perovskite materials

Chapter 20
Designing Perovskite Oxides for Solid Oxide Fuel Cells
Idoia Ruiz de Larramendi, Nagore Ortiz-Vitoriano,

Isaen B. Dzul-Bautista and Teófilo Rojo
Additional information is available at the end of the chapter
http://dx.doi.org/10.5772/61304
Abstract
Perovskite-type oxides with the general formula ABO3 have been widely studied and
are utilized in a large range of applications due to their tremendous versatility. In
particular, the high stability of the perovskite structure compared to other crystal
arrangements and its ability, given the correct selection of A and B cations, to maintain
a large oxygen vacancy concentration makes it a good candidate as electrode in solid
oxide fuel cell (SOFC) applications. Utilizing this novel structure allows the engineer‐
ing of advanced, effective electrolytes for such devices. This review details the
development of current state-of-the-art perovskite-type oxides for solid oxide fuel cell
(SOFC) applications.
Keywords: SOFC, Nanostructure
1. Introduction
The development of new energy technologies has become important with the present situation
of increasing energy demand, rising energy prices, and reinforcement of countermeasures for
global warming and its detrimental climatological, ecological, and sociological effects [1]. The
supplies of fossil fuels are constantly decreasing and some believe that we have reached the
peak for oil production. A reappearing problem in the energy field is the conversion from
available to usable form. This concerns the conversion of chemical energy in the form of fossil
resources and derivatives, such as hydrogen and alcohols, into electrical energy. It has become
increasingly important to reduce the losses associated with the applied conversion techniques
partly due to industrialization and technological progress. Traditional conversion to electrical
energy is by gas turbine, steam turbine, or reciprocating engine driving a generator, where the
© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons
Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution,
and reproduction in any medium, provided the original work is properly cited.
590 Perovskite Materials - Synthesis, Characterisation, Properties, and Applications
Carnot cycle sets a limit to the efficiency [2]. A fuel cell provides an alternative, whereby
electrical energy can be made available with small losses, and no Carnot limit [3]. The effluents
are in principle water, heat and CO2 if the fuel is clean.
The energy situation has caused a push for sustainable energy technologies. Here, fuel cells
play an important role in the renewable energy sector because of their highly efficient energy
conversion and their especially high reliability. During the last decades, fuel cells have
attracted much attention because of their potential for producing electricity more efficiently
than conventional power generation like heat engines, which normally are limited by the
Carnot cycle. The discovery of the fuel cell is ascribed to Sir William Grove (1839), demon‐
strating the reversibility of electrolytic water separation [4]. In 1899, Nernst contributed by
demonstrating that certain oxides attained remarkably high electrical conductivity by doping
with other oxides [5]. In the late twentieth century, the development accelerated and the
interest in fuel cell technology increased. Today, there are five different types of fuel cells, all
named after their electrolyte materials:
• Alkaline fuel cells (AFC)
• Polymer exchange membrane fuel cells (PEMFC)
• Phosphoric acid fuel cells (PAFC)
• Molten carbonate fuel cells (MCFC)
• Solid oxide fuel cells (SOFC)
Depending on the electrolyte, each fuel cell has certain characteristics such as operation
temperature, electric efficiency, and demands for fuel composition (Table 1).
Fuel Cell AFC PEMFC PAFC MCFC SOFC
Electrolyte KOH Polymer H3PO4 Li2CO3+K2 CO3 ZrO2+Y2O3
Charge carrier OH –
H +
H +
CO3 2–
O2–
Fuel Pure H2 Pure H2 Co-free H2 H2, CO, CH4 H2, CO, CH4, NH3
Toper.(°C) 65%–220 60%–130 150%–220 650 700%–1000
Electrical efficiency 45%–60% 40%–60% 35%–40% 45%–60% 45%–60%
Table 1. Most important characteristics for different types of fuel cells
Low-temperature fuel cells (AFC, SPFC, and PAFC) have potential for the propulsion of cars,
where a short heating time is needed and the efficiency has to be compared with about 20%
for a combustion engine, whereas high-temperature fuel cells (MCFC and SOFC) are suitable
for continuous power and heat production, where the cell temperature can be maintained. The
high-temperature fuel cells have higher efficiency and are more tolerant to the choice of fuel
compared to the low-temperature fuel cells [3].
Designing Perovskite Oxides for Solid Oxide Fuel Cells 591
http://dx.doi.org/10.5772/61304
2. What is a solid oxide fuel cell?
Solid oxide fuel cells (SOFC) are electrochemical devices which convert chemical energy
directly into electrical energy with high efficiency and low environmental impact and are
expected to become the emerging technology for stationary power production [6].
SOFCs are considered by many researchers to be the most suitable for generating electricity
from hydrocarbons because of their simplicity, efficiency, and ability to tolerate some degree
of impurities. There are many advantages of SOFC with respect to other fuel cells. Some of the
main advantages are [7]:
• The highest efficiencies of all fuel cells (50–60%)
• A potential long-life expectancy of more than 40,000–80,000 h
• Constructed from readily obtainable ceramic materials
• Few problems with electrolyte management
• High-grade waste heat is produced, for combined heat and power (CHP) applications
increasing overall efficiencies to over 80%, and
• Internal reforming of hydrocarbon fuels is possible

