1 s2.0 S1385894721041814 Main

Chemical Engineering Journal 428 (2022) 132603
Contents lists available at ScienceDirect
Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej
Recent advancements, doping strategies and the future perspective of

perovskite-based solid oxide fuel cells for energy conversion
Muhammad Bilal Hanif a, b, *, Martin Motola b, Sana qayyum c, Sajid Rauf d, Azqa khalid e,
Chang-Jiu Li a, Cheng-Xin Li a, *
a
State Key Laboratory for Mechanical Behavior of Materials, School of Materials Science and Engineering, Xi’an Jiaotong University, Xi’an, Shaanxi, China
b
Department of Inorganic Chemistry, Faculty of Natural Sciences, Comenius University in Bratislava, 842 15 Bratislava, Slovakia
c
Department of Chemistry & Chemical Engineering, Lahore University of Management Sciences (LUMS), Pakistan
d
College of Electronics and Information Engineering, Shenzhen University, Guangdong Province, 518000, China
e
Department of Chemical Polymer & Composite Material Engineering, University of engineering and technology New campus, Lahore, Pakistan
A R T I C L E I N F O A B S T R A C T
Keywords: Solid oxide fuel cells (SOFCs) have the potential to be used in energy conversion technology. Most of the studies
Perovskite materials aimed at modifications of anode concerning various issues such as component degradation, sulfur poisoning, and
Energy storage applications carbon deposition at high temperatures, hindering its applications at the industrial level. Different perovskite
Solid oxide fuel cells
structure-related compounds are discussed in this article, which could be possible electrode materials in SOFCs.
Doping
Design strategies
Literature also revealed the successful utilization of various cathode materials in a wide range of temperature in
which cobalt-based materials exhibits higher conductivity than cobalt-free once. The selection of initial
composition, dopants addition in different electrodes with critical challenges inherent to this material family
have been assessed herein which play a vital role in enhanced electrochemical performance. The other aim of this
review article is to provide some useful recommendations and prospective directions for designing future elec
trode materials of SOFCs. The review analysis is done based on different processing parameters and their effect
on thermal expansion coefficient, electrical conductivity, mechanical and electrochemical properties, etc. In a
nutshell, a detailed overview is critically analyzed for energy conversion and storage applications, which can
open many gateways towards the advancement of SOFCs.
1. Introduction fuel cell (PAFC), and solid oxide fuel cell (SOFC) [1-9].
PEMFC are designed to allow the passage of protons through elec
The rising threat to the environment due to fossil fuel emission trolytes assimilated by a polymer membrane. These cells are charac
pushes the world to divert its attention towards renewable energy. Fuel terized by high power density and designed to operate at a wide
cells (FC) have the potential to cope with the present energy demand of temperature range from 25 to 80 ◦ C. While in PAFC, electrodes are made
the globe because of their efficiency, stability, and wide range of ap up of platinum or its alloy, and concentrated phosphoric acid is used as
plications, especially in the transport sector. In this regard, fuel cell an electrolyte material. These cells are functional at a temperature range
technology has drawn attention because of its inherent ability to pro of 150–200 ◦ C [10]. MCFC cells possess electrolyte materials comprised
duce electricity with minimal hazardous waste. Additionally, fuel cells of liquid lithium, sodium, or potassium carbonates. Operated optimum
can be used in certain applications with strict demands for perilous temperature is found to be approximately 650 ◦ C at which carbonyl
sources of energy consisting of constant supplies of power, power sta electrolyte shows enhanced conductivity. AFCs operate at temperature
tions, and distributed grids. All the fuel cells have different reactions at ranges from 25 to 80 ◦ C, have substantial applications in space, and are
different temperatures, possessing their pros and cons. The major fuel widely used for water and electricity generation. These cells contain an
cells are as follows: molten carbonate fuel cell (MCFC), proton exchange alkaline solution of KOH which serves as an electrolyte. Due to cathodic
membrane fuel cells (PEMFC), alkaline fuel cells (AFC), phosphoric acid reactions, these cells show remarkable cell performance. DMFCs contain
* Corresponding authors at: State Key Laboratory for Mechanical Behavior of Materials, School of Materials Science and Engineering, Xi’an Jiaotong University,
Xi’an, Shaanxi, China (M.B. Hanif, C.-X. Li).
E-mail addresses: muhammadbilal@stu.xjtu.edu.cn (M. Bilal Hanif), licx@mail.xjtu.edu.cn (C.-X. Li).
https://doi.org/10.1016/j.cej.2021.132603
Received 20 August 2021; Received in revised form 17 September 2021; Accepted 20 September 2021
Available online 23 September 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
M. Bilal Hanif et al. Chemical Engineering Journal 428 (2022) 132603
similar electrolytes as used in PEMFCs. Working temperature for DMFCs combining H2, CO/H2 electrochemically. Gaugain and Becquerel
is lower than other cells, ranging from 50 to 130 ◦ C. A solid oxide fuel experimentally studied and reported the thermoelectric mechanism of
cell is an assembly of electrolyte solution and 2 electrodes; one of which fuel cells by establishing the metal contact between glass and porcelain.
is a cathode that produces oxide ions and the other one is anode which Furthermore, Buff expanded his research and correlated the thermo
helps in speeding up the reaction which in return produces electricity electric force with the galvanic cell’s voltage and batteries, comprising
and other by-products [11-15]. The reaction can be stated in Kröger of electrodes made up of mercury, zinc amalgam, and various solid
Vink representation as follows. (Equation 1–4). metals.
