Inorganic Chemistry Communications 152 (2023) 110724

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Inorganic Chemistry Communications

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Short communication

Recent advances on electrolyte materials for SOFC: A review

Prerna Vinchhi a, Mukesh Khandla b, Kiran Chaudhary b, Ranjan Pati b, *
a
Department of Solar Energy, School of Energy Technology, Pandit Deendayal Energy University, Gandhinagar, India
b
Department of Chemistry, School of Energy Technology, Pandit Deendayal Energy University, Gandhinagar, India

A R T I C L E I N F O A B S T R A C T

Keywords: In recent years, solid oxide fuel cells (SOFC) have gained popularity as one of the highly efficient energy con­
Solid electrolytes version devices, which can achieve an efficiency of over 80 % with regeneration. The components of SOFC
YSZ include an anode, cathode, electrolyte, sealants, and interconnects. In this review, material selection for elec­
High-temperature
trolytes, fundamentals of operation and operating mechanisms, and processing of the materials, are discussed in
SOFC
detail. The major challenge SOFCs face is the hindered O2 migration that converts chemical energy into electrical
Ionic conductivity
energy in the solid electrolyte among others. Yttria stabilized zirconia (YSZ) is one of the most explored con­
ventional electrolyte materials for solid oxide fuel cells (SOFC) for high-temperature applications. Nano­
crystalline YSZ is regarded as a promising material in terms of high mechanical strength and structural stability
in both oxidizing and reducing atmospheres. This enhances its potential and enables its application. Different
parameters such as high-temperature operation, thickness, and compatibility with anode and cathode are prime
areas of focus. Generally, the two most important aspects of SOFC are: the electrolyte materials and what
temperature they operate. This review emphasizes about the history, recent advances, electrolytes materials used
in SOFC operated at both high and low temperature and electrolytes for the future.

1. Introduction (PAFC), direct methanol fuel cell (DMFC) and while others operating at
higher temperature (200–1000 ◦ C) such as molten carbon fuel cell
1.1. Definition and background (MCFC) and solid oxide fuel cells (SOFC). PEMFC, AFC, PAFC use liquid
electrolyte while MCFC and SOFC use solid electrolyte material. Among
In today’s world, the energy crisis has led to the urge of finding them, SOFC and PEMFC have gained lot of attention as efficient source
alternative sources of energy with use of minimum resources and high of energy conversion. However, SOFCs have the highest operating
energy yield. Many energy storage and conversion devices have been temperature as they use electrolyte in the form of solid making it operate
explored since past century from which “Fuel Cells” are one of them. A at elevated temperatures.
fuel cell is regarded as one of the leading and promising technologies for Moreover, in SOFC, there is no obligation of using noble metal
power generation due to its high efficiency, low emissions and quiet catalyst such as Pt, which is an important part in PEMFC. On the other
operation. Fuel cells are basically, electrochemical devices that directly hand, the metal like Ni acts as a catalyst in SOFC, which lower downs the
converts the chemical energy of gaseous fuel into electricity and heat cost of the cell. The electrolyte used in SOFC being in solid state, makes it
without any requirement of direct combustion of fuel as an intermediate leak proof and even easier to manage. In addition to this, it also gives the
step, in much efficient manner than conventional energy conversion advantage of fuel flexibility unlike PEMFC, which particularly requires
devices [1]. They are purely energy conversion devices and does not hydrogen as the fuel. Due to these properties, it has got wider applica­
store charge. They are also not limited by the Carnot cycle as compared tions as an industrial unit of combined heat and power source (CHP) and
to the conventional energy devices, which makes it more environmen­ also can be one of the good sources for stationary power generation.
tally friendly [2]. Depending upon the operating temperature and the
fuels fed, they can be categorized into three main classes: one operating
at low temperatures (<200 ◦ C) like alkaline fuel cell (AFC), polymer 1.2. History of fuel cell
electrolyte membrane fuel cells (PEMFC), phosphoric acid fuel cell
W. R. Grove in 1839 was the person to demonstrate the energy

* Corresponding author.
E-mail address: ranjan.pati@sse.pdpu.ac.in (R. Pati).

https://doi.org/10.1016/j.inoche.2023.110724
Received 31 August 2022; Received in revised form 9 April 2023; Accepted 13 April 2023
Available online 20 April 2023
1387-7003/© 2023 Elsevier B.V. All rights reserved.
P. Vinchhi et al. Inorganic Chemistry Communications 152 (2023) 110724

