Renewable and Sustainable Energy Reviews 51 (2015) 18

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Renewable and Sustainable Energy Reviews

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

A review on the selection of anode materials for solid-oxide fuel cells

Shabana P.S. Shaikh n, Andanastuti Muchtar, Mahendra R. Somalu
Fuel Cell Institute, Universiti Kebangsaan Malaysia (UKM), 43600 Bangi, Selangor, Malaysia

art ic l e i nf o a b s t r a c t

Article history: Solid-oxide fuel cells (SOFCs) are the most widely used fuel cells because they exhibit exibility, power
Received 12 September 2014 generation efciency, and low pollution formation. Research on SOFC anodes is a major and challenging
Received in revised form task in the eld of SOFCs. This review highlights the anode materials that may be used for SOFC
3 May 2015
applications. The use of cermet-based oxide materials as anodes for SOFCs is also discussed in detail. A
Accepted 26 May 2015
Available online 18 June 2015
literature survey conducted over the last 10 years shows that increased power generation efciency may
be attributed to anode materials used in such cells. Oxide-based anode materials with perovskite and
Keywords: several oxides with cubic uorite structures are further described. Based on the review conducted, we
Mixed ionicelectronic conductor (MIEC) nd that cubic uorite-structured compounds are the most promising anode materials reported thus far.
Anode
Analyses of the structure and electrical performance of anode materials show as well that copper
Cermet
gadolinium-doped cerium oxide (CuGDC) cubic uorite-structured anodes exhibit higher electronic
DC conductivity
Symmetric cell conductivity potential than yttria-stabilized zirconia-based anode materials.
Solid-oxide fuel cell (SOFC) & 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2. Common anode materials for SOFCs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. Potential alternative anode materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1. CuCeO2 cermets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2. NiCGO cermets. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.3. CuNiCGO cermets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.4. CuCGO cermets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.5. Summary of anode performance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

1. Introduction Currently, many scientists, researchers, and engineers around the

Solid-oxide fuel cells (SOFCs) are the most widely used alter-
native energy sources and power-generating devices that are
expected to yield highly efcient energy using hydrocarbon and
fossil fuels. SOFC technology is used to produce electricity with
negligible amounts of pollution and is thus an environment-
friendly energy-conversion method of producing electrical energy
with a high efciency of approximately 60% [1].
n
Corresponding author. Tel.: 603 89118534; fax: 603 89118035.
E-mail address: shabanamsrl@gmail.com (S.P.S. Shaikh).
globe are showing keen interest in commercializing fuel cell technol-
ogy. Thus, one of the most popular and innovative sources of
renewable energy for the future is the hydrogen economy. The
regenerative fuel cell might be the answer that hydrogen economists
are looking for. It produces an electrical current through an electro-
chemical reaction between hydrogen and oxygen at a porous
electrode (anode and cathode) interface, by completing an electrical
circuit with the emission of the harmless byproduct, water. Unlike a
battery, SOFCs more efciently generate electricity up to 100 kW,
compared with other types of fuel cells through the internal
reforming process, as long as the fuel is provided to the electrode
externally. SOFC can work at intermediate as well as high tempera-
tures within the range of 7001000 1C with 60% efciency [2].

http://dx.doi.org/10.1016/j.rser.2015.05.069
1364-0321/& 2015 Elsevier Ltd. All rights reserved.
2 S.P.S. Shaikh et al. / Renewable and Sustainable Energy Reviews 51 (2015) 18