However, there are some drawbacks related to the choice of materials in relation to costs. There
are roughly two design types, tubular and flat plate. For the tubular cell, the material problems
are less, but fabrication costs are high, whereas for the flat plate design, fabrication costs are
less but more materials problems arise [8].
The operating principle of the solid oxide fuel cells is illustrated in Figure 1.
Figure 1. Sketch of solid oxide fuel cell operated on hydrogen and air.
SOFCs consist of three layers of functional materials: the anode, the electrolyte and the cathode.
The anode is where the oxidation reaction takes place, and the cathode is where the reduction
takes place. The cathode is fed with air or oxygen while the anode is fed with fuel gas. At the
cathode, oxygen molecules are reduced to oxygen ions (½ O2 (g) + 2 e– → O2–). The oxygen ions
are conducted through the electrolyte to the anode. At the anode, oxygen ions oxidize the fuel
gas and forms water and carbon dioxide, while the resulting free electrons are transported via
the external circuit back to the cathode (H2 (g) + O2– → H2O (g) + 2 e–).
To limit cathode overpotential, the traditional SOFC with yttria-stabilized zirconia (YSZ)
electrolyte and strontium-doped lanthanum manganite (LSM) cathodes operate at relatively
high temperatures (800°C–1000°C). These high temperatures encourage cell degradation—
increasing cell, stack, and system maintenance. In addition, even higher temperatures are
required for fabrication, encouraging electrode–electrolyte reactions, often forming undesir‐
able, insulating secondary phases and consequently increasing cell resistance. Lowering the
operating and fabrication temperature to 400°C–800°C could reduce both cell degradation and
manufacturing costs. Cells which operate in this temperature range are known as intermediate
temperature SOFCs (IT-SOFC). The advancement of this technology, limited by the high
temperatures required, can be overcome by reducing operating temperatures, thus increasing
theoretical efficiency. In order to operate efficiently at these reduced temperatures and to
develop the next generation of hydrogen-related energy devices, new materials are required
and the utilized processing routes must be optimized [6,9].
Among the new generation of materials, those with ABO3-type perovskite structures stand out
due to their great versatility. Through the correct choice of A and B site cations and the
introduction of dopants, it is possible to obtain a large variety of materials with a wide range
of properties and applications. This chapter will cover a selection of key materials developed
for use in SOFC devices, their advantages and disadvantages and the optimization strategies
published so far.
3. Evolution of perovskite-type structured materials as electrodes in SOFCs
The general formula unit of the perovskite is ABO3, where A is a larger cation with a coordi‐
nation number of 12 and B is a smaller cation with a coordination number of 6 (Figure 2). The
large A cations can be rare earth, alkaline earth, alkali, and others [10] whereas the smaller B
site accommodates many transition metals. These elements are typically the source of elec‐
tronic conductivity. Cations of a rather wide range of ionic radii and valence are able to enter
one or another site in the perovskite structure, exhibiting versatile physical and chemical
properties and, thus, high concentrations of oxide vacancies and high ionic conductivity may
be achieved [11]. This ability to hold a large content of oxygen vacancies makes them good
candidates as electrodes in SOFC applications.
Figure 2. Atomic structure and oxygen transport in mixed conducting perovskites. On the left, the positions of the ions
in a cubic structure. On the right, corner-sharing BO6 octahedra and oxygen vacancy migration path.
http://dx.doi.org/10.5772/61304
The B cations are located in the corners of the cube and the A cation occupies the center. The
oxygen is placed at the centers of the twelve cube edges, giving corner-shared strings of BO6
octahedra. The A cation has the same size as the oxide ion, while the B cation is smaller.
Depending on the type of cations, it is possible to create oxygen vacancies in the structure.
These oxygen vacancies move along the structure giving rise to ionic conduction (Figure 2).
The composition and the microstructure of electrode materials greatly influence the perform‐
ance of SOFCs. The high temperature and the reducing or oxidizing atmospheres limit the
choice of these materials.
3.1. Cathode materials
One of the major research efforts in SOFC technology is directed towards decreasing the cell
operating temperature. The best performance of the electrolyte, anode, and cathode materials
typically is seen at an operating temperature above 800°C. This makes the use of expensive
alloys as interconnectors and current collectors necessary. Decreasing the operating tempera‐
ture would make it possible to use soft steel alloys with a remarkable decrease of the initial
cost of the device. It is necessary, however, to develop new materials which exhibit good
performance at lower temperatures in terms of conductivity, and chemical and mechanical
compatibility. The widely used materials also need to be optimized in order to minimize
technical problems at elevated temperatures. These problems are often associated with a
mismatch between the thermal expansion coefficients of the electrolyte and cathode or as a
consequence of oxygen loss from the cathode material.
The role of the cathode as the active site for the electrochemical reduction of oxygen is an
important parameter to take into account in the material’s design. SOFCs operate at high
temperatures for long periods of time and, therefore, some requirements must be fulfilled [12]:
(i) high electronic conductivity (σ > 100 S cm–1); (ii) a thermal expansion coefficient (TEC) match
with other SOFC components; (iii) chemical compatibility with the electrolyte and interconnect
materials; (iv) adequate porosity to allow mass transport of oxygen; (v) high thermal stability;
(vi) high catalytic activity for the oxygen reduction reaction (ORR); and (vii) low cost.
The cathodic reaction is quite complex and compromises a number of single steps such as
diffusion, adsorption, dissociation, ionization, and finally, incorporation of oxygen into the
electrolyte [13]. Oxygen molecules adsorb on the surface where they form partially reduced
ionic/atomic species. These electroactive species must be transported along surfaces, interfaces,
or inside the bulk of the electrode material to the electrolyte, where they are fully incorporated
as O2–.
The cathode materials can be classified into two groups: mainly, electronic conductors (with
poor ionic conduction) and mixed ionic-electronic conductors (MIECs). Depending on the type
of material, the conduction mechanism in the cathode will be different (Figure 3). In a poor
ionic conductor, adsorption, dissociation, and diffusion of oxygen between the gas phase,
electrode, and electrolyte [14] occurs through the triple phase boundary (TPB). In the MIECs,
the conduction mechanism also occurs through the double phase boundary (DPB) [15,16]. The
mixed conducting nature of the oxide ensures that electrochemical reactions occur at the MIEC/
gas double phase boundary (DPB).
Figure 3. Schematic representation of conduction mechanisms (DPB: double phase boundary; TPB: triple phase boun‐
dary).
The deposition technique is also an important parameter which influences the electrochemical
behaviour. Conduction in porous electrodes occurs through the three-phase boundary (TPB),
whereas in MIECs, this also occurs through the DPB. In the case of dense electrodes, there is
no direct contact between the cathode, electrolyte, and gas (hence, no TPB conduction exists).
In this case, the oxygen reduction reaction occurs anywhere on the cathode surface, forming
oxide anions which diffuse into the bulk of the electrode material towards the electrolyte. The
material must present mixed ionic and electronic conduction [17].
La1-xSrxMnO3-δ (LSM) and La1-xSrxCoO3-δ (LSC) have been widely used as cathodes in SOFC.
LSM has high electronic conductivity due to the introduction of Sr2+ on the La3+ site which will
be charge-compensated by the Mn (Mn3+–Mn4+), making it a good cathode at high temperatures
(1000°C). At intermediate temperatures (500°C–700°C), however, a large increase in the cell
overpotential (from <1 to 2000 ohm cm2) is observed, which hinders its use as a cathode [18].
One of the main limitations of LSM is its low ionic conductivity (~10–7 S/cm at 900°C), which
is related to the Mn charge compensation where oxygen vacancies are not generated. The ease
with which oxygen vacancies form is strongly influenced by the Sr content [19]. The influence
of the cation vacancy on the transport properties of these materials has led to a study of the
defects in these materials, such as LMO, and the effect of substitutions on the lanthanide site
[20]. DeSouza et al. found that in both rhombic and rhombohedral structures, nonstoichiom‐
etry leads to the formation of vacancies on both cation positions, presenting a tendency toward
the formation of vacancies [21]. These details are essential in understanding the behaviour of
the materials and the degradation processes which can lead to the formation of insulating
phases affecting the cathode performance. To obtain better performance from dense or porous
LSM on YSZ electrolytes, a two-layer cathode is necessary—a 0.3 mm porous layer and in
between a dense film of YSZ (~1 µm) [22]. This structure combines the best properties of both
types of cathode in a single process and with more favorable properties than when using only
the porous cathode.
Several authors have investigated other rare earths in the lanthanide position such as Pr, Sm,
or Nd in order to improve the performance of manganites and avoid problems associated with
http://dx.doi.org/10.5772/61304
the formation of the pyrochlore-insulating phases at the LSM/YSZ interface [23]. By substitut‐
ing La with Sm, new materials with lower energetic barriers for adsorption and diffusion of
oxygen species have been obtained [24]. In addition, they present excellent compatibility with
YSZ and electronic conductivity well above that required in a SOFC (100 S/cm) [25]. The most
promising electrode materials are Pr0.7Sr0.3MnO3-δ and Nd0.7Sr0.3MnO3 in terms of thermal
expansion coefficient, reactivity, and conductivity [26]. The study of the compatibility of (Ln,
Sr)MnO3-δ with electrolytes has been limited to YSZ due to its widespread use. The performance
of Nd1-xSrxMnO3-δ with gadolinia-doped ceria electrolyte (most suitable for use in IT-SOFC),
however, revealed no reaction between the components at the interface after prolonged high-
temperature treatments [27]. The same authors indicated that Pr0.5Sr0.5MnO3-δ shows very
promising properties with an electrical conductivity of 226 S/cm at 500°C [28]. Most studies
on manganites have focused on doping the lanthanide site with Sr. In terms of chemical
compatibility and electrical conductivity, however, the use of calcium as a dopant can offer
very promising results, as in the case of Pr0.7Ca0.3MnO3-δ, which does not react with the
electrolyte and has a maximum conductivity of 266 S/cm [29].
While looking for alternative materials to manganites, lanthanum cobaltites doped with
bivalent metals such as Ca or Sr emerged [30]. These materials exhibit high conductivity values
when 30% or 40% of Ca or Sr are added, respectively. In addition, the substitution of La by
other lanthanides such as Pr and Sm has also lead to promising results. Despite the good results
that these cobaltites exhibit, other drawbacks such as their high TECs and the appearance of
secondary phases, limit their application.
In order to use the beneficial properties of these cobaltites, these materials are doped with Fe.
Although, the addition of Fe promotes the decrease of the conductivity of the orthoferrites,
lower TEC values are also achieved. Among these cobalto-ferrites, the Ba0.5Sr0.5Co0.8Fe0.2O3
material stands out for SOFC cathode application. Shao et al. reported excellent performance
at intermediate temperatures, proving that the orthoferrites are an interesting alternative for
IT-SOFCs [30]. At the same time, the use of La1-xSrxFe1-yCoyO3 has been widely investigated [31–
33]. These cobalt-based cathodes exhibit higher electrocatalytic performances than those of the
conventional LSM cathodes. Unfortunately, they have high TEC, high cost of cobalt, and easy
evaporation and reduction of cobalt [34,35].
Rare earth orthoferrites with perovskite-type structure are interesting materials for many
electronic applications because of their mixed conductivity [36,37]. A site–doped rare earth
orthoferrite compounds have been studied as candidates to replace manganites and cobaltite
cathodes due to its high catalytic activity and mixed ionic and electronic conductivities at
reduced temperature (σ total = 100 S/cm at 600°C–800°C) [35,38]. Lanthanum is a com‐
mon element and key component of most SOFC, where several of its oxides provide the
necessary electronic conductivity and high catalytic activity for oxygen reduction and some,
in addition, combine ionic and electronic conductivity [39]. The choice of using Pr as the
rare earth element is due to its peculiarity to show 3+ and 4+ oxidation states, which might
induce interesting electrical properties [35]. Some of the Pr-doped orthoferrites display good
performance as cathode materials in high-temperature solid oxide fuel cells because of their
mixed, electronic and ionic, conductivity [40]. In particular, Pr0.8Sr0.2Fe0.8Ni0.2O3−δ presents
low electrical resistivity and good oxygen ion conductivity [41]. Fe-based perovskite oxides
have also attracted much attention as possible alternatives to cobaltites due to their
interesting transport properties. When the Fe fraction is higher than 0.5, the materials exhibit
its highest electronic conductivity as observed for the LaNi0.2Fe0.8O3 phase in which a
conductivity of 135 S/cm, at 800°C, was obtained [42,43]. Calcium is another effective dopant
for the A site, with low cost. For example, Pr0.4Ca0.6Fe0.8Ni0.2O3 material exhibits an ASR
value of 0.09 ohm cm2 at 850°C [35]. Taking into account the low ASR value and the
electrical conductivity of this cathode (at temperatures above 600°C, which is over 100 S/
cm), this material is a promising cathode for IT-SOFC applications. Pr1-xMxMnO3 (M = Ca,
Sr) have also been studied where Ca-doped PrMnO3 phases exhibit better performance than
those doped with Sr. Ca-doped materials show higher electrical conductivity, lower cathodic
overpotential and more similar thermal expansion coefficient [44]. Moreover, calcium could
be a good candidate because of the similarity of its ionic radius with La3+ giving rise to
higher stability than that of strontium-substituted phases [45].
While a large number of studies concerning cathode materials report the presence of secondary
phases, they are often left unidentified [46] and are typically considered undesirable and
associated with insulating phases that give rise to low conductivity values and poor perform‐
ance [47]. Conversely, actual research in SOFC cathodes is focused on the development of
composite materials, as the inherent requirements are so wide-ranging that no single material
is capable of fulfilling every aspect [48]. The creation of composite cathodes is a good way to
enhance the cathodic performance. They are composed of a solid electrolyte and an electronic
conducting electrocatalytic material as in the La0.6Ca0.4Fe0.8Ni0.2O3-δ/samarium-doped ceria
(SDC) symmetrical cells reported in a previous work [49]. The investigated composite cathodes
include Sm0.5Sr0.5CoO3 (SSC)-Ce0.8Sm0.2O1.9 (SDC), La0.6Sr0.4Co0.2Fe0.8O3 (LSCF)-SDC, LSCF-
Ce0.8Gd0.2O2 (CGO), and Ba0.5Sr0.5Co0.2Fe0.8O3 (BSCF)-SDC, all of which exhibit low polarization
resistance at 600°C [50,51]. The electrochemical performance of these cathodes is generally
governed by triple phase boundary (TPB) kinetics, mass transport, and ohmic drop. The
primary disadvantages of utilizing composite materials arise from the need for two independ‐
ent materials; this increases both production complexity and the possibility of undesirable
phases forming through inter-reaction of the component phases. Recently, the La1-
xCaxFe0.8Ni0.2O3-δ (LCFN) system has been proposed and applied as a cathode featuring highly
competitive performance [48]. Contrary to expectations, the formation of perovskite brown‐
millerite pseudo-composites resulted in a clear enhancement of the electrochemical perform‐
ance and excellent thermomechanical compatibility with conventional electrolytes.
Furthermore, new insights are gained into material surface properties controlling oxygen
reduction processes.
The development of double perovskite materials such as GdBaCo2O5+x [52], PrBaCo2O5+x [53],
SmBaCo2O5+δ [54], or NdBaCo2O5+δ [55] have also been investigated for IT-SOFCs. Their ORR
activity is higher than many single perovskites [56]. They present high thermal expansion
coefficients, however, which make them incompatible with the electrolytes developed so far.
Table 2 summarizes the most widely study cathode materials for SOFC.
http://dx.doi.org/10.5772/61304
Composition TEC (K–1) Resistivity Conductivity Diffusion Ref.
ASR T (°C) σ (S/cm) T (°C) k (cm/s) D (cm /s) T (°C)