conversion by fuel cell using liquid sulfuric acid as the electrolyte and recombine with proton, delivered via electrolyte to produce water.
hydrogen and oxygen were used as anode and cathode respectively. Fig. 1 shows the schematic diagram of a typical solid oxide fuel cell
Subsequently, hydrogen and oxygen mixed with each other and pro­ (SOFC). The redox reactions happen across the anode and cathode
duced water. Grove is known as the father of fuel cell [3]. In 1889, respectively can be expressed as follows [8]:
Ludwig Mond and Carl Langer [4] developed Grove’s model and named
Anode Terminal : H2(g) + O2− → H2 O + 2e−
it as fuel cell. Later on E. Buar and H. Preis [5] experimented with high-
temperature solid oxide electrolytes in 1921, while in late 1930′ s [6], an
CO(g) + O2− →CO2 + 2e−
alkali fuel cell (AFC) was developed by Francis Bacon. The proton ex­
change membrane fuel cell (PEMFC) was invented by Willard Thomas
1
Grubb and Leonard Niedrich of General Electric in 1955 [7]. Subse­ Cathode Terminal: O2 (g) + 2e− → O2− (s)
2
quently, the Central Technical Institute of the Netherland started
research on SOFC in 1959 [8]. NASA first used alkali fuel cell in the
2. Development of electrolytes for SOFC
Apollo Space Mission in 1960 [9]. Later on 1961, G. V. Elmore experi­
mented on the phosphoric acid fuel cell [10].
An electrolyte is the heart of a SOFC unit, which conducts oxide ions
from the cathode to the anode where it reacts with hydrogen ions to
1.3. Solid oxide fuel cell (SOFC) produce H2O or with hydrocarbons to form H2O and CO2, and thus
completes the overall electrochemical reaction. The oxide ion conduc­
SOFCs are environmentally friendly and quiet and their high effec­ tion occurs via the oxygen vacancy hopping mechanism, which is a
tiveness decreases greenhouse gas emissions. They comprise of three thermally activated process. To achieve electrolyte materials having
essential parts: a porous anode, a porous cathode and a dense electrolyte high ionic conductivity, their crystal structure must possess large
layer. The electrolyte should be dense enough to separate the air and interionic open space that allows high level of point defect disorder, and
fuel, should have enough ionic conductivity to allow oxygen ions to low migration enthalpy [15]. Typically in such electrolyte materials, the
migrate properly, and act as an electrical protector. Generally, SOFC size of the metal cation is one of the deciding factors for getting high
operates at elevated temperatures, results heat release as by-product, ionic conductivity. Generally, in a crystal lattice, the host metal ion is
can be used for co-generation purposes, thereby increasing its effi­ larger than the dopant metal ion. Thus, it is expected that the smaller-
ciency even more, which is more than 40 % with a total efficiency of sized cations are more likely to possess appreciable mobility in the lat­
more than 80 % [11]. tice. However, inside the lattice, the metal cations also possess large
Depending on different operating temperature ranges, SOFCs can be charge valence, which restricts them from free movement, which is
classified as follows: high-temperature SOFCs (HT-SOFCs): 850 ◦ C- achieved by creating an oxygen vacancy defect inside the lattice and by
1000 ◦ C; intermediate temperature SOFCs (IT-SOFCs): 650 ◦ C-850 ◦ C; applying a driving force to facilitate the diffusion of oxide ions inside the
and low temperature SOFCs (LT-SOFCs) lower than 650 ◦ C. lattice. The best known examples of this kind are ZrO2, CeO2, Bi2O3
Due to their high operating temperatures, SOFCs have certain limi­ based oxides with the fluorite structure, LaGaO3 and Ba2In2O5 based
tations such as high cost of maintenance and reduction in the cell perovskites, Bi4V2O11 and La2Mo2O9 based derivatives, and so on [16].
durability with time. Each cell component gets exposed to high tem­ The main requirements for an electrolyte to work efficiently are [17]:
perature leading to generation of interfacial issues, which degrade the (i) oxide ion conductivity must be sufficiently high (0.1 S cm− 1 at
cell performance. operating temperature), (ii) low electronic transference number, (iii)
There are various electrolytes used in the SOFC such as, yttria sta­ thermodynamic and chemical stability over wide range of temperatures
bilized zirconia (YSZ), scandia stabilized zirconia (ScSZ), magnesia at different oxygen partial pressure, (iv) negligible volatilization, (v)
stabilized zirconia (MgSZ), and calcia stabilized zirconia (CaSZ) [12,13]. chemically inertness toward electrode materials both during processing
ScSZ, as compared to YSZ, gives high ionic yield but it is only because Sc and service, (vi) compatibility of solid electrolyte with the electrodes
is expensive, becomes less of a choice for electrolyte material. Among and (vii) possessing reliable mechanical properties.
all, YSZ is considered to be a state-of-art electrolyte material for high Fluorite structure oxides possess face-centered cubic arrangement of
temperature operation, having highest mechanical and chemical sta­ cations with anions occupying all the tetrahedral sites. CeO2, ZrO2,
bility along with high ionic conductivity [14]. The high operating HfO2, ThO2 and UO2 are the few examples of MO2 oxides that crystallize
temperature leads to restrictions in the material selection part especially
the choice of interconnects and the sealants. These and other operational
issues hinder the commercialization of SOFCs. Moreover, reducing the
operating temperature leads to lower ionic conductivity and also
degradation in the material properties such as mechanical and chemical
stability. Hence, efforts can only be made in increasing the ionic con­
ductivity of the electrolyte and modifying the fabrication and structural
designs.

1.4. Structure of an SOFC

As mentioned earlier, each component of the cell must have speci­

fications such as being chemically and thermally stable. These compo­
nents must have good chemical compatibility, that is, there should not
have or can have rather very negligible mismatch, as, if mismatch per­
sists it will lead to degradation of the cell. Also, the components must be
stable in both oxidizing and reducing atmospheres [2].
The anode serves as the negative electrode, distributes the hydrogen
gas uniformly across its surface. It coordinates the electrons transported
from the anode to be utilized as a substantial power in the external
circuit. While the cathode acts as a positive electrode, diffuses the ox­
ygen delivered to the surface. At cathode, oxygen gets reduced and Fig. 1. A schematic diagram showing all the components of a typical SOFC.