At the cathode side: In 1853 Gaugain discovered the solid electrolyte which led to the
SOFCs existence. Furthermore, in 1899 Nernst reported the conductivity
1
VO.. +2e− + O2 →OxO (1) of 15-mol.% Y2O3-doped-ZrO2 (15YSZ) and found that reported material
2
exhibits higher conductivity values at elevated temperatures as
At the anode side: compared to other metal oxide mixtures as described in Fig. 2. In 1905,
OxO + H2 →VO.. + 2e− +H2 O (2) Haber assembled the fuel cells manipulating porcelain and glass as solid
electrolytes while Pt and Au as electrodes. In 1935, Schottky suggested
OxO + CO→2e− + VO.. + CO2 (3) that 15YSZ can serve as an excellent candidate for solid electrolytes
[18,19]. Wanger’s experimental studies in 1943 revealed that ionic
(3n + 1)OxO + Cn H2n+2 = (3n + 1)VO.. + nCO2 + (6n + 2)e− + (n + 1)H2 O conduction is caused by oxide solid- solutions, while oxygen vacancies
(4) can be created by a doping mechanism in the crystal lattice of the host.
Warner’s studies were further investigated by Baur and Presis in the
Whereas, OxO =
O2-ions on a regular O2-site in the electrolyte lattice, coming years, fabricating a solid ceramic oxide fuel cell working with
VO.. = Oxygen vacancies. Fig. 1. illustrates the working principle of YSZ at a temperature of 1000 ◦ C. A couple of experimental studies were
SOFCs. reported in literature allied to the utilization of electrolyte material as a
Perovskite materials are represented by general formula as, ABO3. A thin layer of solid ceramic and various fabrication designs (planer and
in the formula is for large cations while B represents smaller cations tubular) for SOFCs for performance enhancement. Blum et. al very well
having coordination no of 12 and 6 respectively. Large cations may summarized the development progress of SOFC in their studies. More
comprise of alkali, alkaline earth metals, rare earth, or other metals over from the 1970 s to 2010, studies and research were focused on
whereas, B represents various transition metals. The research of perov lowering the operating temperature of SOFCs to 300 ◦ C by employing
skites was initiated by prof. John B. Goodenough as old as 60 years and nanocomposite (5–10 µm) and thin-film heterolayer electrolytes
reported in his autobiographic book named, “Witness to Grace,”. Along [20,21].
with a major contribution towards lithium-ion batteries, his research Moreover, anodic materials used in SOFCs must meet the following
was a masterpiece in the field of perovskite oxide materials. As of yet, requirements; they should be porous, they should have significant
perovskite materials serve as an excellent candidate in the field of en chemical and mechanical stability with higher electronic conductivity,
ergy storage and conversion. A history of perovskite materials devel and compatibility with other components of SOFCs. Unfortunately, very
opment is summarized in Fig. 2. In 1838, William Grove an English few metallic or ceramic materials have been reported which meet all of
scientist invented the first fuel cell and named it, ‘‘Grove cell’’ or ‘‘wet cell the mentioned criteria. Among these materials, one is the Ni-based
battery’’. The operational mechanism for this type of cell was reverse cermet that comprehends all these reported properties but certain
electrolysis of water [16,17]. Those cells were capable of directly con problems are associated with its application i.e., Ni deposition over
verting the chemical energy of the fuel to electricity and heat by electrode because of low resistivity towards coke formation, resulting in
Fig. 1. Working principle of SOFC.
2
Fig. 2. Trend of energy storage applications for perovskite and SOFC in previous 20 decades.
cell degradation. This suggests that within the search of new fuels, fabrication strategies of anodes, kinetic studies of an anode and, anodic
perceptive construction of coking-resistant anode is necessary to reaction mechanisms for SOFCs [22,23]. However, there is still a need to
commercialize the hydrocarbon-fueled SOFCs. The use of this anodic summarize all the basic features required to develop the anodic mate
material is associated with the deposition of carbon generated from rials for SOFCs employing directly oxygenated hydrocarbon fuels.
hydrocarbon fuel during internal-reforming. Increased oxygen to carbon Material section based on necessity and application plays a signifi
(O/C) ratio is being utilized as an effective approach (steam/ oxidant) to cant role in the operational mechanism of the device. Likewise, the se
suppress the formation of coke. However, an increased amount of steam lection of materials plays a major role in the functioning of SOFCs. The
affects the operation stability and efficiency of SOFCs. The only solution material must meet several features to be applicable as a cathode. It
to this problem is the utilization of fuel with a high O/C ratio. The major should possess ionic (10-1-10-4 Scm− 1) as well as electronic conductiv
factors associated with the fuel selection include the physical state of ities (>100Scm− 1) and compatible coefficient of thermal expansion
fuel (at standard conditions), energy density, cost, and availability. (CTE) with other modules of SOFC listed as, electrolyte, sealant, and
Several publications are currently buckling down to develop several interconnection to eliminate delamination and cracking during
3
functioning and manufacturing of SOFCs. Porosity is an essential prop overall efficiency of the fuel cell. The material chosen for the anode
erty required (~30–40%) for the diffusion of gases into cathode material should be of greater electrical conductivity to asses less resistance for
for the proper functioning of SOFCs as it is involved in the formation of transported electrons on a channel. It must also exhibit high carburi
remarkable gaseous phases of TPB. The performance of SOFCs is sub zation and sulfide resistance should be non-reactive towards electro
stantially affected by the lack of porosity as it is directly concerned with lytes, and ought to retain its higher electro-catalytic activity. The current
TPB. Porosity is responsible for providing mechanical strength to the section gives a detailed overview of different processing parameters and
thin layer of electrolyte. However, enhanced porosity might be their effect on thermal expansion coefficient, electrical conductivity,
responsible for the reduction of mechanical and electrical properties. In mechanical and electrochemical properties, etc. We mainly focused on
addition, two important parameters are considered for cathode mate chromite-based single perovskites, SrTiO3-based perovskites, LST-based
rials including, enhanced catalytic and chemical compatibility of elec perovskites, modified double-perovskites, and their composites in
trolyte and interconnect at the time of fabrication and working. Cathode depth.
