxNbxO2 at 800 °C.[176] Degrada-
tion of the chromium niobate upon high temperature reduction
prevented attempts to increase the conductivity through further
formation of oxygen vacancies.
Some metal vanadates have been investigated as sulphur-
resistant SOFC anode materials. It has been reported that
Ce0.9Sr0.1VOx (x = 3,4) is a potential sulphur tolerant anode
material for SOFCs at high temperatures.[177–179] Recently
it was found that Sr- and Ca-doped CeVO4 is redox stable in
5%H2/Ar at a temperature below 600°C but the conductivity
is well below 1S/cm therefore cannot be used as SOFC anode
materials.[180,181] However, Sr-doped CeVO3, Ce0.85Sr0.15VO3
is redox reversible and exhibits a conductivity of 2.5–6 S cm−1
between 700 to 25 °C in 5%H2/Ar which is suitable to be used
as SOFC anode in terms of conductivity.[182] Co2V2O7[183] and
FeVO4[184] were also investigated as potential SOFC anode but
it was found that they are unstable in a reducing atmosphere
therefore are not suitable candidates. As has been shown pre-
viously, poisoning by sulphurous impurities causes signifi-
cant difficulties in the application of anode materials as many
fuels contain a trace amount of hydrogen sulphide. Without a
prior purification process, the longevity of the material will be
severely compromised. With this in mind, molybdenum sul-
phides were investigated, primarily as an anode catalyst for the
hydrodesulphurisation of natural gas.[185] A MoS2 framework
was impregnated with gold nanoparticles to prevent CO poi-
soning when using syn-gas.[186] Despite this, fuel cell perform-
ance was observed to degrade over time which was attributed
to sintering of the gold nanoparticles. Addition of Ni3 ± xS2 was
used to reduce the volatility of MoS2 in air by preventing MoO3
formation, however, despite promising fuel cell performance,
significant reductions in performance were noted, ascribed to
nickel sulphide agglomeration.[187] Further investigation into
Anode Performance Reference
Temperature (°C) Fuel
- 800 10% H2/N2 [167]
- 800 H2 [160]
- 800 5% H2S/N2 [165]
- 800 H2 [152]
- 800 Humidified 5% H2/Ar [46]
- 900 5% H2S/N2 [166]
- 800 H2 [229]
- 800 5% H2/Ar [54]
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transition metal sulphides found that MoV2S4 demonstrated low
polarisation resistance of 1.5 Ωcm2 at 800 °C in a H2S stream
with stable operation observed over 3 days.[188] The utilisation of
these materials as H2S catalysts in conventional fuel cells might
be viable, although it would be more practical to use these sys-
tems, when efficient, as to remove the H2S from the fuel prior
to use in a conventional SOFC. This could be applied in the
same way as an internal reforming layer, such as Cu1.3Mn1.7O4
which improved both stability and performance of a Ni/SDC
anode operating with methane fuel.[189]
5. Fuel Considerations
One of the main advantages to the use of SOFCs is the
sheer variety of different fuels that can be utilised. Alongside
hydrogen, methane,[190] ethane,[191] propane,[149] butane,[192]
ethanol,[193] methanol,[193] dimethyl ether[194] and ammonia[195]
have all been investigated as to their efficacy as SOFC fuels.
Many of these show reduced performance when compared to
pure hydrogen, however direct utilisation of these fuels would
be a major advantage due to the higher energy storage den-
sity and lesser associated problems concerning storage and
transportation.
One main difficulty associated with the use of hydrocarbon
fuels is coking, carbon deposition upon fuel oxidation, which
can cause significant degradation to anode performance.[28]
In some cases the use of steam reforming, addition of water
vapour to the fuel gas, can be used to partially alleviate this
effect.[196]
While the use of these fuels and other similar fuel mixtures,
such as coal derived syngas, is eminently desirable, it does
present further problems to anode development, as these gases
contain various impurities which have been found to have a det-
rimental effect on SOFC performance.[197,198] As is also found
for hydrogen, sulphurous impurities can be found in various
hydrocarbon gases and a substantial amount of research has
been conducted on the deleterious effect of these compound on
fuel cell anode performance.[199]
The presence of chlorine, arsenic and phosphorous based
compounds, which have all been detected in coal-derived
syngas, have also been found to interfere with the current Ni/
YSZ anodes through formation of Ni-impurity compounds.[197]
Previous results were found to conflict on the effect of HCl on
fuel cell performance,[200] although recent research by Marina
et al.[201] convincingly demonstrated that fuel cell performance
at intermediate temperatures showed reversible degradation up
to 100 ppm HCl, with no further effect on fuel cell performance
observed with increasing HCl concentrations. The presence of
a lesser concentration of arsenic impurities was found to cause
observable anode degradation, with 10 ppm of AsH3 causing a
10% drop in fuel cell performance at 750°C[202] and even lower
concentrations of 1 ppm and 0.1 ppm show gradual degrada-
tion over 600 h.[203] Irreversible degradation is observed upon
exposure to PH3, through microstructural changes caused by
the formation of both Ni3(PO)4 and Zr2P2O7.[204]
Degradation of anode materials by syngas impurities is not
limited to nickel-based cermets, as irreversible degradation of a
LSCF-GDC composite at 800 °C was found for phosphine levels
Adv. Energy Mater. 2011, 1, 314–332 © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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as low as ∼1 ppm.[6] The surface formation of both LaPO4 and
REVIEW
FePx suggests that further investigation into the effect of phos-
phine impurities will be necessary before syngas is considered
for long term use with current alternative SOFC anode mate-
rials. Previously the stability of LSCM to sulphurous impu-
rities was called into question[5] with the formation of MnS2,
La2O2S and α-MnOS observed upon exposure to 10% of H2S
at 950 °C. Additionally, despite studies showing the stability of
metal-LSCM-YSZ composite anodes to coking, further inves-
tigation by Kin et al.[205] determined that the addition of ceria
is required to completely prevent carbon deposition. For both
palladium and nickel composite anodes a weight increase of
10% was observed upon exposure to methane for 24 hours at
800 °C, reduced to < 3% upon ceria addition. These studies do
bring into question the stability of LSCM based anodes at high
concentration of H2 S during long term fuel cell testing with
commercial and hydrocarbon fuels.