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P. Vinchhi et al. Inorganic Chemistry Communications 152 (2023) 110724

with fluorite structure. Other oxides such as Bi2O3 possess defective coatings, oxygen sensors, dental industries etc. It basically exists in three
fluorite structure in which two of the tetrahedral sites are unoccupied. crystal structure: monoclinic, tetragonal and cubic structures. At room
Among these oxides, only ZrO2, CeO2 and Bi2O3 have been of interest to temperature, it is present in monoclinic phase. When its temperature is
researchers as an electrolyte material in SOFC. Cubic fluorite oxides raised to about 1100 ◦ C, it undergoes transformation to reversible
have received a lot of attention in these studies due to their compara­ martensitic phase to tetragonal structure. It persists the tetragonal phase
tively open structure. Since the phase stabilization temperature for between temperature 1180 ◦ C to 2370 ◦ C and on further elevation of
acquiring cubic structure is very high, some alternative stabilizers are temperature it gets converted to cubic fluorite phase [22,23].
used in order to lower down the temperature. Phase stabilizers are Fig. 2 shows all the polymorphs of Zirconia: cubic, tetragonal and
basically, aliovalent cations such as Y3+, Ca2+, Mg2+ and Sc3+. These monoclinic. In the cubic ZrO2, Zr is coordinated to eight oxygen atoms
dopant cations, either divalent or trivalent, on introducing in the ZrO2 occupying the vertices as well as the center of each faces, while O atoms
crystal lattice, produce significant concentrations of charge carriers are four fold coordinated to Zr located at (1/4, 1/4, 1/4) sites of the FCC
resulting into charge imbalance [18]. Oxygen vacancies, which are the structure making the entire unit cell consists of 4 Zr atoms and 8O atoms.
mobile species, are formed to maintain the charge neutrality. The oxy­ The tetragonal phase structure has body centered crystal structure,
gen vacancies and the dopant cations form linked pairs. This oxygen having Zr atoms are located at (0, 0, 0) and (0.5, 0.5, 0.5) sites. In this
vacancy generation can be well expressed by Kroger-Vink equation as structure, alternative oxygen atoms are slightly deviated from their
follows [19]: lattice site by an amount dz = Δc/c, where c is the axis of deviation,
giving a bit of elongated structure than cubic. On the other hand,
(1)
ZrO2 ′
M2 O3 ̅̅̅→ 2[MZr ] + VO•• + 3OxO monoclinic phase exists at room temperature has Zr atoms attached to
These vacancies migrate through the crystal at elevated temperature seven O atoms. Oxygen atoms attach with Zr atoms having three and
generating ionic conduction. It is widely explored that Y3+ is an optimal four fold coordination [25].
dopant cation, when doped in ZrO2, substitute Zr4+ and generate oxygen In order to enhance the oxide ion conductivity, numerous composi­
vacancies. Similar phenomenon is observed in case of CeO2, when it is tions of ZrO2 have been explored. Acceptor dopants such as trivalent
doped with oxides of Sm, and Gd. lanthanide cations, and divalent alkaline earth cations, were extensively
The binding energy varies on dopant concentration owing to the used with varying doping levels to understand the correlation between
Columbic interaction and exhibits minimal value for trivalent dopants the physical properties of dopants and conductivity. It is well known that
due to the charged character of the defect pairs. The activation energy CeO2 shows improved performance in the intermediate temperature
for conduction determines how differently the doped fluorite oxides range when it is doped with lanthanide cations. However, in the case of
conduct, and the pair binding energy contributes significantly to this ZrO2, the higher activation energy for oxygen diffusion was observed
activation energy [14]. The dopant size affects the pair binding energy, when compared to that of CeO2. It is observed and reported by several
which reaches a minimum when Rdopant = Rhost. When the dopant cat­ research groups that in the case of ZrO2, ionic conductivity decreases as
ions are larger compared to the host cations, the dependency on size is the mismatch between the ionic size of host and dopant cations increases
significantly stronger for the smaller ions. Acceptor dopants have been [18,26-28]. Larger sized dopant cations stabilize the cubic fluorite
added to the cation sub-lattice in order to stabilize the cubic structure at structure of ZrO2, but leads to significant increase in the activation en­
the lower temperature and enhance the concentration of oxygen va­ ergy. This is the reason why Sc3+ exhibits much higher ionic conduc­
cancies [20]. Ca2+ and Y3+ are common aliovalent dopants (also known tivity compared to other dopants, as it possesses an ionic radius close to
as acceptors), which together produce the zirconia ceramics calcia- that of Zr4+. However, this scenario is different in the case of doped
stabilized zirconia (CaSZ) and yttria-stabilized zirconia (YSZ), the CeO2 systems. Ionic conductivity in doped CeO2 increases with
latter of which exhibits excellent oxide-ion conductivity above 700 ◦ C increasing dopant size, reaches its maximum value at Sm3+, and then
[21]. Among all, YSZ have been one of the most extensively studied solid decreases. The ionic conductivity of the resultant electrolyte material
electrolyte for fuel cells [22]. In order to maintain ionic conductivity, was found to be influenced not only by the ionic radius but also the
the difficulty occurs in maintaining the ohmic losses and polarization valency of the dopant cations and by the doping level. The oxygen va­
resistance. Superior ionic conductivity is also demonstrated by Sc-doped cancies introduced upon doping, compensate the negative charge of the
zirconia (ScSZ), but its application is constrained due to the expensive acceptor dopant cations. The conduction occurs in these materials via
cost of scandium. The detail survey of which is discussed in the later vacancy diffusion mechanism, thus, the ionic conductivity is observed to
section. increase with an increase in oxygen vacancy concentration. In the case
of doped ceria electrolytes, high ionic conductivity is essentially due to
low activation energy, which in turn, is related to an optimal balance
2.1. Yttria stabilized zirconia between elastic and electronic columbic defect interactions [18]. In the
ZrO2 based systems, ionic conductivity initially increases with the rise in
Pure zirconia (ZrO2) is poor ionic conductor in nature. It is an concentration of dopant cations, reaches a maxima when the dopant
extensively explored important ceramic material having its applications concentration approaches the minimum amount required to completely
in various different fields, such as solid oxide fuel cells, thermal barrier stabilize the cubic fluorite structure of at room temperature [29]. This

Fig. 2. Crystal structure of all the three phases of zirconia (a) cubic, (b) tetragonal and (c) monoclinic [24].