materials based on lanthanum strontium manganite (LSM) have been
reported for significant performance at elevated temperatures 2.1. Chromite-based single perovskites and their composites
(1000 ◦ C). Polarization resistance (Rp) indirectly influenced and
increased with decreased operating temperatures for SOFCs because low Over the last few decades, numerous research studies have reported
temperatures (~600 ◦ C) favor the increased activation energy of oxi that the single perovskites of Sr-doped lanthanum-chromite (LSCr) have
dation–reduction reaction (ORR) making SOFCs (IT-SOFCs) incompat been used as anode materials in SOFCs. According to literature, Cr has
ible for intermediate temperature range functioning. Thus, present strong coordination with O2-deficiency; this is why the cations intro
studies are being focused on the advancement and development of duction having lower coordination number can increase the catalytic
several materials with higher ionic and electronic conductivities for activity [31]. In reducing atmospheres and at high temperatures, oxygen
intermediate temperature (600–800 ◦ C) range functioning of SOFCs. But vacancies can be generated because of the presence of these cations,
ORR process is dependent on many parameters so it is reported in resulting in improved anode electrical conductivity of LSCr. Irvine and
several publications that the presence of mixed ionic and electronic Tao, firstly reported La0.75Sr0.25Cr0.5Mn0.5O3-δ(LSCM) oxygen-deficient
conducting (MIEC) cathode material is not a standard or an ample perovskite as hydrocarbon-fueled anode material for SOFCs. These
condition for reduced Ea of the ORR. Several studies based on the materials show compatible electrochemical performance and remark
incorporation of dopants to lanthanum and manganese were performed able catalytic activity at elevated temperatures to traditional Ni/YSZ
to enhance several properties (mechanical and thermal stability, cata cermets. Polarization resistance of LSCM in 3%H2O/97%H2 was found
lytic activity, and conductivity) of Lanthanum manganite (LaMnO3) to be 0.2 Ωcm2 at 900 ◦ C [21]. However, the two drawbacks of LSCM
systems [24]. Additionally, oxygen vacancies in a system can be material were identified as, its low electronic conductivity (σe) in
enhanced by partially substituting A-site cations with lower valence reducing atmosphere as compared to Ni-YSZ cermet and being impotent
state cations. Increased oxygen vacancies comprehend the neutrality of to abide the poisoning of sulfur impurities present in the fuel.
the system correspond to higher ionic conductivity and enhanced cata To improve the electrical conductivity and catalytic activity of LSCr-
lytic properties. According to current studies, oxygen vacancies can be based single perovskites, four directions have been pursued such as to
mitigated by substituting smaller ions with lower valences at B-sites so, change the chemical composition of an anode, to make a composite with
perovskite materials exhibit higher values of electronic conductivities transition metals having redox activity, to add nanoparticles to make
associated with mixed-valence states of different elements at the B-site anode composite, and to partially substitute with metal-cations at A or/
[25,26]. However, for the commercialization of SOFCs researchers are and B-site. However, the method in which composites with transition
being focused on the development of cost-effective materials. So, to metals are prepared has many associated constraints i.e., the prepara
overcome the cost factor many, symmetric solid oxide fuel cells have tion is complicated due to the lower melting point of copper and nickel
now become significant as these cells are fabricated by using analogous can be deactivated easily by sulfur poisoning. In this section, the studies
materials as cathode and anode. Implementation of this new conception reported in the literature regarding the dopant and nanoparticles addi
leads towards many benefits. By swapping the flow of gas, sulfur tion on A/B sites of an electrode from doped LSCr will be reviewed.