At such high temperatures, there is no need for a separate
reformer to extract the hydrogen from the fuel in SOFC technology.
Since SOFC can be used as a cogeneration system for home use, the
major issue for commercialization is to balance the reliability and
durability with a low cost.
Globally, many researchers are studying to commercialize SOFC
to solve the energy problem in near future, as high temperature
SOFCs showed high efciency. During the literature survey, a few
case studies were observed for SOFC technology as follows:
1. Tokyo Gas worked to develop cell stack performance to its
maximum possible extent in order to prepare for the early
stage of the commercialization of SOFC[3].
2. Fuel Cell Energy developed a direct fuel cell of 250 kW products in
corporation by launching its rst commercial unit in 2003, which
was already operating at more than 50 stations. These units are
now operating at more than 50 services worldwide [4].
3. Wellington states that the fuel cell, which received nancial
backing from Global Energy's (GE's) Ecomagination program,
could generate electricity at any location with a supply of
natural gas. It could start up quickly, did not need new
transmission lines, and produced lower emissions than con-
ventional power plants [5].
The high temperature SOFC showed tremendous promise, with
high efciency and low pollution, for a wide range of applications.
Now, SOFCs are in demand as they are very clean and pollution
free with a high efcacy of 6065%, and a low cost compared with
solar and wind energy. The fuel cell can be used to generate energy
for small to medium scale stationary appliances, and is tolerant to
carbon monoxide and sulfur impurities.
The advantages above validate the interest for the fuel cell in
high as well as intermediate temperature as the next generation of
electric and thermal products. However, due to its high cost, it is
difcult to commercialize in many applications such as residential,
industrial, transportation, and stationary. Recently, many scientists
have used stainless steel in place of platinum, as a rare metal like
platinum is very expensive. As a result, fuel cell technology is
difcult to commercialize. Thus, there is need to search for
economical friendly and alternative anode materials that can act
as a catalyst in SOFCs [6]. SOFCs consist of three major layers that
are composed of ceramic materials such as cathodes, electrolytes,
and anodes. The electrolyte is a dense layer of ceramic oxide
material, and anode/cathodes are both porous electrodes. It is
urgent to conrm the high durability, reliability, and low cost of
SOFCs for commercialization. Therefore, in this review, the authors
attempted to identify issues regarding the conrmation of relia-
bility of SOFCs through various evaluating parameters, fundamen-
tal properties, and advanced synthesis techniques for different
anode materials for SOFC, to commercialize it at an early stage by
reducing its manufacturing cost.
Compared with solar cells and wind energy, SOFCs are a
cheaper, durable, and reliable source of energy. In addition, SOFCs
emit negligible amounts of greenhouse gases, which reduce
pollution and improve the environment. According to the litera-
ture survey, it was observed that in the last few years, the cost of
the fuel cell unit declined from approximately $8000/kW in 2004
to $4800/kW in 2006. Still, globally, many scientists and research-
ers are attempting to further reduce the manufacturing cost of the
SOFC unit by searching for new electrode materials and low cost
synthesis techniques. Thus, it was observed that SOFCs have a key
disadvantage of high cost. As a result, it is the main objective of
researchers to minimize the manufacturing cost by selecting
economical synthesis techniques and suitable alternative catalytic
anode materials, which can work at lower as well as intermediate
temperatures.
A number of companies such as Acumentrics, General Electric,
Ion America, Rolls Royce, and Siemens Power Corp. are trying to
lower the cost to commercialize SOFCs by developing new anode
and cathode materials for the SOFC stack. From this review it is
observed that, SOFC techniques might be needed $0.024/kW for
the operation and its maintenance with production cost of $2850/
kW. According to Fuel Cell Energy (FCE) of Danbury, Connecticut,
additional hydrogen can be produced within the fuel cell stack, in
which hydrogen and electricity can be coproduced using methane
or natural gas as a fuel at the anode site. With reference to Table 1
[7], few companies believes that they could offer a 50% reduction
in operating cost compared with the more conventional unit,
using a novel electro-chemical hydrogen separation unit with
68% of hydrogen production efciency [3], so that hydrogen can
be used in transportation and industrial applications [3].
According to a survey conducted by Bloom Energy Fuel Cells,
the solar cell has a number of major disadvantages; the cost of
solar cell is very high compared with SOFCs, and solar energy can
only generate electricity during the daytime. Weather can also
affect the efciency of solar energy, and the pollution produced is
higher compared with SOFCs [8]. Table 2 shows the advantage and
disadvantages of solar energy, wind energy and Fuel Cell Energy
techniques [3,9,10].
Several researchers have improved the performance of
intermediate-temperature SOFCs (IT-SOFCs) by enhancing the
structural, mechanical, and electrical properties of the electrode/
electrolyte interface in anode symmetric cells. Previous studies
published over the last 10 years have described anodes, where fuel
oxidation takes place, as basic components of SOFCs. Selecting the
appropriate anode materials is signicant to improving the elec-
tronic conductivity of single cells in IT-SOFCs.
An anode is a charged porous electrode in an electrical circuit.
This electrode functions as an actively charged pole that facilitates

Table 1
Estimated cost of hydrogen production by different methods.

Sources for hydrogen Hydrogen production method Hydrogen production

production cost

Natural gas SOFC Internal steam reforming method $1.47 per kg

Biomass(Syngas) Thermo chemical and bio chemical $57 per kg
process
Coal Gasication process $2.002.50 per kg
Water Electrolysis method $67 per kg
methanol Steam methane reforming $25/kg [Ref]
Distributed wind Electrolysis $7.26 per kg

*References are mentioned in main text. Cost will be varying with respect to synthesis technique.
 S.P.S. Shaikh et al. / Renewable and Sustainable Energy Reviews 51 (2015) 18 3

Table 2
A comparative study of advantage and disadvantage of different energy generation techniques.