* * 2
(Ω cm2)
La1-xSrxMnO3 11.6××10–6 0.18 750 180 800 — 3 × 10–9 800 [57,58]
La1-xSrxFeO3−δ 12.1 × 10–6 0.1 800 125 800 1 × 10–5 6 × 10–7 1000 [59–61]
La1-xSrxFe0.8Co0.2O3−δ 15.4 × 10–6 0.34 750 404 550 6 × 10–6 3 × 10–5 626 [62-65]
La1-xSrxFe0.8Ni0.2O3 15.6 × 10 –6
0.16 700 435 800 — — — [66,67]
La0.6Ca0.4Fe0.8Ni0.2O3 11 × 10–6
0.10 800 260 600 — — — [6]
La0.6Sr0.4Fe0.8Cu0.2O3 14.6 × 10 –6
0.138 750 135 275 --- --- --- [68]
Pr0.6Sr0.4Co0.8Fe0.2O3 19.6 × 10 –6
0.046 800 1040 300 --- 9.4 × 10 –5
600 [69]
LaNi0.6Fe0.4O3 11.4 × 10–6 0.018 800 600 600 --- 2 × 10–7 950 [70,71]
Pr1-xSrxCo0.2Fe0.8O3 14 × 10–6 0.454 600 2190 600 --- --- --- [72,73]
Sm0.5Sr0.5CoO3−δ 22.8 × 10 –6
0.20 600 1000 850 6 × 10–5
8.6 × 10 –7
890 [74,75]
Ba0.5Sr0.5Zn0.2Fe0.8O3−δ 16.5 × 10 –6
0.48 650 9.4 590 --- --- --- [76]
Ba0.5Sr0.5Co0.8Fe0.2O3 19.9 × 10 –6
0.15 600 30 600 --- 7.3 × 10 –5
--- [77,78]
PrBaCo2O5+δ 20 × 10–6
0.11 600 2000 150 1 × 10 –3
1 × 10 –5
350 [56,79,80]
PrBaCoFeO5+δ 21 × 10–6 0.049 800 321 350 --- --- --- [81]
NdBaCoFeO5+δ 19.5 × 10–6 0.062 800 172 350 --- --- --- [81]
GdBaCo2O5+δ 20.1 × 10–6 0.15 750 512 500 2 × 10–6 3 × 10–7 350 [82,83]
SmBaCo2O5+δ 16 × 10–6
0.098 750 815 500 --- --- --- [84]
SmBa0.5Sr0.5Cu2O5+δ 14.1 × 10 –6
0.25 650 277.7 485 --- --- --- [85]
YBaCo2O5+δ 16.3 × 10 –6
0.11 700 315 325 --- --- --- [86]
Table 2. The main properties of SOFC cathodes with both single and double perovskite structures
In recent years, advancements in cathode material properties have been made where a variety
of perovskite oxides with a wide range of properties have been investigated. There are still,
however, many chemistries to investigate which may yield superior performance in the future.
3.2. Anode materials
The requirements for a SOFC anode are quite similar to those for cathodes (changing the
oxidizing atmosphere by a reducing environment), including: (i) proper electronic conductiv‐
ity; (ii) thermomechanical and chemical compatibility with the electrolyte and interconnect
materials; (iii) adequate porosity to allow gas transport to the reaction sites; and (iv) low cost.
High ionic and electronic conductivity over a wide pO2 range and high surface oxygen
exchange kinetics and good catalytic properties for the anode reactions are also desirable
properties for a good anode material. Nickel-YSZ cermet has been widely used in the SOFC
anode. This material fulfills most requirements: Ni exhibits good catalytic activity for the
dissociation of hydrogen while remaining stable at operating conditions and YSZ provides
structural support for the Ni particles and inhibits their coarsening while matching the thermal
expansion properties of the rest of the cell components [87]. Areas where this anode compo‐
sition is lacking, however, include poor redox stability, low sulphur and carbon deposition
tolerance when hydrocarbon fuels are used, and the tendency for nickel to agglomerate after
prolonged operation [88]. In the search for alternative anode materials that are capable of
withstanding sulphur contamination and carbon deposition, oxides with perovskite structure
have drawn considerable attention [87]. Several authors have studied anode materials based
on the perovskite structure as very promising alternatives [89,90]. Among the numerous
materials with perovskite structure, SrTiO3-type titanates have received a great deal of
attention due to their high stability under reducing atmospheres and high temperatures [91].
This material, however, suffers from poor electronic conductivity, but this can be overcome
through the introduction of appropriate dopants in the structure [92]. Marina et al. studied the
effect of La doping in SrTiO3 with a clear effect seen from the substitution of the Sr and the
oxygen partial pressure on the total electrical conductivity with values as high as 500 S/cm at
500°C for the La0.3Sr0.7TiO3 phase [93]. Furthermore, doping with Sr in the A site and Nb in the
B site, it was possible to increase the conductivity to 10 S/cm; however, these materials
exhibited a poor ionic conductivity [94]. Ti has also been substituted by other cations such as
Al, Fe, Ga, Mg, Mn, or Sc, affecting significant changes on the redox properties of the material
and conductivities [95]. By adding multivalent cations such as Mn or Fe, reduction or oxidation
occurs in these cations in preference to or together with Ti, leading to a general decrease in the
presence of Ti (III), resulting in a decrease in conductivity [96]. The effect of Co has also been
analyzed, observing that after reduction with H2, the segregation of Co nanoparticles occurs
on the anode surface, which favors the oxidation of the fuel, thus reducing the resistance under
anodic polarization [97]. To improve the behaviour of titanates, various dopants have been
introduced on the A site (Y, La, Ce) [98,99]. The introduction of Ce3+ leads to decomposition
into a variety of phases due to its ready oxidation in air. Some Ce-rich phases migrate to the
grain boundaries, which result in an increase in the catalytic properties of up to an order of
magnitude [100]. It is particularly interesting to note the results obtained by Morales-Ruiz et
al., where (La,Sr)(Ti,M)O3 (M = Ga, Mn) anodes exhibited comparable performance to those of
conventional Ni-YSZ anodes [101]. Recently, AMoO3 perovskite types (A = Ca, Sr, and Ba),
containing Mo4+ ions have received interest for their potential use as anodes [102]. While these
materials have high electrical conductivities (104 S/cm) they also present problems associated
with the diffusion of oxide ions [102]. This limitation can be overcome by doping with other
metals such as Fe or Cr on the Mo site [103,104]. Co is another suitable dopant which also
creates oxygen vacancies, supplying sufficient ionic transport making a material with excellent
catalytic properties for the oxidation of hydrogen [105]. Another alternative is to create
composites with materials which have high ionic conductivity [106]. In this regard, the most
commonly used materials are Y0.08Zr0.92O2 (YSZ), La0.8Sr0.2Ga0.8Mg0.2O3 (LSGM), and
Gd0.1Ce0.9O2 (GDC), which have been traditionally used as electrolytes, facilitating greater
thermal, mechanical, and chemical compatibility with the anode composite. From these
systems, a new material with the general formula Sr2Fe1.5Mo0.5O6 (SFMO) and perovskite-type
structure has been developed, which features suitable mixed ionic-electronic conductivity and
interesting catalytic activity [107]. It exhibits great stability when H2, fuel or natural gas is used
http://dx.doi.org/10.5772/61304
and high tolerance to sulfides [108]. Recently, Sutirakun et al. developed a theoretical model
for analyzing the electrochemical oxidation of H2 on the surface of this material [109]. One
strategy for optimizing the material is to increase either the Mo content or add a small amount
of active transition metal such as Ni in order to reduce the energy required for the formation
of vacancies on the surface of SFMO. The other family of materials which has been widely
studied are the chromites (LaCrO3). These materials initially developed as interconnectors for
SOFCs, which will be discussed later, because of their high stability in both oxidizing and
reducing atmospheres and low tendency to accumulate carbon [110]. Their low catalytic
activity, however, makes their use with some fuels such as methane impossible. To solve this
problem, the effect of different dopants on the properties of this material (Ca and Sr on the A
site and Mg, Mn, Fe, Co, and Ni in the B site) has been studied [111]. (La, Sr) (Cr, Fe)O3 is the
best candidate due to its high redox stability, high conductivity, and electrochemical activity
[111]. In addition, this material works well as a catalyst for methane [112] and has a thermal
expansion coefficient very similar to YSZ and LSGM [113]. Fowler et al. have also studied these
materials, finding that the La0.6Sr0.4Cr0.4Fe0.6O3-δ composition presents the best performance and
highest stability [114]. In recent years, a new generation of anode materials with the double
perovskite structure, such as Sr2MgMoO6 (SMMO) [115], PrBaM2O5 (M = Co, Mn) [116,117],
and La4SrTi5O17 [118] have been developed. These materials have very interesting properties
which permit the use of multiple fuels.
4. Perovskite oxides as electrolytes and interconnectors for SOFC
Electrolyte ceramic materials must meet the following requirements: high ionic conductivity
and low electronic conductivity; the charge carrier must either be from the oxidizer (O2) or fuel
(H2), i.e. O2– or protons [119]. To date, SOFC electrolytes are, in most commercial cases, 8 mol
% yttria stabilized zirconia (8-YSZ) [120]. This material belongs to the group of fluorite-type
solid solutions and up to now is the O2– ion conductor most used as electrolyte material for
SOFC due to its high ionic conductivity and thermomechanical stability. Doping ZrO2 with
Y2O3 has two main functions. First, to stabilize the cubic, fluorite phase, otherwise only stable
at elevated temperatures, and second, to compensate the insertion of the trivalent Y3+ ions by
oxygen vacancies in the zirconia lattice, giving rise to an enhancement of the oxygen ion
conductivity. Generally, yttria-doped zirconia with 8 mol% Y2O3 exhibit an ionic conductivity
higher than 0.1 S/cm at 1000°C and an electrical conductivity lower than 10–4 S/cm [121].
An important aspect to be considered is the chemical stability of the candidate materials at cell
operation conditions, presenting high ionic conductivity (>0.1 S/cm) at intermediate temper‐
atures and thermal expansion coefficients similar to the components of the cell [119]. The
decrease in operating temperature can lead to an increase in chemical stability and cell lifetime,
as well as a reduction in manufacturing costs; however, in the case of YSZ, cell performance
decreases at lower temperatures due to the thermally activated ionic conductivity [122].
In order to obtain materials with improved properties at temperatures below 800°C, two
families with perovskite type structure: gallates and cerates have been developed [123]. Most
studies focus on Sr-doped LaGaO3, but other dopants such as Ba have also been investigated
[124]. Phase segregation occurs when Ba is used due to its large size compared to Sr which
forms a mixture of LaBaGa3O7 and LaGaO3 resulting in poor conductivities [125]. The ionic
conductivity of this material can be increased by introducing Mg in the perovskite B site due
to the introduction of compensating defects in the structure [126,127]. It has also been shown
that the presence of a stoichiometry deficient in Ga may result in an increase in the concen‐
tration of oxygen vacancies [128]. In fact, this material is stable in CO-rich atmospheres, which
allows its use as an electrolyte in direct coal solid oxide fuel cells (DC-SOFCs) [129]. Another
strategy to increase the ionic conductivity of the material is through the production of
composites with doped ceria electrolytes [130]. Through this method, it has been possible to
optimize conduction through the grain boundaries, resulting in up to 10 times higher conduc‐
tivity than ceria electrolytes at 500°C. In summary, the cells employing (La,Sr)(Ga,Mg)O3-δ
electrolytes have high power densities at 800°C, which makes them excellent candidates for
IT-SOFC electrolytes [131,132].
The other family of materials with perovskite structures is based on BaZrO3 and BaCeO3, which
traditionally have been developed as proton-conducting oxides, especially the cerates [133].
The production method, the temperatures employed in the process and the type and concen‐
tration of the dopant will affect proton conduction in the material. The cerates allow the
introduction of precious metals such as Pd, which facilitates oxygen mobility, although the
best results were obtained by using metal nanoparticles and by decorating the surface of the
perovskite which acts as active catalysts [134]. Other dopants, both divalent and trivalent (Y,
Yb, Gd, Sm, Nd, and La) have been employed [135–137]. This makes it possible to design
materials resistant to reducing atmospheres with high conductivity and thermal and chemical
stability in IT-SOFC operating conditions, even at temperatures as low as 500°C.
SOFC interconnect material requirements are as follows: (i) electronic conductivity > 100 S/cm;
(ii) ionic transport number < 0.01 to avoid chemical shortcut permeation; (iii) gas tight; (iv)
tolerate both reducing (H2) and oxidizing (air/O2) atmospheres; (v) be compatible with anode
and cathode electrode materials (TEC and chemistry); and (vi) mechanical strength. LaCrO3
chromites are the most widely used SOFC interconnects and, doped with other elements, their
properties are shown to be improved [138]. The dopants most widely employed in the A site
of the perovskite are Sr, Mg, and Ca, with dissolution limits of 50% [139], 15% [140], and 50%
[141], respectively. Furthermore, the B site is also doped with Co or Fe, in order to limit the Cr
content as much as possible due to its volatility [142]. Doped lanthanum chromites seem ideal
materials for use as interconnects as they are highly stable in both oxidizing and reducing
atmospheres and, at SOFC operating temperatures, do not react with the other cell compo‐
nents. Regarding thermal compatibility, through appropriate doping, it is possible to tailor the
thermal expansion coefficient to that of the other components of the cell. LaCrO3 is a p-type
conductor that, upon divalent cation substitution on the La site, is seen to charge compensate
by a valence change in the Cr (Cr3+–Cr4+), accompanied by an increase in the electronic
conductivity of the material. The main problem associated with these compounds is their
sinterability, as at high temperatures and under high oxygen pressure, volatilization of
chromium oxide can occur. To avoid this, various strategies such as more reactive synthesis
methods at lower temperatures, the introduction of cationic vacancies, and new fabrication
techniques (including microwave sintering, freeze drying with EDTA, and more) have been
analyzed [143].
http://dx.doi.org/10.5772/61304
5. Nanostructured perovskites for improving solid oxide fuel cells
Nowadays, the research in solid oxide fuel cells (SOFCs) is focused on lowering the operating
temperature below 800°C in order to overcome problems such as the ageing of the materials.
Concurrently, lowering the operating temperature has the detrimental consequences of
decreasing the rate of surface reactions and bulk diffusion in the cathode, giving rise to a
worsening of the cell performance. Surface exchange and ionic conduction must therefore be
improved to maximize the yield of the cathode reaction. This improvement can be carried out
not only by new material selection but also by the detailed control of the microstructure [144].
As stated before, a common strategy for improving the electrochemical performance of the
electrodes is the fabrication of composite materials, combining ionic and mixed ionic electronic
conducting materials, where the ionic conductor is homogeneously distributed [49]. Using
composites, the ionic conductivity across the electrode will be enhanced and, simultaneously,
a higher thermomechanical compatibility with the electrolyte can be achieved. The catalytic
activity of the material is associated with its microstructure, so if the latter is improved, the
active surface area will be increased, and a higher electrochemical durability will be obtained
[145]. A significant number of studies have also been conducted to increase active surface area
via microstructural control: the use of organic materials as pore formers, template materials
such as colloidal crystals, meshes, foams or microfibers, glassy carbon microspheres, or
membrane-based templates [146]. These methods look for higher catalytic activities for
electrode reactions and lower annealing temperatures due to the numerous active sites and
large surface areas. The same goal can be achieved using a new tool that has been developed
during the last two decades: nanotechnology [147].
Recently, nanotechnology has been shown to overturn many established theories in a wide
range of scientific fields, often with highly desirable properties [148]. This has naturally
resulted in a great deal of interest from both scientific and industrial communities in the
properties of nanostructured materials. This interest arises from new and unexpected behav‐
iour when compared with bulk materials. Enhancements have been reported in electrical and
ionic conductivity, chemical reactivity, and other properties. The shift from bulk to nanoma‐
terials is therefore a promising approach in the development of new advanced technologies
capable of achieving higher performance and low environmental impact.
Nanomaterials have typically been considered for low-temperature devices, as high temper‐
atures could promote coarsening and therefore loss of the desired properties. This has
generally kept nanomaterials from application in solid oxide fuel cells (SOFCs), but constant
material advances have led to the decrease in their operational temperature. These so-called
intermediate temperature SOFCs (IT-SOFCs), operating at 500°C–850°C, allow new possibili‐
ties for the use of nanomaterials.
The high surface area to volume ratio inherent in nanomaterials provides a large active area
for SOFC electrodes. Nanomaterials are defined as a range of materials where at least one
dimension is below 100 nm, resulting in nanostructures in zero- to three-dimensions. Nano‐
particles, 0-D in nature, are well suited for use in composite electrodes, 1-D nanostructures,
including nanotubes and nanowires, are thought to operate as promising electrodes, and thin
films, 2-D in nature are of interest for application in micro-SOFCs (µ-SOFCs) and interlayers.
Although the electrical properties of these nanostructures have been analyzed as independent
0- or 1-dimensional structures, the 2- or 3-dimesional behavior is more frequently reported, as
it provides reliable results.
When working with SOFCs, there are two main approaches to develop nanomaterials with
improved properties: optimizing existing composites by transforming them to nanocompo‐
sites and exploring novel nanostructured materials with high mixed ionic and electronic
conductivity. In order to fabricate nanocomposites, wet impregnation/infiltration has been
gaining increasing attention in recent years [149]. The infiltration process consists of placing a
drop of a metal salt solution, with the chemistry required to give rise to the MIEC electrode
material after decomposition, on top of a porous material (typically the ionic conductor) [150].
In parallel, MIEC nanostructured materials have also been developed in order to find further
optimization of current state-of-the-art electrode materials. This kind of material features one
dimension below 100 nm, giving rise to different structures such as nanoparticles, nanotubes,
nanofibers, etc. There are several techniques for obtaining these unique phase nanomaterials
with enhanced active areas and lower particle sizes with one of the most commonly used being
via templating. Only some examples utilizing this procedure will be shown, although a large
number of articles have been published on this topic. However, the excellent review by Ruiz-
Morales et al. is recommended for those interested in a more detailed description of this
method [146]. There are just a few materials able to act as templates because they must fulfill
requirements such as removability, compatibility with the process conditions, wettability with
the network forming precursor solution and a narrow particle size distribution to achieve
optimal packing. Some of the most interesting templates are the organic polymer spheres of
polycarbonate (PC), polystyrene (PS), and polymethyl methacrylate (PMMA) [151]. It has been
demonstrated that templated porosity is maintained and highly influences electrochemical
behavior, presenting an effective means of enhancing the triple phase boundary (TPB), and
thus improving cell performance [152]. Another interesting method to obtain economical
nanostructures is based on the use of carbon nanotubes (CNTs) as particle growth controller
templates [153,154]. The growth controller material must fulfill the following two character‐
istics for the desired application: thermal stability and either an ease of removal or sufficient
electrical properties to form a composite material. This facile and economical route allows to
synthesize perovskite nanoparticles with grain sizes as small as 16 nm and surface areas of 151
m2/g, improving electrochemical performance of the electrode by approximately one order of
magnitude [153].
Of all possible nanostructures, nanotube-shaped materials seem to exhibit the most interesting
improvements to electrode performance [155]. Although inorganic nanowires have been
synthesized by several methods such as hydrothermal reaction [156], vapor transport [157],
and electrospinning [158], the complexity of perovskite nanotube synthesis has resulted in the
template-assisted synthesises becoming the most employed method. There are currently
several membranes with different properties which can be used as templates, with anodized
alumina (AAO) membranes being the most common [159]. The most important advantage of
these membranes is their thermal stability, which allows the control of the morphology at high
http://dx.doi.org/10.5772/61304
temperatures. Their high cost and the problems associated with their anodization do, however,
limit their use. These membranes are classified in the literature as hard membranes while there
is another group of templates known as soft membranes, which are primarily polymeric in
nature. While not costly, they decompose between 200°C and 300°C, which means that the
morphology cannot be completely controlled at higher synthesis temperatures. There are
several types of polymeric membranes, with polycarbonates being the most commonly used
[160]. The use of the pore wetting technique with polycarbonate membranes as templates and
subsequent freeze-drying allows the fabrication of highly ordered three-dimensional nano‐
structures [161]. The electrospinning technique has also been used for the production of MIEC
lanthanum strontium cobalt orthoferrite nanofibers [162]. This nanofiber-based cathode
architecture is highly stable at intermediate temperatures (600°C–800°C) and provides
continuous pathways for charge transport throughout the cathode.
Finally, there is a third generation of materials consisting of nanostructured nanocomposites.