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P. Vinchhi et al. Inorganic Chemistry Communications 152 (2023) 110724

minimum amount required to stabilize cubic fluorite phase is also called

low stabilization limit. Both the low stabilization limit and resultant
ionic conductivity, depend on thermomechanical history and micro­
structural features [30]. It is widely accepted that the ionic conductivity
in (Y2O3)x–(ZrO2)1-x is highest when the Y2O3 content is approximately
8 mol.%. In fact, 8 mol.% Y2O3 stabilized ZrO2 is an established elec­
trolyte for SOFCs operating at high temperatures (1000 ◦ C). On further
addition of dopant oxide, i.e., beyond 8 mol.% in the case of
(Y2O3)x–(ZrO2)1-x, the defect interactions become the dominating factor,
which hinder the flow of mobile oxygen vacancy resulting in the
decrease in ionic conductivity [12]. However, since the ionic size of Sc3+
is close to that of Zr4+, an enhanced ionic conduction is observed in
Sc2O3 doped ZrO2. With the increase in size of the dopant, the tendency
to form local defect associates increases, resulting in a decrease in the
ionic conductivity [29]. Another advantage of using stabilized ZrO2
system is its negligible contribution of electronic conduction towards the
total conductivity. There are several work have been reported in the
literature where several dopants were used in the ZrO2 system along
with Y2O3 [13,31-39]. All these electrolyte materials are used for high
temperature SOFC Among them, in one of the work, the effect of doping
a trace amount of Fe2O3 on the structural and electrical properties of
8YSZ has been investigated recently and it has been found that both
ionic conductivity and maximum power density were improved without
reducing the operating temperature [34]. However, this electrolyte
faces compatibility issue with anode and cathode during the fabrication
of cell. Another problem could be the reduction of Fe2O3 to Fe in the
reducing atmosphere during cell operation.
Among all other dopants employed for stabilization zirconia, Y3+ is
Fig. 4. Molar concentration relationship of Y2O3 in stabilization of ZrO2 at
considered to be optimized due to its ionic conductivity and its stability
various temperatures [25].
in various atmospheres. Y2O3 stabilized ZrO2 is one of the most
commonly used electrolyte material. However, in order to provide
strength but 8 mol % YSZ (8YSZ) is observed to have maximum ionic
adequate oxygen ion movement for excellent performance, it must be
conductivity compared to others whereas conductivity decreases as
operated at temperatures exceeding 800 ◦ C.
concentration increases from 8 mol % [40,41]. At about 1000 ◦ C, 8YSZ is
Fig. 3 represents a typical YSZ based SOFC with Ni-YSZ cermet as the
observed to have ~0.1 S cm− 1, however, at such high temperature, for
fuel electrode (anode) and LSM (lanthanum strontium manganate) as
the long time operation, the mechanical and chemical instability could
the air electrode (cathode).
be an issue. Further, on increasing the molar concentration of Y3+, the
Another factor that plays an important role deciding the ionic con­
oxygen vacancies increases in a very large amount, resulting into a
ductivity is the dopant concentration.
decrease in ionic conductivity [42]. Jianxing et al. reported high ionic
The dopant concentration is responsible for the composition of the
conductivity of 8YSZ contributed due to large sum of grain boundaries
crystal structure. The amount of yttria present is the deciding factor for
and point defects, of about 174.1 mS cm− 1 at 1000 ◦ C [43]. Therefore, to
the structural properties and ionic behavior of zirconia. Fig. 4 shows the
improvise the ionic conductivity of the electrolyte material, one alter­
graph of Y2O3 concentration versus the temperature with the phase
native is to replace the Y2O3 by Sc2O3 dopant, which will not only
analysis. Depending on the concentration, the structure is either fully or
enhance the ionic behavior but also reduce the operating temperature
partially stabilized resulting in cubic and tetragonal structure respec­
[44]. This dopant, Sc2O3, sets good compatibility with ZrO2, the ionic
tively [25].
radii of Zr4+ and Sc3+ are nearly similar, and the mismatch in particu­
Phase transformation toughening (PTT) is one of the important
larly is very low as compared to Y3+ and Zr4+.
phenomena discovered by Porter et al. observed in partially stabilized
zirconia (PSZ), shown in Fig. 4. The martensitic phase transformation
occurring from metastable tetragonal phase to monoclinic, induces 2.2. Scandia stabilized zirconia (ScSZ)
stress resulting into ~4% volume expansion [24]. 3–10 mol % YSZ has
been studied of which although 3 mol% YSZ has good mechanical The existing disadvantages of high temperature SOFC cannot be
resolved by lowering down the operating temperature, hence other
alternative has to be worked upon. Therefore, there is a need of finding
other suitable electrolyte material having good ionic conductivity at
intermediate temperatures. Sc3+ has the closest ionic radius to Zr4+,
which makes it more compatible due to minimum lattice mismatch with
the Zr4+ ion, reducing the activation energy and at eventually stabilizes
ZrO2 [18]. However, cost and availability limits its use commercially.
Although YSZ being stable, both mechanically and chemically, the
comparatively lower conductivity has always been a matter of concern.
Large amount work has been reported so far but the higher operating
temperature range and lower conductivity at the expense of high cost of
the cell is a challenging part for ScSZ. The crystal structure of ScSZ being
the foundation of conductivity, Jing chao et al. studied 5–8 mol. % Sc2O3
doped ZrO2 using hydrothermal method and observed that 8ScSZ ma­
Fig. 3. A typical YSZ electrolyte based SOFC. terial was free from amorphous phase and it was also observed that with