Sources of energy technique Advantages Disadvantages

Solar energy  Available naturally  Efciency falls with increase in equator distance
 No noise  Bad weather affects the generation of power
 No moving parts  Highly expensive
 Less pollution  Unable to use for industrial applications
 Excess energy can store in batteries
 Reliable source of energy

Wind energy  No pollution  Very low efciency

 Use in remote areas
 Generate electricity for small application for e.g. home

Solid oxide fuel cell technology
 Mechanically strong  Require longer start-up time
 Inexpensive component materials  Less chemical stability
 Operate at high as well as intermediate temperature
 Tolerant to sulfur and CO poisoning
 High energy output efciency
 Long term stability
 Fuel exibility
 Low emission
 Low cost
 Suitable for stationary and medium to large scale application
 Low maintenance

*References are mentioned in main text.

and strategies for developing and optimizing SOFC anode materials

Fig. 1. Operating principle of SOFCs.
electron ow within and outside a circuit. Electrons ow from a
cathode to an anode inside a cell, and vice versa, outside a cell [11].
Anodes can assist in hydrogen adsorption and oxidation during
fuel ow by allowing oxygen ions from an electrolyte compart-
ment to combine with hydrogen, thereby forming H2O and
liberating electrons to an outer circuit, as shown in Fig. 1.
An anode must meet most requirements applicable to cathodes,
such as adequate electrical conductivity, thermal expansion compat-
ibility, and porosity. In addition, an anode must produce a reducing
atmosphere. The anode acts as a catalyst for steam, reforming the
fuel into hydrogen. These characteristics, combined with electrical
conductivity requirements, are exhibited by cermets. Thus, they are
attractive candidates as anode materials. Distinct challenges caused
by high temperatures encountered by SOFCs have been reported.
These problems are related to material degradation, particularly of
the mechanical and chemical stabilities of an anode in a highly
reducing atmosphere [12]. Anode materials also require compatible
properties, including shrinkage during sintering and thermal expan-
sion. These properties are necessary to minimize stress during
temperature variations caused by operating procedures, such as
startup and shutdown [13].
Several parameters are considered when selecting alternative
anode materials for SOFCs. Recent studies have discussed directions
[11]. Available studies have determined backgrounds, characteristics,
synthesis techniques, and various processing parameters that
improve the performance of SOFCs. Therefore, the current review
explains in detail the selection of efcient materials as anodes for
SOFCs. Literature selection was based on advanced synthesis techni-
ques and the high performance exhibited by SOFCs.
Cermet-based materials and alternative conducting oxide
materials for SOFCs are the most widely used. Such anode
materials must be electro-catalytically active, with low over
potential loss, high current density, ne microstructure, and high
electronic conductivity [12]. Cermet anodes possess structural and
electrical properties that are more enhanced than other anode
materials because the former operates at intermediate tempera-
tures. Since the cermet based anode materials are less expensive to
synthesize by using the nitrate-process in the lab itself with more
improved structural and electrical properties, several researchers
have focused their attention on lowering the operating tempera-
ture of SOFCs by developing new cermet anode materials. The
approximated cost for the manufacturing of anode for SOFC's is
observed to be in the estimated range of $150$300 based on the
materials and the synthesis technique used [14].
2. Common anode materials for SOFCs
One of the most important components of SOFC is the anode, and
it must catalyze the reaction of the fuel with O2 from the electrolyte
and conduct the electrons produced in the electrochemical reaction
to the external circuit according to the following oxidation reaction:
H2 O2  H2O 2e-
It provides the reaction site to carry out the electrochemical
oxidation process of the fuel supplied to the anode [15]. The anode
must possess important properties such as high electrical con-
ductivity, thermal expansion coefcient matching, and capacity to
prevent coke formation at reaction site, ne particle size with
nanostructure, chemical compatibility with electrolyte, large triple
4 S.P.S. Shaikh et al. / Renewable and Sustainable Energy Reviews 51 (2015) 18
phase boundary, high porosity, and good electronic and ionic
conductivity [8].
Common anode materials are traditional materials that have been
used for a long time despite exhibiting poor performance. Over the
last few years, improvements in anode material properties have been
addressed by selecting new materials. Few materials are used as
anodes for high-temperature SOFCs [13]. Iron based anodes undergo
corrosion caused by red Fe oxides. Thus, this anode material is no
longer protected by the reducing activity of a fuel gas when the