An improvement in oxygen reduction reaction (ORR) activity was reported when LSM
nanoparticles were loaded on a porous YSZ framework [163–166]. Also, electrocatalytic
nanoparticles could be produced in oxide anodes for solid oxide fuel cell (SOFC) by an ex-
solution method, i.e., by incorporating metals into a perovskite oxide phase in air followed by
the reduction of the perovskite oxide [167]. The improvement in the performance of the cell
by using these nanocomposites lies in the extension of the TPB to the newly generated surfaces
[168]. Templates such as polycarbonate membranes have also been used for the production of
composite nanotubes with 20 nm wall thicknesses [169]. With this strategy, a clear decrease in
polarization resistance of the electrode is observed, giving rise to higher efficiencies at
temperatures as low as 700°C. Recently, an electrolyte-supported SOFC was fabricated with
all-nanocomposite components and operated below 600°C [170]. The highly active nanocom‐
posite electrodes and easily sintered nanocomposite electrolyte allow an in situ low-temper‐
ature sintering while preserving the microstructure and electrochemical performance stability
upon thermal cycling.
The performance of intermediate temperature SOFCs can be improved by engineering the

electrode architecture on the nanoscale. Lowering the temperature facilitates the use of
nanotechnology in synthesizing new nanostructured materials in which parameters such as
porosity, the distribution of generated pores, and surface area can be closely controlled. These
parameters have a significant influence on the performance of the materials used for energy
conversion and storage, which means that these methods are an important starting point for
the design and optimization of these types of energy devices.
6. Conclusions
The great versatility of the perovskite structure allows for different doping to obtain a variety
of properties, which is a key feature in the development of materials for solid oxide fuel cells
(SOFCs). This chapter not only briefly introduces the foundation and operation of SOFCs but
also shows the evolution of perovskite materials for device components. Among the electro‐
lytes, BaCeO3-based cerates exhibit the highest ionic conduction at intermediate temperatures
while chromites doped with Sr find potential as interconnector materials. By introducing Fe
in the Cr site, these chromites become interesting alternatives to the traditional NiO anode, in
addition to the new trend of double perovskite-type materials such as Sr2MgMoO6, which
present very promising results for anode application. It is in the area of SOFC cathodes in
which the most progress has been made. Initially, in the 1960s, doped manganese perovskites
(La1-xSrxMnO3—LSM) were used as cathodes, but the low ionic conduction forced the devel‐
opment of new materials based on Co and/or Fe-containing perovskites. In addition, they have
mixed ionic-electronic conductivity, allowing the active electrode area to extend across the
surface. This leaves Ba0.5,Sr0.5,Co0.8,Fe0.2O3 perovskite as the most promising cathode material,
although as in the case of anodes, double perovskites are also alternative materials with
interesting properties.
Finally, it is worth mentioning the importance of not only the material composition but also
its structure, morphology and porosity. It has been found that a higher catalytic electrode area
results in a significant improvement in the electrochemical system efficiency. Reducing
operating temperatures of the SOFC has allowed nanotechnology to become a useful tool for
the development of future generations of materials for IT-SOFCs.
Acknowledgements
This work has been partially financed by the Ministerio de Educación y Ciencia under project
MAT2013-41128-R and by the Eusko Jaurlaritza/Gobierno Vasco under project IT-570-13. N.
Ortiz-Vitoriano acknowledges a Marie Curie International Outgoing Fellowship within the
EU Seventh Framework Programme for Research and Technological Development (2007–
2013).
Author details
Idoia Ruiz de Larramendi1, Nagore Ortiz-Vitoriano2, Isaen B. Dzul-Bautista1,3 and

Teófilo Rojo1,2
*Address all correspondence to: idoia.ruizdelarramendi@ehu.es
1 Departamento de Química Inorgánica, Universidad del País Vasco UPV/EHU, Bilbao,

Spain
2 CIC energiGUNE, Parque Tecnológico de Álava, Miñano, Spain
3 Centro de Innovación, Investigación y Desarrollo en Ingeniería y Tecnología, PIIT

Monterrey, CP, Apodaca, Nuevo León, Mexico
http://dx.doi.org/10.5772/61304
References
[1] Goto S, Oguma M, Chollacoop N, editors. EAS-ERIA Biodiesel Fuel Trade Hand‐
book: 2010, Jakarta: ERIA, 2010. p. 6–15.
[2] Ruiz de Larramendi, I. Ln1-xSrxFe0.8M0.2O3-δ (Ln = Pr, Gd; M = Co, Ni, Cr, Ga; x = 0.1,
0.2, 0.3) Perovskite Type Oxides as Cathode Materials for Solid Oxide Fuel Cells [the‐
sis]. University of the Basque Country (UPV/EHU), Bilbao; 2007.
[3] Primdahl, S. Nickel/Yttria-Stabilized Zirconia Cermet Anodes for Solid Oxide Fuel
Cells [thesis]. University of Twente, Faculty of Chemical Technology, The Nether‐
lands and Risø National Laboratory, Materials Research Department, Denmark; 1999.
[4] Grove, W.R. Philos. Mag. 1839; Ser. 3–14: 127–130.
[5] Nernst, W. Material for electric-lamp glowers. USA, US patent No.: U 00685730, 1901.
[6] Ortiz-Vitoriano N, Bernuy-López C, Ruiz de Larramendi I, Knibbe R, Thydén K,
Hauch A, Holtappels P, Rojo T. Optimizing solid oxide fuel cell cathode processing
route for intermediate temperature operation. Appl. Energy. 2013;104:984–991.
[7] Tu H, Stimming U. Advances, aging mechanisms and lifetime in solid-oxide fuel

cells. J. Power Sources. 2004;127:284–293.
[8] Blenow, P. Strontium-Titanate–Based Anodes for Solid Oxide Fuel Cells [thesis].
Lund University, Sweden. 2007.
[9] Zhao Y, Xia C, Jia L, Wang Z, Li H, Yu J, Li Y. Recent progress on solid oxide fuel
cell: Lowering temperature and utilizing non-hydrogen fuels. Int. J. Hydrogen Energ.
2013;38:16498–16517.
[10] West AR. Inorganic functional materials: optimization of properties by structural and
compositional control. The Chem. Rec. 2006;6:206–216.
[11] Mogensen M, Lybye D, Bonanos N, Hendriksen PV, Poulsen FW. Factors controlling
the oxide ion conductivity of fluorite and perovskite structured oxides. Solid State
Ionics. 2004;174:279–286.
[12] Sun C, Hui R, Roller J. Cathode materials for solid oxide fuel cells: a review. J Solid
State Electrochem. 2009;14:1125–1144.
[13] Zhou W, Ran R, Shao Z. Progress in understanding and development of