6. Fabrication Methods
The fabrication method is essential in determining the prop-
erties of the anode material through microstructural devel-
opments. Many of the same techniques detailed in previous
reviews[25,69] are still in use today, with both screen printing and
tape casting the most widely used. Much of the conventional
techniques can be described as ceramic powder processing
methods, which utilise previously prepared powders with a
variety of binders and pressing techniques to form pellets.
These techniques require a high temperature sintering step
to form materials with the required microstructure, which can
introduce a large amount of undesirable defects.
There are a variety of alternative techniques which specialise
in forming thin anodes such as atmospheric plasma spray
(APS),[206] vacuum plasma spraying (VPS),[207] electrochem-
ical vapour deposition (EVD)[208] and laser reactive deposition
(LRD).[209] The high initial cost of equipment for many of these
alternative techniques does, somewhat, limit their use, although
APS is the exception in that it does not require sophisticated
apparatus and a controlled atmosphere.
Infiltration of materials into a ceramic support has found
favour as an integral technique for introducing catalytic pro-
moters, such as palladium,[56] rhodium[131] and ceria.[142] The
amount of the material infiltrated tends to be small, negating
any possible losses in porosity, and has been shown to coat the
surface of the ceramic support with nanoparticles, with the cor-
rect firing temperatures. Infiltration of an electronic conductor
onto an ionic conducting support was found to give promising
results, although sequential infiltration of separate components
was found to be less successful than single infiltration.[139]
Atkinson et al.[210] found that infiltration of nickel in a porous
YSZ can effectively enhance the dimensional stability of anode
thus the redox stability. The synthesis method used in forming
the anode can have a noticeable effect on the particle size dis-
tribution hence the preference for wet-chemical techniques,
which produce smaller sized particles with a higher uniformity
than solid techniques, in the production of anode materials.
The particle size of the powder precursor for anode fabrica-
tion will have a profound effect on anode microstructure. Kwon
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et al.[211] determined that a powder precursor prepared by spray
REVIEW
drying–with a nano-sized phase distribution–used in APS gave
superior conductivity, hardness and microstructural uniformity
than a blended analogue.
Ball milling of the powders post-fabrication of the anode is
a frequently utilised technique to control the particle size. Li
et al.[212] used a novel self-rising synthesis technique to form
Ni-SDC, utilising PVA and urea to form porous metal oxide
powders with a low filled density, which used both a one
step method from the metal nitrates and a separate method
which included a ball milling step. The fuel cell with the ball
milled anode exhibited consistently superior performance to
that without, nearly doubling the maximum power density at
600 °C.
The anodic porosity is important to take into account as this
will control the mass transport within the anode and thus will
significantly affect the fuel cell performance. The porosity of
these materials can be regulated through changes in sintering
temperatures and the use of pore formers such as starch and
graphite. Suzuki et al[213] ably demonstrated the effect of sin-
tering temperature on the microstructure of the anode, with
increasing sintering temperature reducing the anode porosity.
Corbin et al.[214] investigated the effects of structure of Ni/YSZ
cermet on conductivity and thermal expansion coefficient and it
was found that fine scale porosity will have a more detrimental
impact on conductivity compared to a coarse porous structure.
However, Suzuki et al.[215] report a correlation between the
microstructure of the anode electrode of a SOFC and its elec-
trochemical performance for a tubular design. It was shown
that the electrochemical performance of the cell was extensively
improved when the size of constituent particles was reduced so
as to yield a highly porous microstructure.