partial pressure of oxidation products exceeds a critical value in an
anode compartment of an operating cell. Cobalt is stable as an anode,
but is expensive. The use of this element in anodes increases SOFC
costs and promotes causes carbon formation [13].
Nizirconia cermet anodes, which were rst introduced by Liu
et al. [16] in 1995, are also widely used as anode materials for SOFCs.
NiYSZ anode composites are receiving considerable attention as
standard anodes for SOFCs. Ordinarily, the thermal expansion of Ni
mismatches that of stabilized zirconia at high temperatures [17].
However, Ni particles aggregate and reduce the porosity of an anode
by eliminating the triple-phase boundary (TPB) required for cell
operation, thereby decreasing cell performance.
High TPB lengths provide low polarization resistance. In pre-
viously published articles, NiYSZ did not improve anode perfor-
mance because of carbon deposition, which coats Ni particles
when an insufcient amount of water is added to the system [18].
A pioneering research performed by the Westinghouse Electric
Corporation developed NiYSZ cermet anodes to enhance the
compatibility of thermal expansion coefcients between anodes
and YSZ electrolytes. YSZ is electronically insulating; therefore, Ni
phases in the cermet must be present in concentrations high
enough to allow a complete conducting pathway through the
anode. The percolation threshold, which is the common name of
this parameter, has been studied in a number of systems. This
characteristic normally occurs at approximately 30 vol% of the
conducting phase. Studies on balancing thermal expansions and
achieving sufcient conductivity have led to the development of
anodes with Ni concentrations of 40  60 vol% [19].
Ni promotes carbon formation. Anode materials used in SOFC
prototype demonstration units have typically been limited to NiYSZ
cermets to achieve the necessary electrical performance and stability
under H2/O2 fuel conditions. Anode specications have changed as
fuel requirements are increasingly focusing on hydrocarbon fuels
with low steam ratios. Discussions on anode materials have high-
lighted direct oxidation of hydrocarbon fuels at the anode. Traditional
Ni-based cermets are unsuitable in this process due to carbon
deposition. The usual method of producing NiYSZ cermets involves
calcining mixed powders of NiO and YSZ to set up channels for ion
conduction in YSZ. NiO is then reduced to Ni metal to achieve
porosity. YSZ is densied at temperatures of at least 1300 1C, higher
than the temperature range usually applied in CuYSZ. Thus, the
performance of lanthanum chromite (LaCrO3) anodes is poorer than
that of NiYSZ cermet anodes. NiYSZ cermets as anode materials
have been extensively studied only for high-temperature SOFCs [20].
This material remains the most promising anode material for
hydrogen conversion [21], but exhibits properties that are highly
dependent on particle size, porosity, and microstructure of the nal
electrode [2224]. Anode porosity affects the fuel supply and reaction
product removal in SOFCs.
Thus, despite its many advantages, due to low sulfur tolerance
and carbon deposition in Ni/YSZ composite, there is degradation in
its performance and hence it is not a not a good choice of selection
as an anode for SOFC. Thus there is need to search alternative
cermet based anode to solve these problem. It is observed that the
ceramics are the best mixed electronic and ionic conductor under
the reducing atmosphere as an anode. Also they possesses excel-
lent catalytic activity for the hydrocarbon fuels and are resistant to
carbon deposition which in turn allows the direct supply of fuel to
the anode[1].
It has been emphasized by Sun et al., 2006 as cited in Sun et al.
[41]. Thus, alternative porous anode materials for SOFCs must be
developed. Though these are the most commonly used anode
material for SOFC, many scientists and researchers have recently
begun searching for alternative composite anode materials such as
Cu, Co, and phosphorous cermets [15]. As Ni/YSZ is not a good
choice of selection as an anode material for SOFC, there is a need
to investigate alternative anode materials that can operate at low
operating temperatures.
LaCrO3, CrTi2O5, and Ti0.34Nb0.66O2 are not suitable anode
materials as they exhibit weak mechanical strength and lattice
expansion in reducing atmospheres in hydrocarbons [25,26]. Thus,
little research [27] has attempted to replace La and Cr with Sr and
titanium, to develop strontium titanate (SrTiO3)-based anode
materials. These materials exhibit n-type instead of p-type con-
ductivity in reducing atmospheres with size changes [19]. Thus,
the overall performance of LaCrO3 anodes is poor compared with
other anode materials.
Direct electrochemical oxidation of various hydrocarbons, such
as methane, ethane, 1-butene, n-butane, and toluene, at 700 and
800 1C has been reported. Pudmich et al. [19] and other research-
ers, such as Yano et al. [28], demonstrated that several perovskite
based on LaCrO3, and SrTiO3 can be used as anodes in SOFCs. These