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P. Vinchhi et al. Inorganic Chemistry Communications 152 (2023) 110724

decrease in grain size the total ionic conductivity was decreased while operation at high temperatures, can also lower the performance of Ni-
specific grain boundary ionic conductivity was found to be increasing YSZ. Therefore, it is preferable to replace this material with perovskite
[45]. materials [53]. With zirconia-based electrolytes, perovskite anodes
Fig. 5 shows the comparison between the ionic conductivity between exhibit high electrical conductivity and substantial chemical and ther­
YSZ and ScSZ. It can be clearly seen from Fig. 5 that the ionic conduc­ mal durability. Additionally, as compared to Ni-based cermet materials,
tivity of ScSZ is higher as compared to YSZ [46]. It is well known fact perovskite materials are less reactive with sulfur containing gases.
that the performance of SOFCs is heavily dependent on the conductivity Perovskite anodes indeed offer these advantages, however, high cost and
qualities of solid electrolytes. As a result, the critical purpose of modi­ limited catalytic activity prevent the commercialization of SOFC made
fying the ScSZ electrolyte at the SOFC application’s low-to-intermediate from them [54,55]. Another alternative proposed by Son et al. is the
working temperature is to produce better ion conductivity and to ceria (CeO2) added Ni/YSZ anode functional layer for single layer YSZ
maintain high efficiency throughout the operation. The strong ionic electrolyte to improve the cell durability under negative voltage con­
conductivity and stability of the ScSZ electrolyte, may be maintained in ditions [56], which can essentially enhance the performance of more
two ways [46]. First, by co-doping a stabilizer with a metal oxide ionic traditional electrodes. However, the cermet anode induces deposition of
conductor. The cubic fluorite structure of solid electrolytes may theo­ carbon from the hydrocarbon fuels, resulting in the degradation of
retically be stabilized by doping trivalent metal oxides down to room cracking reactions, which ultimately deteriorates the cell performance
temperature, thereby producing an extra oxygen vacancy, which is ad­ [57]. Many researchers have also reported Cu based cermets for anode
vantageous for ionic conduction. Among which Grosso et al. reported Dy material [58]. Lin et al. reported Ni-Cu-8YSZ anode material with
co-doped ScSZ having 17.6 mS cm− 1 ionic conductivity [47]. Another different variation of Ni and Cu concentration, from which 50 % Cu-Ni/
alternative is the formation of bilayer with ScSZ, which enhances the YSZ showed best electrical conductivity of 1503 S cm− 1 at 650 ◦ C with
overall efficiency of the electrolyte [46]. low cracking rate [59].

2.3. Anode materials for YSZ 2.4. Cathode materials for YSZ

The anodes need a lot of catalytic activity since they are situated in The three-phase boundary (TPB), where the electrode (electrons),
strongly reducing environments. By manipulating the microstructure of electrolyte (ions), and gases meet, is where oxygen hits the cathode.
anode materials by nanofabrication, the oxidation of the fuel at the Here, the oxygen is reduced to oxygen ion and the produced oxygen ions
anode can be made more efficient. The anode material that is now most move through the electrolyte. Therefore, cathodes require a material,
often used is Ni-YSZ cermet. In this, Ni serves as the electronic which can match the thermal expansion efficiency of the electrolyte
conductive medium and the YSZ plays role of the ionic conductor. For an material, and should have high electrical conductivity, sufficient
anode supported SOFC, the anode material should fulfill certain re­ amount of porosity to enable gas diffusion and should be a good catalyst
quirements like, it should have good mechanical strength, a proper to facilitate oxygen reduction reactions (ORR) to take place [60]. La1-
electronic pathway and enough porosity to facilitate the fuel. Ni being a xSrxMnO3 (LSM) is the most commonly used cathode material due to its
metal is highly stable in reducing atmospheres and of course is abun­ high catalytic activity and also work at high temperatures [61-63]. LSM-
dantly available in nature. As compared to other metals, just like Ni, Ru YSZ composite improvises cathode properties like porosity, thermal
also has high electrocatalytic activity but the high cost of Ru makes it a compatibility with YSZ and also provides enough electronic conductiv­
lesser choice over Ni. The thermal properties of Ni and YSZ match quite ity. Due to the lack of oxygen vacancies in LSM and the consequent re­
well, with the thermal expansion coefficient of Ni is 13.3 × 10-6 K− 1 striction of the oxygen reduction reaction to the TPB, the usage of LSM is
while for YSZ, it is 10.7 × 10-6 K− 1 [48] making them a good match as a nonetheless restricted when the working temperature is lower than
cermet. Due to the performance and chemical stability Ni-YSZ, it is the 800 ◦ C [60]. Abgede et al. fabricated LSM, LSM-YSZ and LSM-YSZ/LSM
most often utilized anode in high temperature SOFC [49]. High elec­ double layer cathode material over YSZ hollow fibers via dip coating and
trical conductivity at high operating temperatures and high catalytic observed no delamination with proper adhesion with electrolyte. The
activity at reducing atmospheres are the two main characteristics of Ni LSM-YSZ cathode had maximum conductivity with least activation en­
[50]. Unfortunately, employing hydrocarbon fuels or syngas can result ergy [64]. Another parameter is the microstructure of the material used.
in sulfur poisoning and the deposition of a significant quantity of carbon The microstructure of a cathode is its most crucial feature, responsible to
[51], which resulted in the degradation of a cell’s efficiency by blocking increase the number of active sites since the activation of oxygen ac­
the TPB or the gas passageways in the anode [52]. Ni agglomeration, counts for a sizeable portion of the energy generated. Therefore, the
which may happen in a reducing environment for extended period of microstructure of the cathode is essential for high performance [65,66].
La1-xSrxCoO3-δ, La1-xSrxFeO3-δ, and Sr-doped LaFeO3 are other materials
that are often utilized as cathodes. Because LSCF creates a secondary
phase like SrZrO3 or La2Zr2O7 via inter-diffusion when used directly
with a zirconia-based electrolyte, the cathode material, which can
function at low temperatures, is often employed with doped ceria elec­
trolyte materials [67].