Despite exhibiting lower conductivity, the anode with the
highest porosity, 57% pre-reduction, was found to demonstrate
the highest fuel cell performance, 1.1 Wcm−2 at 600 °C, par-
tially due to the increased gas diffusion and the smaller nickel
particle size. An increase in performance was also noted when
using a porosity graded anode,[216] although it must be noted
that the increase was small compared to that noted by Suzuki,
partially due to the lack of optimisation of the FC and the small
increase in porosity with each 10μm thick functional layer. The
opposite effect was noted when using pure ceramic anodes,[75]
a LST-YSZ composite, where a reduction in the porosity from
50% to 30% increased the fuel cell performance from 0.2 Wcm−2
to 0.23 Wcm−2. This effect is likely due to the lower electronic
conductivity compared to Ni/YSZ cermets and thus electronic
conduction through the anode is likely to limit the performance
to a greater extent than mass transport effects.
7. Conclusions
A significant amount of research has been conducted in this area
in the short span since the last full scale review in 2007, with
improvements noted for both cermet and cermet-alternative
materials. Despite this increase in fuel cell performance much
of the progress has been made through alterations of the syn-
thesis route and incorporation of catalysts rather than the devel-
opment of significant new materials.
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Viable performance of cermet anodes, generally considered
to be 0.5 Wcm−2, is in the range of 600 °C to 800 °C and occurs
for a wide variety of different materials. The main disadvan-
tages, coking and poisoning by sulphurous impurities, still
remain for a majority of cermet anodes, yet newly developed
anodes, such as Ni-Fe alloys, have shown promising improve-
ments in this area. The redox stability of these compounds can
still be called into question, although this can be somewhat
neutralised using modern processing techniques.
For composite ceramic anodes only a small proportion of
the materials reach reasonable fuel cell performance and at a
higher temperature, ∼800 °C, than is found for cermet anodes.
The role of catalysts in these materials has been shown to be a
major factor in fuel cell performance, with huge improvements
in fuel cell performance upon infiltration of a small amount of
anode catalyst. The effect of impregnation of both the anode cat-
alyst and the electronic conducting phase has also been proven
to be a useful technique for improving fuel cell performance,
increasing the TPB whilst retaining the maximum surface cata-
lytic active sites.
While progress in the improvement of anode performance
has been made, there is still scope for further enhancement.
The stability of cermet anodes when using hydrocarbon fuels is
still not ideal while for cermet-alternatives demonstrate insuf-
ficient fuel cell performance at lower temperatures. Recent
alloys for cermets have been developed which show prom-
ising stability to coking while for alternative materials an area
of interest for future research will be various mixed transition
metal-molybdenum oxides. Both fields have exhibited signs
that future research could provide solutions to both of these
problems, creating further potential for commercialisation of
this technology.
Acknowledgements
We would like to thank EPSRC for funding. One of the authors (Cowin)
thanks ScotChem SPIRIT scheme for a PhD studentship.
Appendix 1. Glossary of Abbreviations:
APS, Atmospheric plasma spray
ASD, A-site deficient
ASR, Area specific resistance
BSD, B-site deficient
EPD, Electrophoretic deposition
DFT, Density functional theory
FC, Fuel cell
GDC, Gadolinium doped ceria–Electrolyte–GdxCe1-xO2
LCO, Lanthanum doped ceria–LaxCe1-xO2
LSCF, Perovskite cathode–La0.6Sr0.4Co0.8Fe0.2O3-d
LSCM, Perovskite anode–La0.75Sr0.25Cr0.5Mn0.5O3-d
LSCNi, Perovskite anode–La0.75Sr0.25Cr1-xNixO3-d
LSCRu. Perovskite anode–La0.75Sr0.25Cr1-xRuxO3-d
LSGM, Perovskite electrolyte–La1-xSrxGa1-yMnyO3-d
LSSM, Perovskite cathode–La0.8Sr0.2Sc0.2Mn0.8O3-d
LST, Lanthanum doped strontium titanate–Anode–Sr1−x
LaxTiO3
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MIEC, Mixed ionic electronic conductor
Metal/Electrolyte, An anode cermet comprising of a metal and
ceramic electrolyte
PEMFC, Polymer electrolyte membrane fuel cell
pO2, Partial pressure of oxygen
Redox, Reduction and Oxidation
Rp, Polarisation resiatance
ScSZ, Scandium doped zirconia–Electrolyte–ScxZr1-xO2
SDC, Samarium doped ceria–Electrolyte–SmxCe1−xO2
SMMO, Perovskite anode–Sr2Mg1−xMnxMoO6
SOFC, Solid oxide fuel cell
STO, Strontium titanate–Anode–SrTiO3-d
TEC, Thermal expansion coefficient
TPB, Triple phase boundary
TPR, Temperature programmed reduction
YST, Yttrium doped strontium titanate–Anode–Sr1−xYxTiO3
YSZ, Yttrium stabilised zirconia– Electrolyte–YxZr1−xO2
Received: March 5, 2011
Published online: April 15, 2011
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