researchers have found that perovskite containing lanthanides and
those partially substituted by alkaline-earth elements and transi-
tion metals (such as Cr, Ti, Fe, and Co) show extremely wide-
ranging physical properties. Titanium-rich anode materials exhibit
high conductivity [19,28], while Cr-rich samples show low con-
ductivities under reducing conditions. Impedance measurements
also show that La0.7Sr0.3Cr0.8Ti0.2O3 perovskite electrodes are
active toward hydrogen oxidation.
Other titanates considered as potential anode materials for
SOFCs consist of A-sites without lanthanides, such as neodymium
and praseodymium [29], and Fe-doped barium TiO3 [30]. The
electro-catalytic performance of SOFC anodes must be high. Thus,
the addition of ruthenium [31] or Ni [3234] in small amounts is
often performed to increase the electro-catalytic performance of
these anodes.
Lanthanides, yttrium (Y) [3538], and transition metals, includ-
ing Co, Cr, Fe, Ni, and Cu, that can replace Sr have been doped in
LaTiO3 or SrTiO3 [39]. The factors described above reasonably
explain the degradation of performance of La, Cr, Ti, Fe, Co, Ni,
zirconium oxide, and Y-oxide transition metal-based anode mate-
rials at temperatures Z1000 1C [40]. Currently, ceria and doped
ceria are commonly used as components in cermet anodes for IT-
SOFCs [13,1519].
From the review of recent articles, it was found that composite
cermet with YSZ such as CuNi/YSZ, (Cu, Co, Fe) NiYSZ, (Ni, Co)
YSZ, (Ni, Fe)YSZ, (Ni, Cu)YSZ, and (Cu, Co)YSZ are also unsui-
table as the power density of YSZ is lower than that of some metal
elements. Therefore, to increase the stability and chemical com-
patibility of the anode, many researchers have tried to make
composite anode, namely CuCGO and CuNiCGO, as an anode
with better performance than existing conventional anode mate-
rials for SOFC [41].
CuCGO and CuNiCGO anodes exhibit mixed ionic and elec-
tronic conductivity. It was found that more potential anode materi-
als can be prepared by using low-cost and less time-consuming
synthesis techniques such as the microwave assisted glycinenitrate
process[1,42]. CeO2 based anode materials show efcient catalytic
activity and good electronic conductivity due to the reduction of
Ce4 to Ce3 . In addition, Cuceria based anodes have high
resistance to carbon deposition, which permits the direct supply
of hydrocarbon fuel to the anode [43].
 S.P.S. Shaikh et al. / Renewable and Sustainable Energy Reviews 51 (2015) 18
Thus, there is still a need to improve the anode performance of
SOFC. The thermal expansion coefcient of Nickel (16.9  10  6 K  1)
is much larger than that of YSZ (11.0  10  6 K  1). As a result, the
ionic conductivity of the material increases [44,45]. However, in Cu/
CGO, CuNi/CGO anode cermets show excellent performance with
high ionic and electronic conductivity and a good thermal expansion
coefcient that strongly inuences the area specic resistance of the
anode. The performance of the anode cell also depends on other
parameters such as metal composition, sintering temperature, thick-
ness, grain size connectivity of particles in composite, microstructure,
porosity, and triple phase boundary length. Therefore the best
solution is to improve the performance of SOFC by using alternative
composite anode materials at intermediate temperature.
3. Potential alternative anode materials
Alternative anode materials can resist sulfur poisoning and carbon
deposition. Cermet-based anode materials have gained signicant
research attention in recent years. Cucerium (II) oxide (CeO2), Ni
(CGO), CuNiCGO, and CuCGO anodes are potential alternative
anode materials for SOFCs at intermediate temperatures.
3.1. CuCeO2 cermets
Cu increases the electronic conductivity of anode materials for
SOFCs. Thus, several researchers have attempted to replace Ni with
Cu, which is an inert metal. Cu resists coke formation while the
SOFC is in operation.
Cubic uorite-structured cerium oxide plays a major role in
reducing the operational temperature of SOFC. Cermet anodes
behave like mixtures of electronic and ionic conductors as the
Ce4 phase is reduced to the Ce3 phase in a reduced atmosphere.
This reduction results in an irreversible formation of oxygen ion
vacancy and the migration of ions, which are associated with the
transformation of CeO2 into Ce2O3. These CeO2-based materials
exhibit excellent catalytic activities [41,46,47].
Studies on the requirements necessary to develop high-
performance anodes have been reported. Doped cerium dioxide,
Ce(1 x)MxO2 (where Mrare earth element), has been considered
as an alternative to YSZ because it presents conductivity that is four
to ve times higher than that of YSZ. Ceria doped with trivalent
cations exhibits high oxygen ion conductivity. Thus, this compound is
a leading electrolyte candidate for SOFCs operating at a temperature
range of 500 700 1C. This material exhibits a uorite-type structure
[48]. The highest level of oxide ion conductivity among ceria-based
ionic conductors has been observed in characteristic solid solutions
of Ce(1 x)MxO2 at 800 1C [49,50]. Steele [49,50] reported that