3. Recent advances

In YSZ electrolyte, first and foremost challenge is the very high

operating temperature. Another challenge is to improvise its ionic con­
ductivity. Efforts have been made to overcome these challenges. Fabri­
cation of YSZ plays an important role for achieving high ionic efficiency
and also setting the compatibility with other components of the fuel cell.
Also efforts have been made in reducing the thickness of the YSZ layer
for obtaining high conductivity with lowering the operating
temperature.
Fig. 5. Comparison between the ionic conductivity between YSZ and Various fabrication techniques have been explored in order to opti­
ScSZ [46]. mize the microstructure and enhance the ionic yield. Da Silva et al.

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P. Vinchhi et al. Inorganic Chemistry Communications 152 (2023) 110724

reported the synthesis of YSZ using combustion technique with glycine oxygen conductivity at atomic level. In order to oxygen diffusion, H. C.
as fuel and they got relatively high density (97.5 %) [68]. Whereas Huang et al studied molecular dynamics simulations for single as well as
Flegler et al., studied the effect of sintering additives, where metals were bicrystals of YSZ and found that grain boundaries (GB) exhibit blocking
doped on the surface. As per their study, surface doping with iron in YSZ effect along its plane and it was observed that blocking effect was
electrolyte exhibited the dense structure [69]. They also found that inversely proportional to the grain size [81]. which is shown in Fig. 6.
doping not only reduced the sintering temperature of YSZ but also Similarly, Guan et al. reported series of molecular dynamics simu­
maintained its cubic structure with better oxygen conductivity. To lations for different compositions of YSZ over wide range of tempera­
improve ionic conductivity and reliability, Lee et al. reported addition of ture. They also studied the vacancy migration path and validated with
100 ppm CuO with YSZ electrolyte, which resulted in enhanced per­ DFT [82]. By using Y − Zr − O global neural network (GNN) potential,
formance of about 1.5 times (0.5 W cm− 2) than pure YSZ (0.36 W cm− 2) they were able to perform a series of long-time MD simulations for YSZ
at 800 ◦ C [70]. In another report, upon adding alumina to YSZ elec­ at different concentrations of yttria starting from 6.7 mol % over a wide
trolyte using co-precipitation process, the additional grain produced temperature range (525–1725 ◦ C). This study quantitatively resolved
improves ionic conductivity by reducing the ohmic barrier and interfa­ the effects of temperature and composition on the oxygen ion conduc­
cial polarization barrier [71]. To outline the YSZ electrolyte with the tivity. They confirmed that 8 mol % YSZ has the highest ion conduc­
nanowire structure, Lui et al. used the electrospinning technique [72]. tivity, 0.16–0.51 S cm− 1, (agrees well with the experimental findings) at
The advantage of this advancement may coordinate the molecular ox­ 925–1325 ◦ C, and also the ion conductivity of 8YSZ exhibits the non-
ides in low-temperature working attempts owing to the enhancement of Arrhenius behaviors with two different activation energies. The phys­
grain limit conductivity. It displays strong ionic conductivity due to low ical origin for these peculiar phenomena is revealed at the atomic level,
porosity [73]. Chasta et al. synthesized dense and compact spin coated which confirms that the presence of monoclinic phase and the aggre­
YSZ thin film to study the effect of ethyl cellulose on microstructure and gation of oxygen vacancy along are two key factors to retard oxygen
electrical properties of YSZ. The adhesion was reported to be better with diffusion. The MD simulations also confirmed that for 8 mol % YSZ, the
good ionic conduction [74]. oxygen movement is dominated by local vibrations below 725 ◦ C, which
Powder structure and chemical and physical characteristics depend gets delocalized above 725 ◦ C, resulting in the gradual aggregation of
on the density of YSZ. Hence the experimental method is important to oxygen vacancy along a new direction.
the purity of the phase. In general, smaller particle size causes great­
er densification, which results in a larger electrolyte surface energy. 4. Ceria based electrolytes
There are many methods to develop electrolytes such as the hydro­
thermal method, sol–gel, and co-precipitation but among all of these co- In recent years, ceria (CeO2) based materials gained lots of attention
precipitation method gives high densification. According to Maurya et because of its use as electrolyte in SOFC operates at low to intermediate
al. [75], the traditional pressure-less sintering approach generates YSZ temperature. The cubic fluorite structure of CeO2 remains stable from
electrolytes with greater decreased modulus and hardness than spark room temperature to its melting point ~2400 ◦ C at ambient pressure.
plasma sintered YSZ electrolytes. CeO2 was added to improve the me­ The Ce4+ and O2 ions are located at 4a (i.e., 0, 0, 0) and 8c (i.e., 1/4, 1/4,
chanical properties of electrolytes. Less traditional pressure sintering 1/4) Wyckoff positions, respectively. The structure also possesses four
methods have led to improved grain coalescence when the pore size is large unoccupied octahedral sites, which provide a path for rapid oxide
lower and densification is greater. Vickers hardness testing was used by ion diffusion. Ionic conduction in these oxides takes place via vacancy
Selvaraj et al. to study the mechanical characteristics of a YSZ-based diffusion mechanism [29]. However, pure CeO2 does not possess suffi­
synthetic electrolyte [76]. The synthetic electrolyte had greater impact cient amount of oxygen vacancies to exhibit appreciable ionic conduc­
strength than the pure electrolyte due to superior densification even at tivity. In order to achieve high ionic conductivity, oxygen vacancies are
high temperatures with the addition of metal oxide, which reduce the introduced into the structure via substitution of host Ce4+ by acceptor
pore size and increased particle bonding. Ionic conductivity is also cations, such as, Gd3+, Sm3+, or Y3+. Although doped CeO2 shows phase
affected by mechanical strength. With this solid YSZ electrolyte, Araki stability while operating in intermediate temperatures (500 – 700 ◦ C),
et al. used molecular dynamics modeling to explore the impact of
physical pressure on ionic conductivity [77]. The strain energy was
identified and a load of stress up to 1 GPa was applied. The findings
showed that decreasing the activation energy and enhancing the tran­
sport of oxygen one can achieve an increase in the ion conductivity of
solid electrolytes. The effect of conductivity qualities, which are corre­
lated to the efficiency and power density of the cell, makes the YSZ
electrolyte’s analyzed mechanical properties significantly. The working
temperature of SOFCs is often more than 500 ◦ C, making consideration
of the thermal analysis concerns vital to preserve the durability and
performance of YSZ electrolytes. Park et. al synthesized YSZ using
atomic layer deposition (ALD) to avoid damage to cell components [78].
Sputtering at 450 ◦ C was used to deposit anodic Al2O3 with various
depositions on the YSZ electrolyte. As a result, the agglomeration was
decreased and the surface thermal barrier was enhanced. Since long,
efforts have been made in modifying the surface structure, among which
Gu et al reported symmetric SOFC with YSZ electrolyte and
PrBaMn2O5+δ (PBMO) electrode using phase inversion and infiltration
method resulted in an improvement of power output observed by 100 %
at 800 ◦ C [79]. Satheeshkumar et al. successfully developed reported
microwave assisted combustion synthesis of YSZ films having thickness
<200 nm [80]. Fig. 6. Simulations of YSZ bicrystals separated by grain boundaries (a)Σ 5
Lot of theoretical simulations have been performed using molecular (3 1 0) GB and (b)Σ 1 3 (5 1 0) Red, gray, and blue particles represent O, Zr and
dynamics in the form of Born − Mayer − Huggins (BHM) models by Y, respectively [81]. (For interpretation of the references to colour in this figure
various authors for getting broader understanding of the behavior of legend, the reader is referred to the web version of this article.)