poisoning and the formation of coke at the anode can be eradicated Mn and Fe co-doping in La0.75Sr0.25Cr0.5-xFexMn0.5O3-δ (LSCFMx)
without any destruction in the cell that enhances the stability and life resulted in enhanced catalytic activity as compared to anodes having
cycle of fuel cells. The manufacturing process comprises single-step either Fe or Mn alone for application involving methane oxida
heating due to the identical composition of cathode and anode mate tion–reduction. It was anticipated that ionic transport (under reducing
rial [5,27-30]. environment) and oxygen deficiencies will increase because of the
In this review, recent developments in perovskite cathode and anode presence of Fe. The measured power density, polarization resistance,
materials of solid oxide fuel cells are summarized with prospects. Here, and ohmic resistance of La0.75Sr0.25Cr0.3Fe0.2Mn0.5O3-δ in dry CH4 at
our main purpose is to deliver a brief tutorial corresponding to the temperature of 750 ◦ C were found to be, 550 mWcm− 2, 0.48 Ω cm2, and
structure, properties, and electrochemical behavior of perovskite-based 0.12 Ωcm2, respectively [31]. The LSCr-based perovskites have shown
anodes, and cathode in test cells with various dopants together and rather poor electrical conductivity under a reducing environment (e.g.,
inherited challenges regarding this material family, which is the novelty 6.45 Scm− 1 for LSCrF and 0.222 Scm− 1 for LSCrM at a temperature of
of this review article. In addition to this, a perspective has been proposed 800 ◦ C), exhibiting poor electrochemical reaction kinetics in comparison
on the development routes or designs for perovskite oxide-based mate to Ni-YSZ.
rials with high performance in energy conversion and storage applica Perovskites having a composition of La0.33Sr0.67Cr1− x− yFexR
tions as well as the way forward to cope with the challenges involved in uyO3− δ(LSCrFeRu) were prepared through solid-state reaction with
the research route regarding the performance of each component. negligible secondary phase reforming. Instead of adding the Ru nano
Perovskite-based materials for Solid oxide fuel cells (SOFCs) particles separately, they were precipitated onto the anode surface upon
heating in a hydrogen environment at the start of operation of SOFC.
2. Recent advancement of anode materials Upon reduction, the formation of metal nanoparticles was found to be the
reason for the improvement of anode’s catalytic activity. The introduction
The anode is considered as the most imperative component in SOFC of Ru nanoparticles was also effective in reducing the anode polarization
where the electrochemical oxidation of fuels takes place. It provides an resistance. Y. Wan, et al. developed a new methodology to enhance the
active electrochemical reaction site and an electron transport pathway. electrocatalytic performances of LaCrO3-based perovskites. Doping of
The selection of anode material is an important factor to determine the bismuth at A-site was found to promote performance greater than the
4
doping of Ru and Pd at B-site. For instance, as shown in Fig. 3(a-d) at a

LaXLa + FeXFe →Bi’La + Fe.Fe (6)
temperature of 800 ◦ C, the 10% doping of bismuth resulted in a 47%
increase of peak power density with hydrogen, 85% with ethanol, and 1
44% with syngas fuel, also 10% decrease in interfacial polarization 2LaXLa + OXO →2Bi’La + VO.. + O2 (7)
2
resistance was achieved.
Fig. 3(e) indicates that nanoparticles used under microscopic char
LaXLa + CrXCr →Bi’La + Cr.Cr (5) acterization are rich in Ru. A peak in the spectrum is also clearly
Fig. 3. Peak power densities with different fuels at variable temperatures (a). Nyquist plots of LSCrF and Bi-LSCrF for symmetrical cells determined at a temp. of
800 ◦ C in (b). Humidified hydrogen environment and (c). Air respectively, (d). Peak power densities with different fuels at variable temperatures [32] EDX spectrum,
acquired for a section comprising of Ru nanoparticle (e). Schematic of the proposed mechanisms for the hydrogen dissociative adsorption in LSCrF-Ru anodes,
containing (f). active dissociation of molecular H2 by Ru, (g). H atom “spillover” from Ru, and (h). adsorption of H atom onto the oxide surface. [11] SEM images of
(i). 63LSCNi-15 and (j). 73LSCNi-15 materials reduced at 800 ◦ C for 4 hrs. While EDX analysis for points 5 and B of the TEM image of 63LSCNi-15 on the left side of
(k). The schematic of the generation of oxygen vacancies and the Ni exsolution process for perovskite with A-site deficiency (l).[34].
5
showing the Fe particles which were substituted on the B-site along with step is normal (Fig. 3(h)). With the enhancement of adsorption kinetics
Cr and Ru. Some other spurious peaks can be seen in the spectrum by the addition of Ru particles, it is presumed that one of the later steps
resulting from the carbon present in the support film, copper present in including water desorption, charge transport, and oxygen ion transport
the sample holder and sample grid, zinc present in the sample holder, becomes the rate-determining [33].