Ba0.5Sr0.5Co0.8Fe0.2O3-δ-based cathodes for intermediate-temperature solid-oxide fuel
cells: A review. J. Power Sources. 2009;192:231–246.
[14] Janardhanan VM, Heuveline V, Deutschmann O. Three-phase boundary length in

solid-oxide fuel cells: A mathematical model. J. Power Sources. 2008;178:368–372
[15] Ciucci F, Chueh WC, Goodwin DG, Haile SM. Surface reaction and transport in
mixed conductors with electrochemically-active surfaces: a 2-D numerical study of
ceria. Phys. Chem. Chem. Phys., 2011;13:2121–2135.
[16] Muñoz-García AB, Ritzmann AM, Pavone M, Keith JA, Carter EA. Oxygen transport
in perovskite-type solid oxide fuel cell materials: insights from quantum mechanics.
Acc. Chem. Res. 2014;47:3340–3348.
[17] Ruiz de Larramendi I, Vivès S, Ortiz-Vitoriano N, Ruiz de Larramendi JI, Arriortua

MI, Rojo T. La0.6Sr0.2Ca0.2Fe0.8Ni0.2O3 thin films obtained by pulsed laser ablation: effect
of the substrate on the electrochemical behaviour. Solid State Ionics. 2011;192:584–
590.
[18] Jacobson AJ. Materials for solid oxide fuel cells. Chem. Mater. 2010;22:660–674.
[19] Pavone M, Muñoz-García AB, Ritzmann AM, Carter EA. First-principles study of
lanthanum strontium manganite: insights into electronic structure and oxygen va‐
cancy formation. J. Phys. Chem. C. 2014;118:13346–13356.
[20] Takeda, Y.; Sakaki, Y.; Ichikawa, T.; Imanishi, N.; Yamamoto, O.; Mori, M.; Mori, N. y
Abe, T. Stability of La1−xAxMnO3−z (A=Ca, Sr) as cathode materials for solid oxide fuel
cells. Solid State Ionics. 1994;72:257–264.
[21] DeSouza RA, Islam MS, Ivers-Tiffee EJ. Formation and migration of cation defects in
the perovskite oxide LaMnO3. Mater. Chem. 1999;9:1621–1627.
[22] Herle JV, McEvoy AJ, Thampi KR. A study on the La1−xSrxMnO3 oxygen cathode.
Electrochim. Acta. 1996;41:1447–1454.
[23] Skinner SJ. Recent advances in perovskite-type materials for solid oxide fuel cell
Cathodes. Int. J. Inorg. Mater. 2001;3:113–121.
[24] Choi Y, Choi MC, Liu M. Rational design of novel cathode materials in solid oxide
fuel cells using first-principles simulations. J. Power Sources. 2010;195:1441–1445.
[25] Wen TL, Tu H, Xu Z, Yamamoto O. A study of (Pr,Nd,Sm)SrMnO cathode materials

for solid oxide fuel cell. Solid State Ionics. 1999;121:25–30.
[26] Sakaki Y, Takeda Y, Kato A, Imanishi N, Yamamoto O, Hattori M, Iio M, Esaki Y.

Ln1−xSrxMnO3 (Ln = Pr, Nd, Sm and Gd) as the cathode material for solid oxide fuel
cells. Solid State Ionics. 1999;118:187–194.
[27] Kostogloudis GC, Ftikos C. Characterization of Nd1-xSrxMnO3±δ SOFC cathode materi‐

als. J. Eur. Ceram. Soc. 1999;19:497–505.
[28] Kostogloudis GC, Vasihkos N, Ftikos C. Preparation and characterization of Pr1-

xSrxMnO3 ± δ (x = 0, 0.15, 0.3, 0.4, 0.5) as a potential SOFC cathode material operating at
intermediate temperatures (500–700°C). J. Eur. Ceram. Soc. 1997;17:1513–1521.
http://dx.doi.org/10.5772/61304
[29] Rim HR, Jeung SK, Jung E, Lee JS. Characteristics of Pr1−xMxMnO3 (M = Ca, Sr) as
cathode material in solid oxide fuel cells. Mater. Chem. Phys. 1998;52:54–59.
[30] Shao Z, Halle SM. A high-performance cathode for the next generation of solid-oxide
fuel cells. Nature. 2004;431:170–173.
[31] Tai LW, Nasrallah MM, Anderson HU, Sparlin DM, Sehlin SR. Structure and electri‐
cal properties of La1 − xSrxCo1 − yFeyO3. Part 2. The system La1 − xSrxCo0.2Fe0.8O3. Solid
State Ionics. 1995;76:273–283.
[32] Singhal SC, Kendal K, editors. High Temperature Solid Oxide Fuel Cells. Elsevier.
2004.
[33] Mai A, Haanappel BAC, Uhlenbruck S, Tietz F, Stöver D. Ferrite-based perovskites as

cathode materials for anode-supported solid oxide fuel cells: Part I. Variation of com‐
position. Solid State Ionics. 2005;176:1341–1350.
[34] Wang H, Tablet C, Feldhoff A, Caro J. A cobalt-free oxygen-permeable membrane

based on the perovskite-type oxide Ba0.5Sr0.5Zn0.2Fe0.8O3–δ. Adv. Mater. 2005;17:1785–
1788.
[35] Ortiz-Vitoriano N, Ruiz de Larramendi I, Gil de Muro I, Larrañaga A, Ruiz de Larra‐

mendi JI, Rojo T. A novel one step synthesized Co-free perovskite/brownmillerite
nanocomposite for solid oxide fuel cells. J. Mater. Chem, 2011;21:9682–9691.
[36] Stevenson JW, Armstrong TR, Carneim RD, Pederson LR, Weber WJ. Electrochemical
properties of mixed conducting perovskites La1 − xMxCo1 − yFeyO3 − δ (M = Sr, Ba, Ca). J.
Electrochem. Soc. 1996;143:2722–2729.
[37] Liu X, Cheng B, Hu J, Qin H, Jiang M. Preparation, structure, resistance and meth‐
ane-gas sensing properties of nominal La1−xMgxFeO3. Sens. Actuator B-Chem.
2008;133:340–344.
[38] Plonczak P, Gazda M, Kusz B, Jasinski P. Fabrication of solid oxide fuel cell support‐
ed on specially performed ferrite-based perovskite cathode.J. Power Sources.
2008;181:1–7.
[39] Yoon KJ, Zink PA, Gopalan S, Pal UB, Pederson LR. Defect chemistry and electrical
properties of (La0.8Ca0.2)0.95FeO3 − δ fuel cells and energy conversion. J. Electrochem.
Soc. 2009;156:B795-B800.
[40] Hashimoto SI, Kammer K, Larsen PH, Pulsen FW, Mogensen M. A study of
Pr0.7Sr0.3Fe1−xNixO3−δ as a cathode material for SOFCs with intermediate operating
temperature. Solid State Ionics. 2005;176:1013–1020.
[41] Ruiz de Larramendi I, López Antón R, Ruiz de Larramendi JI, Baliteau S, Mauvy F,
Grenier JC, Rojo T. Structural and electrical properties of thin films of
Pr0.8Sr0.2Fe0.8Ni0.2O3−δ. J. Power Sources. 2007;169:35–39.
[42] Chiba R, Yoshimura F, Sakurai Y. An investigation of LaNi1−xFexO3 as a cathode ma‐

terial for solid oxide fuel cells. Solid State Ionics. 1999;124:281–288.
[43] Ruiz de Larramendi I, Ortiz N, López-Antón R, Ruiz de Larramendi JI, Rojo T. Struc‐
ture and impedance spectroscopy of La0.6Ca0.4Fe0.8Ni0.2O3−δ thin films grown by pulsed
laser deposition. J. Power Sources. 2007;171:747–753.
[44] El-Himri A, Marrero-López D, Ruiz-Morales JC, Peña-Martínez J, Núñez P. Structur‐

al and electrochemical characterisation of Pr0.7Ca0.3Cr1−yMnyO3−δ as symmetrical solid
oxide fuel cell electrodes. J. Power Sources. 2009;188:230–237.
[45] Ortiz-Vitoriano N, Ruiz de Larramendi I, Ruiz de Larramendi JI, Arriortua MI, Rojo
T. Synthesis and electrochemical performance of La0.6Ca0.4Fe1−xNixO3 (x = 0.1, 0.2, 0.3)
material for solid oxide fuel cell cathode. J. Power Sources. 2009;192;63–69.
[46] Taguchi H, Masunaga Y, Hirota K, Yamaguchi O, Synthesis of perovskite-type

(La1−xCax)FeO3 (0 ≤ x ≤ 0.2) at low temperature. Mater Res. Bull. 2005;40:773–780.
[47] Montini T, Bevilacqua M, Fonda E, Casulla MF, Lee S, Tavagnacco C, Gorte RJ, For‐
nasiero P. Relationship between electrical behavior and structural characteristics in
Sr-doped LaNi0.6Fe0.4O3−δ mixed oxides. Chem. Mater. 2009;21:1768–1774.
[48] Ortiz-Vitoriano N, Ruiz de Larramendi I, Cook SN, Burriel M, Aguadero A, Kilner

JA, Rojo T. The formation of performance enhancing pseudo-composites in the high‐
ly active La1–xCaxFe0.8Ni0.2O3 system for IT-SOFC Application. Adv. Funct. Mater.
2013;23:5131–5139.
[49] Ortiz-Vitoriano N, Ruiz de Larramendi I, Ruiz de Larramendi JI, Arriortua MI, Rojo
T. Optimization of La0.6Ca0.4Fe0.8Ni0.2O3–Ce0.8Sm0.2O2 composite cathodes for inter‐
mediate-temperature solid oxide fuel cells. J. Power Sources. 2011;196:4332–4336.
[50] Dusastre V, Kilner JA. Optimisation of composite cathodes for intermediate tempera‐
ture SOFC applications. Solid State Ionics. 1999;126:163–174.
[51] Wang K, Ran R, Zhou W, Gu H, Shao Z, Ahn J. Properties and performance of

Ba0.5Sr0.5Co0.8Fe0.2O3−δ + Sm0.2Ce0.8O1.9 composite cathode. J. Power Sources.
2008;179:60–68.
[52] Tarancón A, Morata A, Dezanneau G, Skinner SJ, Kilner JA, Estradé S, Hernández-
Ramírez F, Peiró F, Morante JR. GdBaCo2O5+x layered perovskite as an intermediate
temperature solid oxide fuel cell cathode. J. Power Sources. 2007;174:255–263.
[53] Frontera C, García-Muñoz JL, Castaño O, Ritter C, Caneiro A. The effect of oxygen
disorder on magnetic properties of PrBaCo2O5.50layered cobaltite. J. Phys.: Condens.
Matter. 2008;20:104228(8)
[54] Kim JH, Kim YM, Connor PA, Irvine JTS, Bae J, Zhou WZCS. Structural, thermal and
electrochemical properties of layered perovskite SmBaCo2O5+d, a potential cathode
http://dx.doi.org/10.5772/61304
material for intermediate-temperature solid oxide fuel cells. J. Power Sources.