6
P. Vinchhi et al. Inorganic Chemistry Communications 152 (2023) 110724

Ce4+ have a tendency to reduce and form Ce3+ in the fuel environment This, as a result, facilitates oxygen vacancy diffusion, and enhances the
(typical of an SOFC device). This leads to several disadvantages, such as, ionic conductivity in this system. Thus, it was predicted that among the
high electronic conductivity, chemical expansion (due to larger size of rare earth trivalent cations, Pm3+ is the best dopant for achieving high
Ce3+ when compared to that of Ce4+), and inferior mechanical ionic conductivity in CeO2. As Pm3+ is a radioactive element and cannot
properties. be used for electrolyte applications, a co-doping scheme with Sm3+ and
In CeO2, as discussed earlier, the trivalent dopants exhibit much Nd3+ as co-dopants was suggested for CeO2. The hypothesis was
higher conductivity than divalent dopants due to the lower ionic size experimentally tested by keeping the molar ratio 1:1 between the co-
mismatch between the trivalent dopants and the host Ce4+ cation. dopants such that an average effective ionic radius is near to that of
Similar to doped ZrO2-based systems, increasing dopant concentration Pm3+. The observed grain ionic conductivity of a 10 mol.% co-doped
initially enhances ionic conductivity. However, at a certain doping level, composition samples was found to be 14 % higher than that of
conductivity reaches its maximum value and then decreases due to the Gd0.1Ce0.9O2-δ at 550 ◦ C [90,91]. Recently, Omar et al. have shown
low mobility of defect associates. The extent of formation of these as­ relation of ionic conductivity on lattice elastic strain in 10 mol.%
sociates increases with the increasing ionic-radii mismatch of dopant trivalent cations doped CeO2 at high temperatures in air [88]. It was
cations with respect to the host cation [83,84]. Doping has also been observed that at a 10 mol.% concentration, the ionic conductivity is an
used to lower the elastic strain generated in the lattice and reduce the increasing function of the size of the dopant, with Nd3+ exhibiting the
activation energy for oxide ion conduction [85]. The dependence of highest grain ionic conductivity. Furthermore, the rc values were
ionic conductivity on the dopant size of trivalent cation doped CeO2 has calculated at intermediate temperatures using the high temperature
been discussed by Mahato et al. in details. The strong dependence arises elastic strain data. It is important to note that the rc value reported by
due to the formation of local defect complexes between oxygen va­ Kim [86] was determined from the elastic strain data taken at room
cancies and dopant cations. The phenomenon of relaxation of the dopant temperature, while the conductivity was measured at high tempera­
cations in CeO2 towards oxygen vacancy occurs in the case of smaller tures. A slight decrease in rc value was observed with the rise in tem­
sized dopant cation, such as, Sc3+ (r = 0.84 Å), Y3+ (r = 1.019 Å), which, perature which indicates that the structure-conductivity relationship
as a result, increases the stability of the complex [85]. On the other based on rc is not sufficient to explain the ionic conductivity behavior in
hand, in the case of larger sized dopant cations, such as, Gd3+ (r = 1.053 doped ceria [88].
Å) and La3+ (r = 1.18 Å), the energy associated with the reduction in As doped ceria materials exhibit higher ionic conductivity than YSZ,
elastic strain in the crystal becomes significant when an oxygen vacancy they can be utilized in the intermediate temperatures. In this category,
is introduced into a neighboring site. The two opposing effects lead to solid solutions, such as, Ce1-xMxO2-δ (where, M = Gd or Sm, x = 0.10 –
minimum binding energy (0.17 eV) corresponding to Gd3+. The 0.20) show the highest level of oxide ion transport [16]. For example,
computed values of the binding energies corresponding to Sc3+, Y3+, Ce0.9Gd0.1O1.95 shows grain ionic conductivity of 0.01 S cm− 1 at 500 ◦ C,
Ce3+ and La3+ are 0.62, 0.38, 0.25 and 0.26 eV, respectively [85]. while Ce0.8Gd0.2O1.9 exhibits lower conductivity (0.0053 S cm− 1) [92].
Therefore, it can be concluded that Gd3+ can be considered to be an ideal The major issue which limits their applications as electrolyte is the
dopant for CeO2. Kim et al. [86] studied the effect of ionic radius and tendency of Ce4+ to reduce to Ce3+ ions in low oxygen partial pressure
valence of the dopant cation on the lattice parameter of ceria. After and high temperature conditions, which typically occurs at the anode
thorough analysis on the experimental data, an empirical model pre­ side during SOFC operations [84,93,94].
dicting the change in the lattice parameter of doped ceria as a function of