and aluminum present in the collimator [32]. Fig. 3(f-h). shows the Sun et al. reported in another study that in-situ exsolution of Ni-
possible mechanism through which Ru assists hydrogen dissociative nanoparticles on Ni-doped LSCr- i.e., La0.6Sr0.3Cr0.85Ni0.15O3− δ with A-
adsorption. In this model, the presence of Ru particles has increased the site deficiency shows favorable electrochemical performance along with
adsorption rate resulting in the dissociation of hydrogen gas into better redox stability (5000 ppm H2S-H2) at a temperature of 800 ◦ C
adsorbed hydrogen atoms (Fig. 3(f)). As indicated in Fig. 3(g), the pro with a maximum current density and power density of >1200 mWcm− 2
duced hydrogen atoms will then spill over onto the oxide surface, which and 460 mWcm− 2 in comparison with a maximum current and power
is also observed in the case of other composites of ceramic-metallic densities of 300 mWcm− 2 and 135 mWcm− 2 respectively for the stoi
material at elevated temperatures [32,33]. Once the hydrogen atoms chiometric composition of La0.7Sr0.3Cr0.85Ni0.15O3− δ. Numerous
are adsorbed onto the surface of oxides, the process of the subsequent metallic nickel nanoparticles were formed on the A-site deficient
Fig. 4. dependence of polarization with temperature for anodes (LSTX-YSZ) (a). TGA of La4Sr8Ti11XO36+δ(X = Ti, Al, Ga, Fe, Mg, Mn or Sc) (b). Change in con
ductivity of La4Sr8Ti11XO36+δ(X = Ti (2), Al, Ga, Fe or Mn) at 870 ◦ C along with partial pressure of oxygen (c) [38]. Rate of methane conversion and hydrogen
selectivity for the samples of LSCTO, LSMTO, and LSFTO, (d, e). While (f). illustrate the AC Impedance spectra at 800 ◦ C under wet methane (50%) and wet hydrogen
for LSMTO, LSFTO, and LSCTO/ScSZ interface [45]. SEM micrographs illustrating the comparison between the non-stoichiometry formation of exsolutions on
stoichiometric and A-site deficient perovskites (g). exsolutions from the initially A-site deficient, O-stoichiometric La0.52Sr0.28Ni0.06Ti0.94O3 after reduction at 930 ◦ C
(20 hrs) in 5%H2/Ar. (h). A-site stoichiometric, O-excess La0.3Sr0.7Ni0.06Ti0.94O3.09 samples reduced for 20 hrs at 930 ◦ C with no exsolution [48].
6
63LSCNi surface after being reduced at the temperature of 800 ◦ C for a stability under reducing environments (Equation (8)).
total of 4 hrs, whereas, only a few particles were able to be produced in
1
the respective stoichiometric composite [Fig. 4(j)], irrespective of the 2TiXTi + OXO →2Ti.Ti + V ..O + O2 (8)
2
fact that nickel doping content (15%) was the same in both samples. This
indicated clearly that perovskites having A-site deficiency are more Whereas,
prone to B-site species exsolution as compared to the stoichiometric TiXTi = tetravalent B-site ion, Ti.Ti = trivalent ion, OXO = lattice oxygen,
composites. EDX analysis results revealed that the chemical composi VO.. = oxygen vacancies.
tions of nanoparticles (point 5) and that of bulk (point B) were different Scientists have explored several ways to boost perovskite conduc
from each other (Fig. 4(k)). The enhanced kinetics of oxygen and tivity by replacing Ti4+ on the B-site and Sr2+ on A-site. It involves the
hydrogen ions is attributed to the H2-S-O formation with the absorbed production of oxygen that contains sub-stoichiometric compounds
sulfur which explains the stimulating impact of hydrogen sulfide (H2S). which influence the final properties of the product. In addition, various
Furthermore, H2S acts as a carrier of hydrogen, the energy barrier to dopants, such as chromium(Cr)[22], gallium(Ga)[25], Scandium(Sc)
break the H-S bond (363 kJ mol− 1) is lower than that of the H-H bond [31], niobium(Nb)[38], iron(Fe)[39], manganese(Mn)[40], , and on B-
(436 kJ mol− 1) in H2S which facilitates the reaction, leading to site was being investigated. Higher conductivity of 339Scm− 1 (at
improved anodic performance. For exsolution, two possible processes 800 ◦ C) has come across with Nb-doped SrTiO3(SrTi0.98Nb0.02O3-δ)
were hypothesized (Fig. 3(l)). in the first process, because of A-site material. Similarly, due to its better catalytic activity and higher con
deficiency, highly mobile oxygen vacancies will be formed, resulting in ductivity, the Fe-doped SrTiO3 anode has attracted considerable atten
spontaneous exsolution of nickel nanoparticles and perovskite lattice’s tion. By reducing Ti4+ to Ti3+, lanthanum (La) doped to SrTiO3(LST) at
instability after reduction. In the second hypothesized process, under a A-site can increase its conductivity and oxygen stoichiometry. Even in
reducing environment, the Ni cation and oxygen vacancies have the presence of H2S fuel, LST exhibits reasonable chemical and thermal
emerged simultaneously. The catalytic activity and anodic performance stability for SOFC under reducing atmosphere. However, its lower cat
were significantly enhanced in A-site deficient LSCNi as compared to alytic activity for fuel oxidation is not feasible for industrial applica
stoichiometric LSCNi [34,35]. tions. It showed a peak power density(PPD) of 35 and 1.6 mWcm− 2 in H2
Cr-based perovskite composites can also be implied to enhance the and CH4 at 800 ◦ C respectively [26].