electrode materials with low grain boundaries and high lattice
conductivities are more appropriate than those with high grain
boundaries and low lattice conductivities for SOFCs. Increases in
average grain size decrease grain boundary contributed to total
conductivity. Similarly, the microstructural features of alternative
anode materials, including their porosity, nature of grain boundaries,
and grain size, affect lattice conductivity.
3.2. NiCGO cermets
NiCGO is another alternative candidate material for use in
SOFC anodes. The introduction of Ni to doped ceria matrices
generates sufcient electronic conductivity to prevent electrical
losses. Thus, cermets based on doped ceria are preferable for
achieving high electrode performance.
In a NiCGO matrix, oxygen ions are supplied by CGO particles.
These CGO particles prevent sintering of Ni particles and match
the thermal expansion coefcients between the cermet and a CGO
5
electrolyte. The electrical performance of a NiCGO cermet
depends on the percolation theory, wherein the microstructure
of an anode material is believed to affect its performance. Ni
particles in a cermet must be connected to CGO particles and must
be exposed to H2 gas.
Ni cermets have been used as anodes for SOFCs due to their
high electronic conductivity and catalytic activity. However, at
temperatures 4700 1C, coke is formed as anodes are fully covered
by carbon threads at these temperatures [51,52]. SOFCs with
conventional Ni-based anodes are unstable in hydrocarbon fuels
because Ni exhibits a tendency to catalyze carbon formation
[52,53]. In these fuels, carbon formation is unavoidable when Ni
is present. NiYSZ is used with inexpensive compatible intercon-
nections, such as stainless steel or metal alloy, as an anode for
SOFCs; use of this material is suitable for low and intermediate
operating temperatures [54]. Reasonable improvements in SOFCs
are achieved by reducing the working temperature. This process is
performed by deploying a novel anode and enhancing the struc-
tural organization of grains; improvements obtained allow the
resulting cell to efciently utilize hydrocarbon fuels [55].
3.3. CuNiCGO cermets
Several Cu-based anodes have been tested [56]. Results have
demonstrated that Cu is highly resistant to carbon formation. From
2000 to 2012, preliminary results of a study on Cuceria anodes
prepared using multiple synthesis techniques were reported [14,57].
Compared with Ni anodes, Cuceria anodes exhibited improved
stability under coking conditions. Moreover, these anodes performed
adequately in hydrogen and dry hydrocarbons. Cuceria anodes
showed stable performance in all cases. The roles of Cu and ceria
in Cuceria anodes became clear after McIntosh et al. [58] and Lu
et al. [59] published their respective studies. These studies showed
that Cu behaves only as an electronic conductor. In addition, Cu does
not catalytically affect an electrochemical oxidation, while ceria
improves electro-catalytic and/or ionicelectronic conductivities.
McIntosh et al. [60], who explained the role of carbon deposits in
enhancing the performance of Cuceria anodes, found that initial
coking improves the connectivity of the metallic phase; this behavior
is achieved through increasing triple phase boundary (TPB) length.
Cuceria anodes were previously tested on other electrolytes,
such as samaria-doped ceria (SDC) [61]. Results obtained from these
studies conrmed the stability of the anode toward carbon deposi-
tion. The main limitations of Cuceria anodes included the sintering
of Cu and the low thermal stability of ceria. Cu is inert toward
hydrogen or hydrocarbon oxidation and presents no catalytic activity
during CC bond formation. Thus, carbon deposition is prevented.
Ceria catalysts have been added to CuYSZ cermets to improve the
electrode activity of the resultant materials. The performance of the
resultant CuCeO2YSZ anodes signicantly improved after these
anodes were exposed to hydrocarbon fuels, particularly anodes with
Cu contents o30 vol%. Compared with other transition metals, Cu is
relatively inexpensive. In addition, the melting temperature of Cu is
1083 1C, which is lower than that of Ni (1235 1C). However, Cu is only
stable when used during low-temperature operations (o700 1C).
Thus, Cu-based anodes are suitable for operating temperatures
o800 1C. Other experiments using ethane reveal that coking pre-
sents issues in Niceria anodes [62]. Therefore, this type of anode is
not suitable for higher hydrocarbons [63].
The glycinenitrate process (GNP) is the most commonly used
process in synthesizing Cu cermet anode materials [14]. In a
previous study, the performance of SOFC was comparatively
studied using Yttria-stabilized zirconia (YSZ) and NiYSZ that
were both doped using CuCeO2 as anodes in the presence of
H2, CO, and syngas fuels. The cells that were prepared using Cu
CeO2YSZ anode in the presence of both H2 and CO gas
6 S.P.S. Shaikh et al. / Renewable and Sustainable Energy Reviews 51 (2015) 18
atmospheres exhibited excellent performance, whereas cells with
NiYSZ anodes showed poor performance in CO operation com-