ionic radii mismatch, dopant valence and dopant concentration was 5. Electrolytes for the future
defined. Further, the concept of critical ionic radius, rc, was proposed in
relation to the ionic conductivity of doped ceria. It was suggested that a A traditional SOFC consists of a three-layer anode/electrolyte/
dopant with ionic radius equal to rc will not result any change in the cathode structure, where the electrolyte layer is used for ion transport to
lattice parameter of the fluorite structure. The critical ionic radius rc of support the redox reaction and prevent the occurrence of short-
divalent and trivalent dopant cations for CeO2 were calculated to be circuiting. A novel nano-SOFC concept is proposed to replace the
1.106 Å and 1.038 Å, respectively. According to Kilner and Brook [14], traditional electrolyte with a semiconductor membrane, which can
maximum ionic conductivity in doped fluorite structured oxide is deliver superior performance, even at a lower temperature range
observed when the lattice elastic strain is minimal. Based on Kilner’s (<500 ◦ C) [95,96]. Recently, an important breakthrough has been made
observations, it can be concluded that the dopants with the ionic radius in low-temperature SOFCs by introducing semiconductor heterojunction
close to rc should exhibit minimum association enthalpy, and hence high membranes to function alternatively as electrolytes with better perfor­
ionic conductivity. Using a similar argument, Kim suggested that Gd3+ mance. This novel fuel cell design is known as a semiconductor-ionic
exhibits the highest ionic conductivity as the ionic radius of Gd3+ (r = membrane fuel cell (SIMFC) [97].
1.053 Å) lies close to rc [86]. The validity of the argument presented by Shah et al. developed semiconductor heterostructure membrane
Kim was tested by Omar et al. [87] using a co-doping approach in CeO2, based on Mg-doped ZnO and ZnO, which not only block electrons
where the co-dopant pair, i.e., Lu3+ and Nd3+, was selected based on passing through the junction but also trigger the ionic properties of
their respective ionic radius. Both the co-dopants were added in a pro­ membrane to boost the fuel cell performance. This kind of membrane
portion that matched rc, such that the positive elastic strain due to larger can be used for solid oxide fuel cells and proton ceramic fuel cells. The
dopant cation (i.e., Nd3+) can be compensated by the negative elastic Mg doping into ZnO and Mg doping in ZnO/ZnO heterostructure creates
strain due to smaller dopant cation (i.e., Lu3+). This in turn prevents any more oxygen vacancies at the surface of ZnO, leading to enhanced ionic
distortion in fluorite lattice that is usually present in the singly doped transport [98].
ceria systems. It was observed that even though the lattice elastic strain
present in the co-doped compositions is negligible, the ionic conduc­ 6. Conclusion
tivity value is less than that of Gd-doped CeO2 [87]. Furthermore, the
ionic conductivity of Y3+ doped CeO2 has been found to be lower This paper gives a brief discussion about the high temperature SOFC
compared to Sm3+ doped CeO2 and Gd3+ doped CeO2, even though the electrolyte material having oxide ion conduction. Typically, YSZ (Yttria
ionic radius of Y3+ is closer to rc [88]. Using DFT calculations, Ander­ Stabilized Zirconia), emphasizing on the structure such that its me­
sson et al. [89] have estimated the interaction energies involved be­ chanical and electrical properties can be tailored. The cubic fluorite
tween the dopant cations and oxygen vacancies in doped CeO2. It was structure is the most crucial part of the zirconia structure. Various
suggested that in the case of Pm3+ doped CeO2, oxygen vacancies have trivalent and divalent impurities have been widely explored as the
no site preferences and can reside next to both dopant and host cations. dopant material for zirconia, among which Y3+ gives the most stable

7
P. Vinchhi et al. Inorganic Chemistry Communications 152 (2023) 110724

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lationships which may be considered as potential competing interests: [28] K. Eguchi, T. Setoguchi, T. Inoue, H. Arai, Electrical properties of ceria-based
Prerna Vinchhi reports financial support was provided by SERB-DST. oxides and their application to solid oxide fuel cells, Solid State Ion. 52 (1992)
Ranjan Pati reports a relationship with SERB-DST that includes: fund­ 165–172.
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Data availability oxide fuel cells, Ionics 6 (2000) 1–21.
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All the authors gratefully acknowledge Science and Engineering Evaluation of densification effects on the properties of 8 mol% yttria stabilized
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