anode material’s performance. To improve electrochemical perfor
mance, Zhu et al. impregnated La0.75Sr0.25Cr0.5Mn0.5O3(LSCrM) into the 2.3. LST-based single perovskites and their composites
YSZ scaffold. Because of the YSZ phase addition, adhesion was improved
and the electrode polarization resistance was reduced of the anodes of The A or B site dopant properties have shown a great effect on the
LCM/YSZ composites. The primary issue in limiting the electrocatalytic LST molecule’s electrical conductivity, redox, structure, electro-
activity of the anode composite (LSCrM/YSZ) is oxygen vacancy diffu catalytic, and sinterability properties. A series of dopants X (X = Sc3+,
sion in lanthanum-chromite-based materials. Whereas, in the case of Al3+,Mg2+,Ga3+,Fen+,and Mnn+) were studied to find La0.33Sr0.67
ethanol electro-oxidation reaction the infiltration of palladium nano Ti0.92X0.08O3-δ anodes by Miller et al. Fig. 4(a) [41-44]. shows the
particles greatly improved the anodic activity of LSCrM/YSZ, resulting electrical half-cell test results performed in H2-3%H2O at a temperature
in eight times increases in the PPD of the cell without any coke forma of 900 ◦ C. The La0.33Sr0.67TiO3-δ had the lowest polarization resistance
tion. By confining the palladium nanoparticles into the nanocages of followed by doped Ga and Sc, followed by doped Mn, Fe, Mg, and Al. As
porous ceria, agglomeration of palladium at elevated temperatures can indicated in Fig. 4(c), at oxygen partial pressure of 10-18 the conduc
be effectively overcome which results in stability and enhanced activity tivities range from 1.5 to 5.5Scm− 1 of the single valency cation doped X
of palladium nanoparticles [36]. = Mg, Ga, Al, and Sc, undoped X = Ti compounds. As compared to Ga
Before sintering and screen printing as an anode layer, and Al, the conductivities of Mg and Sc are higher because of the
(La0.75Sr0.25)0.97-Cr0.5Mn0.5O3 with 15 wt% Ce0.9Gd0.1O2-δ powders experimental design improvements, leading to stronger reducing con
were pre-coated using 5 wt% of nickel from nitrates as an anode layer. ditions. When dopant is multivalent Fe (0.15Scm− 1) or Mn (0.6 Scm− 1) a
The GDC-impregnated LSCrM is found to have higher polarization per significant conductivity drop was observed which is attributed to the
formance than that of the LSCM/YSZ composite and pure LSCM anodes. fact that Mn and Fe-ions get reduced as compared to the Ti-ions as
The nanosized GDC impregnated LSCrM also has greatly improved indicated in Fig. 4(b). The use of dopants possesses a great impact on the
electrochemical as well as catalytic activities for methane dry reforming. conductivity and stability of the compounds under oxidizing and
M.K. Rath et al. successfully synthesized La0.75Sr0.25Cr0.5Mn0.5O3- reducing atmosphere. It showed variations in conductivity, particle size,
δ-La0.2Ce0.8O2-δ(LSCM-LDC) composite anodes by adjusting different and electrochemical performance by enhancing the annealing temper
weight ratios of LDC via the sol–gel combustion method. The overall ature from 1100 ◦ C to 1300 ◦ C. However, the associated issues with
performance increases as LDC acts as a grain growth block agent in anode material such as degradation and poor long-term stability need to
LSCM, reducing the electrode’s area-specific resistance too. However, in be addressed for successful commercialization.
LSCM-LDC composite anodes the deposition rate of carbon increases Suitable doping elements will further increase the oxygen vacancies
with the increase in LDC content [37]. oxidation state for titanium (i.e., Ti4+/Ti3+). Many catalytic-active ele
ments help to deposit nanoparticles on the surface of LST under reducing
2.2. SrTiO3-based single perovskites and their composites conditions. Precipitated nano-particles such as (Fe, Ni, Pd, Co, CeO2, or
Ru) facilitate oxidation reactions for the fuels through the availability of
In this portion, we will cover recent studies on SrTiO3(ST)-based more active sites, which results in enhanced catalytic and electro
perovskites anodes and the addition of various dopants to ST published chemical performance. Furthermore, the amount of exsolved nano
in the literature till now. It is evident in the literature that SrTiO3 pos particles may not be enough to partake in higher catalytic activity. One
sesses chemical stability in both reducing/oxidizing environments at of the alternative solutions to provide catalytic effect and better ionic
elevated operating temperatures. Moreover, it has great resistance to conductivity is the introduction of an O2– ionic conductive phase into
carbon and sulfur deposition. However, the conductivity and the cata doped-LST material [39]. Yoon and co-workers studied the doping of Fe,
lytic activity of pure-SrTiO3 anode are lower, resulting in higher Rp and Co, and Mn in La0.08Sr0.92M0.20Ti0.80O3-δ, where (M = Fe, Co, and Mn)
lower power density values. Also, it has characteristics of n-type semi and were named as LSFTO, LSCTO and LSMTO respectively [34]. They
conductors along with a wide range of applications. N-type mixed con also studied the effect of perovskite oxide on the catalytic activity of CH4
ducting oxides as anode material are preferred as compared to p-type fuel through oxidation state and surface atom concentration. In CH4
conductors because of their electrical conductivity and structural fuel, Co and Fe-doped perovskite exhibit higher catalytic activity than
7

Mn-doped electrode materials, which results in higher oxygen vacancy growth to interrupt electron pathways. This in turn will result in a
concentration and higher multivalent redox ratio. This suggests that harmful increase in the ohmic resistance which will significantly reduce
increased catalytic activity is attributed to a lower oxidation state with a the electrochemical activity [45]. The Ni-doped La0.2Sr0.8Ti0.9Ni0.1O3-δ
higher concentration of metal ions. Subsequently, ionization of (LSTN) anode material was prepared by Park and Choi, which was then
hydrogen or methane can easily be favored by electrons, which revealed calcined at 1300 ◦ C for 10 hrs. Nearly half of Ni was observed to be
that catalytic activity can be enhanced by no. of metal ions comprising of exsoluted from the LSTN surface in H2 atmosphere at 800 ◦ C for 12 hrs.