pared with that in H2 gas. The catalytic activities of the cells were
considerably improved by adding CO to the CuCeO2YSZ anode in
the presence of H2 at an operating temperature of 700 1C [64].
Several researchers have also studied the effect of both fuel
concentration and dilution on cell performance. Cu-based cermet
anode emerged as a potential anode material due to its relatively
high electronic conductivity compared with Ni-based cermet
anode; the cost of operation is also reduced with the use of Cu-
based cermet anode [57,65,66].
Unlike protons, O2  ions act as mobile charge carriers. There-
fore, such anions can be directly utilized by hydrocarbons through
SOFC operation. Cu shows a reduced catalytic activity in CuNi
CGO, whereas Ni enhanced its coke formation. Thus, they exhib-
ited poor electrochemical performance in the presence of hydro-
carbon fuels [67]. Increasing the percentage of Cu in NiCGO
anode reduces the conductivity of the cells. Cu is an effective
current collector. Gorte et al. [68] studied a CuNiCGO anode by
introducing Cu in NiCGO that does not promote the formation of
coke only in reduced atmospheres, such as N2 gases. Thus, CuNi
CGO can be an alternative for SOFCs in the absence of
hydrocarbon gases.
Ceria provides high catalytic activity for reforming hydrocar-
bons because it possesses a high oxygen storage capacity and ion
transport characteristics. Several researchers have observed that
coke deposition causes variations in SOFC performance because
the deposits are extremely graphitic in nature. Severe coke
deposition occasionally reduces the electrical current, and
decreases anode activity in SOFCs. Among the transition metals
studied thus far, cerium appears to be the most efcient dopant.
Cu cermets exhibit good electronic conductivity and high
catalytic activity; these properties are necessary during reduction
on an anode/electrolyte interface [69,70]. According to Liu et al., a
mixture of CuO and CeO2 particles improves the reducibility of
oxides as catalysts [16,71]. NiYSZ and NiCGO anodes have been
replaced by CuCGO and Cu-NiCGO anodes to prevent coke
formation [72]. As such, Cu cermet-anode materials for SOFCs
have received increased attention because of their Cu-Ce interac-
tions and high electrochemical performance [14,18,73].
Atkinson et al. [73] and other researchers [74] provided key
considerations for selecting alternative anodes. CeO2- and CeO2-
based materials are often used as anodes and catalysts because
they exhibit unique catalytic activities during environmental-
associated reactions [75]. The enhanced redox property of CO2
may be obtained by incorporating a transition metal in cubic CeO2
lattices to form a solid solution [75]. Electronic interactions
Table 3
DC conductivities of materials developed as anodes for SOFCs at 800 1C.
Materials DC conductivity (S cm  1)
Sc0.1Y0.1Zr0.6Ti0.2O1.9 0.14
La0.8Sr0.2Fe0.8Cr0.2O3 0.5
La0.8Sr0.2Cr0.95Ru0.05O3 0.6
(La0.7Sr0.3)1  xCexCr1  xNixO3 5.03
Sr0.88Y0.08TiO3 64
CrTi2O5 177
NiYSZ 250
Ti0.34Nb0.66O2 340
LaSrTiO2 360
NiSDC 573
NiGDC 1070
CuCeO2 5200
CuGDC 8500
*References are mentioned with respect to DC conductivity of different anodes for SOFC.
between CuO and CeO2 affect the overall resultant catalytic
activity, which has been conrmed by cyclic voltametry experi-
ments and temperature-programmed reactions performed in
several previous studies [14,72]. Oxy-ion conductors have uorite
structures, and the ionic effect securing these conductors involves
interstitial anions and anionic vacancies. Studies on steam refor-
mation of methanol over CeO2 catalysts prepared by a reduction of
CuOCeO2 mixed oxides have been reported [75,76]. CeO2 and CuO
reduction occurs simultaneously even at temperatures below
200 1C [77,78].
3.4. CuCGO cermets
Adding CGO to Cu is necessary to achieve desirable perfor-
mance [79,80]. Cu-based anodes exhibit reasonable tolerance to
sulfur, which is an additional advantage [81]. Gross et al. [82]
proposed the fabrication of high-performance anodes through the
direct utilization of hydrocarbons. Steele et al. investigated elec-
tronically conductive oxides; in their study, they used a novel
approach to select anode materials that do not catalyze or promote
carbon formation [83]. Oxides do not catalyze CC bond formation.
Thus, they resist coke formation. Cerium oxide has recently played
a major role in automotive combustion control as an oxygen
storage channel and a thermal stabilizer [84].
When a CGO electrolyte is compressed with a CuCGO anode as
a symmetric cell, the resultant anode works well under reducing
environments. CGO exhibits high oxide ionic conductivity in the
order of 10  2 S cm  1. Thus, Gd3 and Ce4 ions are preferred
over common anode materials compatible with CuCGO anodes. A
CuCGO cermet develops 50 wt% CuO after composite sintering
and reduction, to reveal a homogeneous distribution of Cu
particles surrounded by pores and CGO grains. Such cermets
exhibit metallic electronic conductivity with ne percolation and
good catalytic activity. CuCGO anodes exhibit great potential in