2009;194:704–711
[55] Zhao L, He BB, Xun ZQ, Wang H, Peng RR, Meng GY, Liu XQ. Characterization and
evaluation of NdBaCo2O5+δ cathode for proton-conducting solid oxide fuel cells. Int.
J. Hydrogen Energ. 2010;35:753–756.
[56] Kim G, Wang S,. Jacobson AJ, Reimus L, Brodersen P, Mims CA. Rapid oxygen ion
diffusion and surface exchange kinetics in PrBaCo2O5+xwith a perovskite related
structure and ordered A cations. J. Mater. Chem. 2007;17:2500–2505.
[57] Bak T, Nowotny J, Rekas M, Sorell CC, Vance ER. A manometric method for the de‐
termination of chemical diffusion in non-stoichiometric oxides: Example of
(La,Sr)MnO3. Solid State Sci. 2000;135:557–561.
[58] Marrero-López D, dos Santos-Gómez L, Canales-Vázquez J, Martín F, Ramos-Barra‐

do JR. Stability and performance of nanostructured La0.8Sr0.2MnO3 cathodes deposit‐
ed by spray-pyrolysis. Electrochim. Acta. 2014;134:159–166.
[59] Bouwmeester HJM, Kruidhof H, Burggraaf AJ. Importance of the surface exchange
kinetics as rate limiting step in oxygen permeation through mixed-conducting ox‐
ides. Solid State Ionics. 1994;72:185–194.
[60] Søgaard M, Vang Hendriksen P, Mogensen M. Oxygen nonstoichiometry and trans‐

port properties of strontium substituted lanthanum ferrite. J. Solid State Chem.
2007;180:1489–1503.
[61] Ralph JM, Rossignol Cc, Kumar R. Cathode materials for reduced-temperature
SOFCs. J. Electrochem. Soc. 2003;150:A1518-A1522.
[62] Zomorrodian A, Salamati H, Lu Z, Chen X, Wu N, Ignatiev A. Electrical conductivity

of epitaxial La0.6Sr0.4Co0.2Fe0.8O3−δ thin films grown by pulsed laser deposition. Int. J.
Hydrogen Energ. 2010;35:12443–12448.
[63] Cox-Galhotra RA, McIntosh S. Unreliability of simultaneously determining kchem and

Dchem via conductivity relaxation for surface-modified La0.6Sr0.4Co0.2Fe0.8O3−δ. Solid
State Ionics. 2010;181:1429–1436.
[64] Lu H, Zhu L, Kim JP, Son SH, Park JH. Perovskite La0.6Sr0.4B0.2Fe0.8O3−δ (B = Ti, Cr, Co)
oxides: Structural, reduction-tolerant, sintering, and electrical properties. Solid State
Ionics. 2012;209–210:24–29.
[65] Garcia LMP, Macedo DA, Souza GL, Motta FV, Paskocimas CA, Nascimento RM.
Citrate–hydrothermal synthesis, structure and electrochemical performance of
La0.6Sr0.4Co0.2Fe0.8O3−δ cathodes for IT-SOFCs. Ceram. Int. 2013;39:8385–8392.
[66] Zhu G, Fang X, Xia C, Liu X. Preparation and electrical properties of

La0.4Sr0.6Ni0.2Fe0.8O3 using a glycine nitrate process. Ceram. Int. 2005;31:115–119.
[67] Chiba R, Yoshimura F, Sakurai Y. Properties of La1-ySryNi1-xFexO3 as a cathode

material for a low-temperature operating SOFC. Solid State Ionics. 2002;152–153:575–
582.
[68] Zhou Q, Xu L, Guo Y, Jia D, Li Y, Wei WCJ. La0.6Sr0.4Fe0.8Cu0.2O3−δ perovskite oxide as

cathode for IT-SOFC. Int. J. Hydrogen Energ. 2012;37:11963–11968.
[69] Meng X, Lü S, Ji Y, Wei T, Zhang Y. Characterization of Pr1−xSrxCo0.8Fe0.2O3−δ (0.2≤ x

≤0.6) cathode materials for intermediate-temperature solid oxide fuel cells. J. Power
Sources. 2008;183:581–585.
[70] Hashimoto S, Kammer K, Poulsen FW, Mogensen M. Conductivity and electrochemi‐

cal characterization of PrFe1−xNixO3−δ at high temperature. J. Alloys Compd.
2007;428:256–261.
[71] Rebello J, Vashook V, Trots D, Guth U. Thermal stability, oxygen non-stoichiometry,

electrical conductivity and diffusion characteristics of PrNi0.4Fe0.6O3−δ, a potential
cathode material for IT-SOFCs. J. Power Sources. 2011;196:3705–3712.
[72] Guo YQ, Yin YM, Tong Z, Yin JW, Xiong MW, Ma ZF. Impact of synthesis technique
on the structure and electrochemical characteristics of Pr0.6Sr0.4Co0.2Fe0.8O3−δ (PSCF)
cathode material. Solid State Ionics. 2011;193:18–22.
[73] Kostogloudis GC, Ftikos C. Crystal structure, thermal expansion and electrical con‐
ductivity of Pr1−xSrxCo0.2Fe0.8O3−δ (0≤ x ≤0.5). Solid State Ionics. 2000;135:537–541.
[74] Chang CL, Hsu CS, Hwang BH. Unique porous thick Sm0.5Sr0.5CoO3 solid oxide fuel
cell cathode films prepared by spray pyrolysis. J. Power Sources. 2008;179:734–738.
[75] Yang S, He T, He Q. Sm0.5Sr0.5CoO3 cathode material from glycine-nitrate process:

Formation, characterization, and application in LaGaO3-based solid oxide fuel cells. J.
Alloys Compd. 2008;450:400–404.
[76] Wei B, Lü Z, Huang X, Liu M, Li N, Su W. Synthesis, electrical and electrochemical

properties of Ba0.5Sr0.5Zn0.2Fe0.8O3−δ perovskite oxide for IT-SOFC cathode. J. Power
Sources. 2008;176:1–8.
[77] Lee S, Lim Y, Lee EA, Hwang HJ, Moon J-W. Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) and
La0.6Ba0.4Co0.2Fe0.8O3−δ (LBCF) cathodes prepared by combined citrate-EDTA method
for IT-SOFCs. J. Power Sources. 2006;157:848–854.
[78] Wei B, Lü Z, Huang X, Miao J, Sha X, Xin X, et al. Crystal structure, thermal expan‐
sion and electrical conductivity of perovskite oxides BaxSr1−xCo0.8Fe0.2O3−δ (0.3≤ x ≤0.7).
J. Eur. Ceram. Soc. 2006;26:2827–2832.
[79] Chen D, Ran R, Zhang K, Wang J, Shao Z. Intermediate-temperature electrochemical

performance of a polycrystalline PrBaCo2O5+δ cathode on samarium-doped ceria elec‐
trolyte. J. Power Sources. 2009;188:96–105.
http://dx.doi.org/10.5772/61304
[80] Meng F, Xia T, Wang J, Shi Z, Zhao H. Praseodymium-deficiency Pr0.94BaCo2O6-δ dou‐

ble perovskite: A promising high performance cathode material for intermediate-
temperature solid oxide fuel cells. J. Power Sources. 2015;293:741–750.
[81] Jin F, Xu H, Long W, Shen Y, He T. Characterization and evaluation of double perov‐

skites LnBaCoFeO5+δ (Ln = Pr and Nd) as intermediate-temperature solid oxide fuel
cell cathodes. J. Power Sources. 2013;243:10–18.
[82] Li N, Lü Z, Wei B, Huang X, Chen K, Zhang Y, et al. Characterization of GdBaCo2O5+δ

cathode for IT-SOFCs. J. Alloys Compd. 2008;454:274–279.
[83] Taskin AA, Lavrov AN, Ando Y. Achieving fast oxygen diffusion in perovskites by
cation ordering. Appl. Phys. Lett. 2005;86:091910.
[84] Zhou Q, He T, Ji Y. SmBaCo2O5+x double-perovskite structure cathode material for in‐

termediate-temperature solid-oxide fuel cells. J. Power Sources. 2008;185:754–758.
[85] Ding X, Kong X, Wu H, Zhu Y, Tang J, Zhong Y. SmBa0.5Sr0.5Cu2O5+δ and

SmBa0.5Sr0.5CuFeO5+δ layered perovskite oxides as cathodes for IT-SOFCs. Int. J. Hy‐
drogen Energ. 2012;37:2546–2551.
[86] Xue J, Shen Y, He T. Double-perovskites YBaCo2−xFexO5+δ cathodes for intermediate-

temperature solid oxide fuel cells. J. Power Sources. 2011;196:3729–3735.
[87] Zhu WZ, Deevi SC. A review on the status of anode materials for solid oxide fuel
cells. Mater. Sci. Eng. A 2003;362:228–239.
[88] Sun C, Stimming U. Recent anode advances in solid oxide fuel cells. J. Power Sour‐
ces. 2007;171:247–260.
[89] Atkinson A, Barnett S, Gorte RJ, Irvine JTS, McEvoy AJ, Mogensen M, Singhal SC,
Vohs J. Advanced anodes for high-temperature fuel cells. Nat. Mater. 2004;3:17–27.
[90] Boukamp BA. Fuel cells: The amazing perovskite anode. Nat. Mater. 2003;2:294–296.
[91] Verbraeken MC, Ramos T, Agersted K, Ma Q, Savaniu CD, Sudireddy BR, Irvine JTS,
Holtappels P, Tietz F. Modified strontium titanates: from defect chemistry to SOFC
anodes. RSC Adv. 2015;5:1168–1180.
[92] Yurkiv V, Constantin G, Hornes A, Gondolini A, Mercadelli E, Sanson A, Dessemond

L, Costa R. Towards understanding surface chemistry and electrochemistry of
La0.1Sr0.9TiO3-α based solid oxide fuel cell anodes. J. Power Sources. 2015;287:58–67.
[93] Marina OA, Canfield NL, Stevenson JW. Thermal, electrical, and electrocatalytical
properties of lanthanum-doped strontium titanate. Solid State Ionics. 2002;149:21–28.
[94] Hashimoto S, Kindermann L, Poulsen FW, Mogensen M. A study on the structural

and electrical properties of lanthanum-doped strontium titanate prepared in air. J.
Alloys Compd. 2005;397:245–249.
[95] Canales-Vázquez J, Ruiz-Morales JC, Irvine JTS, Zhou W. Sc-substituted oxygen ex‐
cess titanates as fuel electrodes for SOFCs. J. Electrochem. Soc. 2005;152:A1458–
A1465.
[96] Miller DN, Irvine JTS. B site doping of lanthanum strontium titanate for solid oxide
fuel cell anodes. J. Power Sources. 2011;196:7323–7327.
[97] Cui SH, Li JH, Zhou XW, Wang GY, Luo JL, Chuang KT, Bai Y, Qiao LJ. Cobalt dop‐
ed LaSrTiO3−δ as an anode catalyst: effect of Co nanoparticle precipitation on SOFCs
operating on H2S-containing hydrogen. J. Mater. Chem. A. 2013;1:9689–9696.
[98] Ma Q, Tietz F. Comparison of Y and La-substituted SrTiO3 as the anode materials for
SOFCs. Solid State Ionics. 2012;225:108–112.
[99] Park BH, Choi GM. Ex-solution of Ni nanoparticles in a La0.2Sr0.8Ti1−xNixO3−δ alterna‐

tive anode for solid oxide fuel cell. Solid State Ionics. 2014;262:345–348.
[100] Périllat-Merceroz C, Gauthier G, Roussel P, Huvé M, Gélin P, Vannier RN. Synthesis

and study of a Ce-doped La/Sr titanate for solid oxide fuel cell anode operating di‐
rectly on methane. Chem. Mater. 2011;23:1539–1550.
[101] Ruiz-Morales JC, Canales-Vázquez J, Savaniu C, Marrero-López D, Zhou W, Irvine