low oxidation states. Since electrons can certainly ionize the molecules. However, the catalytic activity was comparatively low. Whereas, the
At temperature below 600 ◦ C, the LSFTO methane conversion rate was PPD and Rp values of the cell LSTN|ScSZ|LSCF-GDC were 150 mWcm− 2
slightly greater than that of LSCTO, whereas, at above 700 ◦ C the rate and 1.66 Ω cm2 respectively in H2 atmosphere at 800 ◦ C [46]. Studies
was significantly greater. In the case of hydrogen selectivity, a similar suggested that the exsolution of Ni-particles from the surface of elec
trend was observed as presented in Fig. 4(b). As presented in Fig. 4(d-e), trode material can easily be accomplished by changing the sintering
the order of enhancement in hydrogen selectivity is LSFTO > LSCTO > temperature and modifying the fuel atmosphere of LSTN anode material.
LSMTO. However, these materials also showed high resistance to po LSTN was then sintered at 1250 ◦ C in H2 atmosphere that showed a
larization in CH4 and H2 atmosphere. At 800 ◦ C, the Rp values of LSFTO, lower Rp value of (~0.6Ωcm2) on a cell supported by ScSZ electrolyte.
LSCTO, and LSMTO were 2.5, 3.6, and 9.0 Ω cm2 in H2, and 7, 8, and 29, However, the power density of the cell was ~ 130 mWcm− 2 for 100 hrs
Ω cm2 in 50% Ar/CH4 respectively as shown in Fig. 5(f). [45]. Rath et al. at 800 ◦ C under air/H2 atmosphere respectively. In another research, it
doped × mol-percent of Ti where (x = 0.2–0.8) and 60 mol-percent of La has been found that cation deficiency in SOFC anodes can produce ox
in SrTiO3, to improve the catalytic activity of La0.08Sr0.92M0.20Ti0.80O3-δ. ygen vacancies and exsolved nanoparticles. Recently, a researcher
It has been found that as the Mn content in La0.6Sr0.4Ti1-xMnxO3-δ in introduced an A-site deficiency on Ni-doped LST anode material (LSNT)
creases, the ratio of and Ti3+/Ti4+and Mn3+/Mn4+ also increased. In to provide an efficient electro-catalytic activity [47]. Fig. 4(g) illustrate
addition, the Mn-rich anode material La0.6Sr0.4Ti0.2Mn0.8O3-δ showed the SEM images of A-site deficient (i.e., La0.52Sr0.28Ni0.06Ti0.94O3) and A-
the lowest Rp values of (0.011 and 0.054 Ωcm2) and the highest PPD site-stoichiometric (i.e., La0.3Sr0.7Ni0.06Ti0.94O3.09) perovskite anode
values of (240 and 290 mWcm− 2) at 800 ◦ C in CH4 and H2 respectively. material after reducing in 5% H2/Ar atmosphere at 930 ◦ C. The exsolved
It has been observed that in SOFC anodes, the oxygen vacancies and Ni nano-particles can be seen homogeneously distributed over the sur
exsoluted nanoparticles can be created through cation deficiency. face of the parent perovskite, while the A-site stochiometric perovskite
Agglomeration of Ni will result in de-percolation, causing particle surface does not facilitate exsolution as shown in Fig. 4(h). Burnat et al.,
Fig. 5. Illustrate the Power density and cell voltage with variable temperatures under H2 for Ba2FeMoO6-δ (a). Electrochemical stability of a single-cell (Sr2FeMoO6− δ
anode) under H2 at 850 ◦ C in (b). [50] Illustration of various models for (c). Structural transformation and (d). Sr2FeMo0.65Ni0.35O6-δ-anode surface morphology
progression in a reduced atmosphere [51].
8
have studied that, higher deficiencies in A-sites lead towards further Ni metal M (M = Co, Ni). The results revealed that in hydrogen and wet
exsolution. In addition, the precipitation and recombination of Ni were methane, Sr2CoMoO6 anode exhibited a higher cell output performance,
completely reversible processes during oxidation–reduction reactions. whereas, Sr2NiMoO6 anode showed notable performance only in dry
This specified that La0.52Sr0.28Ni0.06Ti0.94O3 exsolved by Ni- methane. Furthermore, Ji et al., [55] investigated the performances of
nanoparticles was a promising anode material with good catalytic ac La-doped Sr2NiMoO6-δ (Sr1.2La0.8MgMoO6-δ(SLMM)), where it shows
tivity and higher electronic conductivity [48]. good performance as compared to Sr2MgMoO6-δ(SMM) for the SOFC
Chung and co-workers studied the influence of Ru doping nano which is being operated on moderately desulfurized natural gas at a
particles on the B-site of LST electrode material i.e., La0.4Sr0.6Ti1-xRuxO3- temperature of 800 C. It can be concluded that double-perovskites can
δ(LSTR). Under reducing conditions, trace amounts of Ru metallic be effectively used as anode material in cells operating on natural gas.
nanoparticles were identified on the surface of LSTR which showed a Xie et al., reported that the structural stability enhancement of Sr2Mg1-
decrease in its electrical conductivity from 343.9 Scm− 1 for (pure LST) xNixMoO6-δ(x = 0–0.9) can be achieved up to x = 0.7, suggesting that an
to 202.9 Scm− 1 for (LSTR0.05) respectively at 900 ◦ C. Ionic conductivity increase in nickel doping is attributed to the reduction in the bandgap
was enhanced from 0.0020 Scm− 1 (pure LST) to 0.0028 Scm− 1 for energy and an increment in the electronic defect’s concentration.