the direct oxidation of hydrocarbons.
Literature indicates that the electrical conductivity at 700 1C is
close to the conductivity of pure metallic Cu at 700 1C (70 S m  1).
This nding conrms that the Cu phase is continuous [85,86].
Incorporating Cu in ceria is necessary to achieve reasonable
performance in Cu-based anodes during hydrocarbon oxidation.
Aside from its low catalytic activity, Cu also exhibits a lower
melting temperature than Ni (1083 1C versus 1453 1C).
Materials containing CeO2 and CeO2 are often studied as
components of heterogeneous industrial catalysts or supports for
transition metals because they exhibit superior chemical and
physical stabilities, high O2 mobilities, and strong interactions
with supported metals. As a result, a number of researchers [14,72]
Advantage/Disadvantage References
Operate at high temperature [16]
Low conductivity [28,38]
Expensive [27]
Carbon deposition [25]
High operating temperature [33]
Expensive [25]
High operating temperature [12]
Very Expensive [19]
No compatibility
Coke formation [12]
Coke formation
Electronic performance degradation [12]
Improved electronic conductivity [43,72]
Good thermal expansion and good electronic performance [14]
 S.P.S. Shaikh et al. / Renewable and Sustainable Energy Reviews 51 (2015) 18
Fig. 2. Analysis of the overall performance of different anode materials for SOFCs.
have extensively studied cermet-based anode materials, such as
CuxCe1  xO2  x and CuCGO, to address several problems asso-
ciated with low-temperature and IT-SOFCs.
Table 3 and Fig. 2 show the overall performances (i.e., structural
and electrical properties) of different anode materials at 800 1C in
a reducing atmosphere. Sun et al. [41] obtained the lowest
conductivity for Sc0.1Y0.1Zr0.6Ti0.2O1.9. In 2003, Fagg et al. [87]
reported that CuGDC exhibits the highest conductivity among
several anodes tested.
Thus, it was observed that anodes based on conducting ceramic
offered an alternative approach to the direct utilization of fuel as
oxides unable to dissolve carbon, and hence cannot form carbon bers.
The problem of thermal stability of many oxides can be solved
by the appropriate selection of materials as anodes for SOFC. In
addition, the selection of the metal cermets anode exhibits the
additional advantage of redox stability during the start-up and
shut down cycle [87].
3.5. Summary of anode performance
Many of the problems related to SOFC need to be solved
through material selection. Only materials that are robust and
resistant to oxidation and reduction of SOFC should be used.
Table 1 shows a summary of advantages, disadvantages, and DC
conductivities obtained at 800 1C. These results were obtained
from several studies. According to the electronic conductivities
found, we conclude that CuCGO anodes are potential anodes for
SOFCs, as both Cu and Ce resist carbon deposition and support the
release of more electrons on the anode side. As a result, the
conduction in the circuit increases, as shown in Fig. 1.
The performance of cermet materials mostly depends on their
microstructural features [87,88] and degradation under working
conditions, which is likely caused by the coarsening of Ni particles,
as shown in Table 1 [89]. Fig. 2 shows that CGO-based anode
materials exhibit increased tendencies to oxidize CH4 compared with
other oxide anodes. The data provided in Table 1 show that Cu-
cermet-based anode materials are suitable anodes for SOFCs. These
issues offer research challenges for researchers interested in materi-
als synthesis and characterization of catalyst as an anode for SOFC.
The efciency advantages inherent in fuel cells compared with
other power generation methods suggest that fuel cells must be a
part of our energy future [87,89].
4. Conclusions
The current paper presents a detailed literature review on
suitable anode materials for SOFCs. Most of the recent studies on
SOFCs concentrate on cermet anode materials. Using an
7
appropriate metal cermet instead of conventional anode materials
may enhance the electrochemical performance of most anode
materials for SOFCs. Results of the review show that Ni-based
anode materials are less attractive than Cu-cermet-based anode
materials because of the relatively poor electrical performance of
the former compared with that of the latter. This review provides a
detailed summary of the structural and electrical properties of
different anode materials. We conclude that CuGDC is an excel-
lent next-generation anode material for IT- and LT-SOFCs. From the
review of literature, it is concluded that once a suitable selection of
anode materials is available and the technique to make these fuel
cell commercially affordable is developed, this approach of energy
generation will change the near future and improve the quality of
lives by reducing the environmental degradation caused by con-
ventional power sources.
Acknowledgments
The authors gratefully acknowledge the nancial support of the
Universiti of Kebangsaan Malaysia under Grant nos. 03-01-02-
SF1079 and GUP-2014-070.
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