JTS. Disruption of extended defects in solid oxide fuel cell anodes for methane oxida‐
tion. Nature 2006;439:568–571.
[102] Chamberland BL, Danielson PS. Alkaline-earth vanadium (IV) oxides having the
AVO3 composition. J. Solid State Chem. 1971;3:243–247.
[103] Martínez-Coronado R, Alonso JA, Aguadero A, Fernández-Díaz MT. Optimized en‐

ergy conversion efficiency in solid-oxide fuel cells implementing SrMo1−xFexO3−δ per‐
ovskites as anodes. J. Power Sources. 2012;208:153–158.
[104] Martínez-Coronado R, Alonso JA, Aguadero A, Fernández-Díaz MT. New

SrMo1−xCrxO3−δ perovskites as anodes in solid-oxide fuel cells. Int. J. Hydrogen Energ.
2014;39:4067–4073.
[105] Martínez-Coronado R, Alonso JA, Fernández-Díaz MT. SrMo0.9Co0.1O3−δ: A potential

anode for intermediate-temperature solid-oxide fuel cells (IT-SOFC). J. Power Sour‐
ces. 2014;258:76–82.
[106] Du Z, Zhao H, Yang C, Shen Y, Yan C, Zhang Y. Optimization of strontium molyb‐

date based composite anode for solid oxide fuel cells. J. Power Sources. 2015;274:568–
574.
[107] Zheng K, Świerczek K, Bratek J, Klimkowicz A. Cation-ordered perovskite-type

anode and cathode materials for solid oxide fuel cells. Solid State Ionics.
2014;262:354–358.
[108] Liu Q, Dong X, Xiao G, Zhao F, Chen F. A novel electrode material for symmetrical
SOFCs. Adv. Mater. 2010;22:5478−5482.
http://dx.doi.org/10.5772/61304
[109] Suthirakun S, Ammal SC, Muñoz-García AB, Xiao G, Chen F, zur Loye HC, Carter
EA, Heyden A. Theoretical investigation of H2 oxidation on the Sr2Fe1.5Mo0.5O6 (001)
perovskite surface under anodic solid oxide fuel cell conditions. J. Am. Chem. Soc.
2014;136:8374–8386.
[110] Sfeir J. LaCrO3-based anodes: stability considerations. J. Power Sources.

2003;118:276–285.
[111] Lü MF, Tsipis EV, Waerenborgh JC, Yaremchenko AA, Kolotygin VA, Bredikhin S,
Kharton VV. Thermomechanical, transport and anodic properties of perovskite-type
(La0.75Sr0.25)0.95Cr1−xFexO3−δ. J. Power Sources. 2012;206:59–69.
[112] Tao SW, Irvine JTS. Catalytic properties of the perovskite oxide La0.75Sr0.25Cr0.5Fe0.5O3-δ
in relation to its potential as a solid oxide fuel cell anode material. Chem. Mater.
2004;16:4116–4121.
[113] Wei T, Liu XJ, Yuan C,. Gao QY, Xin XS, Wang SR. A modified liquid-phase-assisted
sintering mechanism for La0.8Sr0.2Cr1−xFexO3−δ—A high density, redox-stable perov‐
skite interconnect for solid oxide fuel cells. J. Power Sources. 2014;250:152–159.
[114] Fowler DE, Haag JM, Boland C, Bierschenk DM, Barnett SA, Poeppelmeier KR. Sta‐
ble, low polarization resistance solid oxide fuel cell anodes: La1–xSrxCr1–xFexO3-δ (x =
0.2–0.67). Chem. Mater. 2014;26:3113–3120.
[115] Huang YH, Dass RI, Xing ZL, Goodenough JB. Double perovskites as anode materi‐
als for solid-oxide fuel cells. Science 2006;312:254–257.
[116] Choi S, Yoo S, Kim J, Park S, Jun A, Sengodan S, Kim J, Shin J, Jeong HY, Choi Y, Kim
G, Liu M. Highly efficient and robust cathode materials for low-temperature solid
oxide fuel cells: PrBa0.5Sr0.5Co2−xFexO5+δ. Sci. Rep. 2013;3:2426-6.
[117] Sengodan S, Choi S, Jun A, Shin TH, Ju YW, Jeong HY, Shin J, Irvine JTS, Kim G. Lay‐
ered oxygen-deficient double perovskite as an efficient and stable anode for direct
hydrocarbon solid oxide fuel cells. Nat. Mater. 2015;14:205–209.
[118] Périllat-Merceroz C, Roussel P, Huvé M, Capoen E, Rosini S, Gélin P, Vannier RN,

Gauthier GH. Pure and Mn-doped La4SrTi5O17 layered perovskite as potential solid
oxide fuel cell material: Structure and anodic performance J. Power Sources.
2015;274:806–815.
[119] Ruiz de Larramendi I, Ortiz-Vitoriano N, Acebedo B, Jimenez de Aberasturi D, Gil de

Muro I, Arango A, Rodríguez-Castellón E, Ruiz de Larramendi JI, Rojo T. Pr-doped
ceria nanoparticles as intermediate temperature ionic conductors. Int. J. Hydrogen
Energ. 2011;36:10981–10990.
[120] McEvoy AJ. Thin SOFC electrolytes and their interfaces—A near-term research strat‐
egy. Solid State Ionics. 2000;132:159–165.
[121] Chen XJ, Khor KA, Chan SH, Yu LG. Influence of microstructure on the ionic con‐
ductivity of yttria-stabilized zirconia electrolyte. Mater. Sci. Eng. A 2002;A335:246–
252
[122] Vlasov AN, Perfiliev MV. Ageing of ZrO2-based solid electrolytes. Solid State Ionics
1987;25:245–253.
[123] Slater PR, Irvine JTS, Ishihara T, Takita Y. The structure of the oxide ion conductor
La0.9Sr0.1Ga0.8Mg0.2O2.85 by powder neutron diffraction. Solid State Ionics.
1998;107:319–323.
[124] Kim S, Chun MC, Lee KT, Lee HL. Oxygen-ion conductivity of BaO- and MgO-dop‐
ed LaGaO3 electrolytes. J. Power Sources. 2001;93:279–284.
[125] Sood K, Singh K, Pandey OP. Structural and electrical behavior of Ba-doped LaGaO3
composite electrolyte. J. Renew. Sust. Energy. 2014;6:063112.
[126] Kurumada M, Hara H, Munakata F, Iguchi E. Electric conductions in La0.9Sr0.1GaO3−δ

and La0.9Sr0.1Ga0.9Mg0.1O3−δ. Solid State Ionics. 2005;176:245–251.
[127] Mineshige A, Izutsu J, Nakamura M, Nigaki K, Abe J, Kobune M, Fujii S, Yazawa T.

Introduction of A site deficiency into La0.6Sr0.4Co0.2Fe0.8O3–δ and its effect on structure
and conductivity. Solid State Ionics. 2005;176:1145–1149.
[128] Ahamd-Khanlou A, Tietz F, Stöver D. Material properties of La0.8Sr0.2Ga0.9+xMg0.1O3−δ

as a function of Ga content. Solid State Ionics. 2000;135:543–547.
[129] Zhang L, Xiao J, Xie Y, Tang Y, Liu J, Liu M. Behavior of strontium- and magnesium-
doped gallate electrolyte in direct carbon solid oxide fuel cells. J. Alloys Compd.
2014;608:272–277.
[130] Wang XP, Zhou DF, Yang GC, Sun SC, Li ZH, Fu H, Meng J. Nonstoichiometric
(La0.95Sr0.05)xGa0.9Mg0.1O3−δ electrolytes and Ce0.8Nd0.2O1.9–(La0.95Sr0.05)xGa0.9Mg0.1O3−δ
composite electrolytes for solid oxide fuel cells. Int. J. Hydrogen Energ. 2014;39:1005–
1013
[131] Feng M, Goodenough JB, Huang K, Milliken C. Fuel cells with doped lanthanum gal‐
late electrolyte. J. Power Sources. 1996;63:47–51.
[132] Lo Faro M, Aricò AS. Electrochemical behaviour of an all-perovskite-based inter‐

mediate temperature solid oxide fuel cell. Int. J. Hydrogen Energ. 2013;38:14773–
14778
[133] Yamazaki Y, Blanc F, Okuyama Y, Buannic L, Lucio-Vega JC, Grey CP, Haile SM.
Proton trapping in yttrium-doped barium zirconate. Nat. Mater. 2013;12:647–651.
[134] Liu Y, Ran R, Li S, Jiao Y, Tade MO, Shao Z. Significant performance enhancement of
yttrium-doped barium cerate proton conductor as electrolyte for solid oxide fuel cells
through a Pd ingress–egress approach. J. Power Sources. 2014;257:308–318.
http://dx.doi.org/10.5772/61304
[135] Stevenson DA, Jiang N, Buchanan RM, Henn FEG. Characterization of Gd, Yb and
Nd doped barium cerates as proton conductors. Solid State Ionics. 1993;62:279–285.
[136] Oishi M, Yashiro K, Sato K, Mizusaki J, Kitamura N, Amezawa K, Kawada T, Uchi‐

moto Y. Oxygen nonstoichiometry of the perovskite-type oxides BaCe0.9M0.1O3−δ (M =
Y, Yb, Sm, Tb, and Nd). Solid State Ionics. 2008;179:529–535.
[137] Nguyen NTQ, Yoon HH. Preparation and evaluation of BaZr0.1Ce0.7Y0.1Yb0.1O3−δ

(BZCYYb) electrolyte and BZCYYb-based solid oxide fuel cells. J. Power Sources.
2013;231:213–218.
[138] Fergus JW. Lanthanum chromite-based materials for solid oxide fuel cell intercon‐
nects. Solid State Ionics. 2004;171:1–15.
[139] Devi PS, Rao MS. Preparation, structure, and properties of strontium-doped lantha‐
num chromites: La1−xSrxCrO3. J. Solid State Chem. 1992;98:237–244.
[140] Flandermeyer BK, Nasrallah MM, Agarwal AK, Anderson HU. Defect structure of
Mg-doped LaCrO3 model and thermogravimetric measurements. J. Am. Ceram. Soc.
1984;67:195–198.
[141] Coutures JP, Badie JM, Berjoan R, Coutures J, Flamand R, Rouanet A. Stability and
thermodynamic properties of rare earth perovskites. High Temp. Sci. 1979;13: 331–
336.
[142] Lee HC, Kang BK, Lee JH, Heo YW, Kim JY, Kim JJ. Adhesion behavior between yt‐
trium-stabilized zirconia added La0.8Ca0.2Cr0.9Co0.1O3−δ interconnector and yttrium-sta‐
bilized zirconia-based substrate. Ceram. Int. 2013;39:8737–8741.
[143] Ruiz-Morales JC, Canales-Vázquez J, Marrero-López D, Peña-Martínez J, Pérez-Coll

D, Núñez P, Rodríguez-Placeres JC, Ballesteros-Pérez B, Dorta-Martín VI, Savaniu C.
Pilas de Combustible de Óxidos Sólidos (SOFC) Ed. Centro de la Cultura Popular
Canaria. ISBN: 978-84-7926-567-0, 2008.
[144] Choi J, Kim B, Shin D. Fibrous mixed conducting cathode with embedded ionic con‐
ducting particles for solid oxide fuel cells. Int. J. Hydrogen Energ. 2014;39:14460–
14465.
[145] Hueso L, Mathur N. Dreams of a hollow future. Nature. 2004;427:301–304.
[146] Ruiz-Morales JC, Marrero-López D, Gálvez-Sánchez M, Canales-Vázquez J, Savaniu

C, Savvina SN. Engineering of materials for solid oxide fuel cells and other energy
and environmental applications. Energy Environ. Sci. 2010;3:1670–1681.
[147] Pinedo R, Ruiz de Larramendi I, Ortiz-Vitoriano N, Jimenez de Aberasturi D, Rojo T.

Nanotechnology for improving solid oxide fuel cells. Materials and processes for en‐
ergy: communicating current research and technological developments (A. Méndez-
Vilas, Ed.). 512–522. 2013.
[148] Jimenez de Aberasturi D, Serrano-Montes AB, Liz-Marzán LM. Modern applications

of plasmonic nanoparticles: from energy to health. Adv. Optical Mater. 2015;3:602–
617.
[149] Jiang SP. A review of wet impregnation—An alternative method for the fabrication
of high performance and nano-structured electrodes of solid oxide fuel cells. Mater.
Sci. Eng. A. 2006;418:199–210.
[150] Liu Z, Liu B, Ding D, Liu M, Chen F, Xia C. Fabrication and modification of solid ox‐
ide fuel cell anodes via wet impregnation/infiltration technique. J. Power Sources.
2013;237:243–259.
[151] Marrero-López D, Ruiz-Morales JC, Peña-Martínez J, Canales-Vázquez J, Núñez P.

Preparation of thin layer materials with macroporous microstructure for SOFC appli‐
cations. J. Solid State Chem. 2008;181:685–692.
[152] Pinedo R, Ruiz de Larramendi I, Gil de Muro I, Insausti M, Ruiz de Larramendi JI,
Arriortua MI, Rojo T. Influence of colloidal templates on the impedance spectroscop‐
ic behaviour of Pr0.7Sr0.3Fe0.8Ni0. or solid oxide fuel cell applications. Solid State Ionics.
2011;192:235–240.
[153] Pinedo R, Ruiz de Larramendi I, Jimenez de Aberasturi D, Gil de Muro I, Aguayo

AT, Ruiz de Larramendi JI, Rojo T. A straightforward synthesis of carbon nanotube–
perovskite composites for solid oxide fuel cells. J. Mater. Chem. 2011;21:10273–10276.
[154] Pinedo R, Ruiz de Larramendi I, Khavrus VO, Jimenez de Aberasturi D, Ruiz de Lar‐
ramendi JI, Ritscheld M, Leonhardt A, Rojo T. Microstructural improvements of the
gradient composite material Pr0.6Sr0.4Fe0.8Co0.2O3/Ce0.8Sm0.2O1.9 by employing vertically
aligned carbon nanotubes. Int. J. Hydrogen Energ. 2014;39:4074–4080.
[155] Bellino MG, Sacanell JG, Lamas DG, Leyva AG, Walsöe de Reca NE. High-perform‐
ance solid-oxide fuel cell cathodes based on cobaltite nanotubes. J. Am. Chem. Soc.
2007;129:3066–3067.
[156] Liu J, Wang X, Peng Q, Li Y. Vanadium pentoxide nanobelts: highly selective and
stable ethanol sensor materials. Adv. Mater. 2005;17:764–767.
[157] Kuo TJ, Huang MH. Gold-catalyzed low-temperature growth of cadmium oxide
nanowires by vapor transport. J. Phys. Chem. B 2006;110:13717–13721.
[158] Ostermann R, Li D, Yin Y, McCann JT, Xia Y. V2O5 Nanorods on TiO2 Nanofibers: A
new class of hierarchical nanostructures enabled by electrospinning and calcination.
Nano Lett. 2006;6:1297–1302.
[159] Kwon CW, Son JW, Lee JH, Kim HM, Lee HW, Kim KB. High-performance micro-
solid oxide fuel cells fabricated on nanoporous anodic aluminum oxide templates.
Adv. Funct. Mater. 2011;21:1154–1159.
http://dx.doi.org/10.5772/61304
[160] Boehme M, Ionescu E, Fu G, Ensinger W. Room temperature synthesis of indium tin

oxide nanotubes with high precision wall thickness by electroless deposition. J.
Nanotech. 2011;2:119–126.
[161] Pinedo R, Ruiz de Larramendi I, Jimenez de Aberasturi D, Gil de Muro I, Ruiz de

Larramendi JI, Arriortua MI, Rojo T. Synthesis of highly ordered three-dimensional
nanostructures and the influence of the temperature on their application as solid ox‐
ide fuel cells cathodes. J. Power Sources. 2011;196:4174–4180.
[162] Zhi M, Lee S, Miller N, Menzler NH, Wu N. An intermediate-temperature solid ox‐

ide fuel cell with electrospun nanofiber cathode. Energy Environ. Sci. 2012;5:7066–
7071.
[163] Huang YY, Vohs JM, Gorte RJ. Characterization of LSM-YSZ composites prepared by
impregnation methods. J. Electrochem. Soc. 2005;152:A1347−A1353.
[164] Zhi MJ, Mariani N, Gemmen R, Gerdes K, Wu NQ. Nanofiber scaffold for cathode of
solid oxide fuel cell. Energy Environ. Sci. 2011;4:417−420.
[165] Zhang N, Li J, Li W, Ni D, Sun K. High performance three-dimensionally ordered

macroporous composite cathodes for intermediate temperature solid oxide fuel cells.
RSC Adv. 2012;2:802–804.
[166] Zhang X, Liu L, Zhao Z, Tu B, Ou D, Cui D, Wei X, Chen X, Cheng M. Enhanced oxy‐
gen reduction activity and solid oxide fuel cell performance with a nanoparticles-
loaded cathode. NanoLett. 2015;15:1703−1709.
[167] Park BH, Choi GM. Ex-solution of Ni nanoparticles in a La0.2Sr0.8Ti1−xNixO3−δ alterna‐

tive anode for solid oxide fuel cell. Solid State Ionics. 2014;262:345–348.
[168] Vohs JM, Gorte RJ. High-performance SOFC cathodes prepared by infiltration. Adv.
Mater. 2009;21:943−956.
[169] Pinedo R, Ruiz de Larramendi I, Ortiz-Vitoriano N, Gil de Muro I, Rojo T. Novel

Pr0.6Sr0.4Fe0.8Co0.2O3:Ce0.8Sm0.2O2 composite nanotubes for energy conversion and stor‐
age. J. Power Sources. 2012;201:332–339.
[170] Fan L, Wang C, Zhu B. Low temperature ceramic fuel cells using all nanocomposite
materials. NanoEnergy. 2012;1:631–639.

perovskite materials

Uploaded by

Copyright:

Available Formats

perovskite materials

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

perovskite materials

Uploaded by

Copyright:

Available Formats

Chapter 20

Designing Perovskite Oxides for Solid Oxide Fuel Cells

Idoia Ruiz de Larramendi, Nagore Ortiz-Vitoriano,

Additional information is available at the end of the chapter

Keywords: SOFC, Nanostructure

• Alkaline fuel cells (AFC)

• Polymer exchange membrane fuel cells (PEMFC)

• Phosphoric acid fuel cells (PAFC)

• Molten carbonate fuel cells (MCFC)

• Solid oxide fuel cells (SOFC)

Fuel Cell AFC PEMFC PAFC MCFC SOFC

Electrolyte KOH Polymer H3PO4 Li2CO3+K2 CO3 ZrO2+Y2O3

Toper.(°C) 65%–220 60%–130 150%–220 650 700%–1000

Electrical efficiency 45%–60% 40%–60% 35%–40% 45%–60% 45%–60%

Table 1. Most important characteristics for different types of fuel cells

2. What is a solid oxide fuel cell?

• A potential long-life expectancy of more than 40,000–80,000 h

• Constructed from readily obtainable ceramic materials

• Few problems with electrolyte management

• Internal reforming of hydrocarbon fuels is possible

3. Evolution of perovskite-type structured materials as electrodes in SOFCs

3.1. Cathode materials

Composition TEC (K–1) Resistivity Conductivity Diffusion Ref.

ASR T (°C) σ (S/cm) T (°C) k (cm/s) D (cm /s) T (°C)

La1-xSrxMnO3 11.6××10–6 0.18 750 180 800 — 3 × 10–9 800 [57,58]

3.2. Anode materials

4. Perovskite oxides as electrolytes and interconnectors for SOFC

5. Nanostructured perovskites for improving solid oxide fuel cells

Finally, there is a third generation of materials consisting of nanostructured nanocomposites.

The performance of intermediate temperature SOFCs can be improved by engineering the

Idoia Ruiz de Larramendi1, Nagore Ortiz-Vitoriano2, Isaen B. Dzul-Bautista1,3 and

*Address all correspondence to: idoia.ruizdelarramendi@ehu.es

1 Departamento de Química Inorgánica, Universidad del País Vasco UPV/EHU, Bilbao,

2 CIC energiGUNE, Parque Tecnológico de Álava, Miñano, Spain

3 Centro de Innovación, Investigación y Desarrollo en Ingeniería y Tecnología, PIIT

[4] Grove, W.R. Philos. Mag. 1839; Ser. 3–14: 127–130.

[7] Tu H, Stimming U. Advances, aging mechanisms and lifetime in solid-oxide fuel

[13] Zhou W, Ran R, Shao Z. Progress in understanding and development of

[14] Janardhanan VM, Heuveline V, Deutschmann O. Three-phase boundary length in

[17] Ruiz de Larramendi I, Vivès S, Ortiz-Vitoriano N, Ruiz de Larramendi JI, Arriortua

[25] Wen TL, Tu H, Xu Z, Yamamoto O. A study of (Pr,Nd,Sm)SrMnO cathode materials

[26] Sakaki Y, Takeda Y, Kato A, Imanishi N, Yamamoto O, Hattori M, Iio M, Esaki Y.

[27] Kostogloudis GC, Ftikos C. Characterization of Nd1-xSrxMnO3±δ SOFC cathode materi‐

[28] Kostogloudis GC, Vasihkos N, Ftikos C. Preparation and characterization of Pr1-

[33] Mai A, Haanappel BAC, Uhlenbruck S, Tietz F, Stöver D. Ferrite-based perovskites as

[34] Wang H, Tablet C, Feldhoff A, Caro J. A cobalt-free oxygen-permeable membrane

[35] Ortiz-Vitoriano N, Ruiz de Larramendi I, Gil de Muro I, Larrañaga A, Ruiz de Larra‐

[42] Chiba R, Yoshimura F, Sakurai Y. An investigation of LaNi1−xFexO3 as a cathode ma‐

[44] El-Himri A, Marrero-López D, Ruiz-Morales JC, Peña-Martínez J, Núñez P. Structur‐

[46] Taguchi H, Masunaga Y, Hirota K, Yamaguchi O, Synthesis of perovskite-type

[48] Ortiz-Vitoriano N, Ruiz de Larramendi I, Cook SN, Burriel M, Aguadero A, Kilner

[51] Wang K, Ran R, Zhou W, Gu H, Shao Z, Ahn J. Properties and performance of

material for intermediate-temperature solid oxide fuel cells. J. Power Sources.

[58] Marrero-López D, dos Santos-Gómez L, Canales-Vázquez J, Martín F, Ramos-Barra‐

[60] Søgaard M, Vang Hendriksen P, Mogensen M. Oxygen nonstoichiometry and trans‐

[62] Zomorrodian A, Salamati H, Lu Z, Chen X, Wu N, Ignatiev A. Electrical conductivity

[63] Cox-Galhotra RA, McIntosh S. Unreliability of simultaneously determining kchem and

[66] Zhu G, Fang X, Xia C, Liu X. Preparation and electrical properties of

[67] Chiba R, Yoshimura F, Sakurai Y. Properties of La1-ySryNi1-xFexO3 as a cathode

[68] Zhou Q, Xu L, Guo Y, Jia D, Li Y, Wei WCJ. La0.6Sr0.4Fe0.8Cu0.2O3−δ perovskite oxide as