(LSTR0.05) respectively. The main reason for variation in conductivity Equation (9) shows that the creation of oxygen vacancies is accompa
in B-site deficiency was the production of oxygen vacancies through the nied by the reduction Mo6+ to Mo5+.
reduction of Ti3+. Furthermore, the single-cell anode polarization
1
resistance of LSTR0.05-YSZ was inversely related to time. For example, 2MoxMo + Oxo →2Mo’Mo + Vo.. + O2 (9)
2
the Rp value decreased from (4.17 to 2.74 Ω cm2) after 24 hrs in H2
atmosphere. While, its PPD increased from 52 mWcm− 2 (for LST-YSZ) to Wang et al. employed a sol–gel process to synthesize Sr2MgMo1-
115 mWcm− 2 (for LSTR0.05-YSZ) respectively [49]. xVxO6-δ(SMMV) and studied its potential as an anode for SOFCs that use
biogas as a fuel. It was found that Sr2MgMo0.95V0.05O6-δ prepared in 5%
2.4. Modified double perovskites and their composites hydrogen/argon showed better hydrogen-sulfide tolerance, catalytic
activity, and stability, for combustion of biogas as compared to SMMO
The double perovskite materials are suggested to synthesize anode [56]. Further modification by adding metallic nanoparticles can in
with enhanced performance. Numerous cations can be used to substitute crease the electrical conductivity and catalytic activity for the oxidation
A or B or both sites to make different composites. Based on the A and B- of fuel. Li et al. concluded that H2 adsorption ability and electrical
site positions, perovskite-type oxides can be either partially or reduced conductivity can be increased gradually by the partially decomposed
in a reductive environment. Double perovskite materials can be made by PBFNO in a reducing environment. Table 1 shows the properties of
substituting the B-site cation (A2B1-xBx′ O6), the A-site cation (A1- different perovskite anode materials by varying fuel at different oper
xAxBB́ O6), or both (A1-xAxB1-xBx O6). In this review, the A and B-site
′ ating temperatures.
doping on double perovskites anode materials will be reviewed.
A2FeMoO6-δ (A = Ca, Sr, Ba) oxides have been investigated as 3. Recent advancement of cathode materials
possible double perovskite anode materials for SOFCs. The hybridization
and degeneracy of the Fe2+-Mo6+ and Fe3+-Mo5+ states result in a A cathode is another main component that affects the SOFC perfor
narrow band formation, which imparts the metallic conduction mance. Following are the main requirements for SOFC cathode mate
behavior. The A2FeMoO6-δ anodes’ electrochemical performance in H2 is rials: (a). It should exhibit high electronic conductivity. (b). It should
found to be in the order: Ca2FeMoO6-δ < Ba2FeMoO6-δ < Sr2FeMoO6-δ as exhibit good compatibility and coefficient of thermal expansion (TEC)
depicted in Fig. 5(a)[50]. The poor performance in the case of Ca2Fe equivalent to the electrolyte. (c). It should be of high surface-exchange
MoO6-δ anode was because of its lower oxygen vacancy concentration oxygen kinetics and (d). Resistance to Cr (Chromium) poisoning. The
and its decomposition at elevated temperatures. Whereas, Sr2FeMoO6-δ operating temperature can be minimized by applying MIEC (Mixed ionic
showed a great combination of high thermal stability, electrical con and electronic conducting) electrodes in SOFC which results in sub
ductivity, electrochemical performance, and thermal compatibility, stantial enhancement of three-phase boundary length which further
therefore is a potential anode material to be used in SOFCs as illustrated results in increased active sites. The current review article will focus on
in Fig. 5(b). Yang et al., prepared another anode material with compo the defect chemistry, reactivity, electronic structure, stability, conduc
sition of lanthanum-doped Sr2FeMoO6-δ (Sr2-xLaxFeMoO6-δ) for SOFCs tivity, performance, and surface segregation of lanthanum, Barium,
[51]. Du and co-workers discovered the decomposition of Sr2FeMo0.65 Praseodymium, Neodymium and Samarium, Gadolinium, Yitria, and
Ni0.35O6-δ perovskite into Sr3FeMoO7-d, FeNi3 nano-particle catalyst, Strontium-based perovskite cathodes and addition of different dopants
and Sr(Fe,Mo)O3-d, after reduction as presented in Fig. 5(c). Fig. 5(d) for SOFCs.
explains under reducing environment the surface morphology of SFMNi.
The results reveal that ionic conductivity and oxygen vacancies can be 3.1. Lanthanum, Barium-based perovskites cathode and their composites
greatly improved by Fe-Ni nanoparticles exsolution, resulting in better
performance of anode. La1-xSrxMnO3-δ (LSM) is widely manufactured worldwide and
Good-enough and co-workers investigated the nature of regarded as traditional cathode material. It is attributed to pure elec
Sr2Mg1–xMnxMoO6-δ anode material by using natural gas (fuel) at tronic conductivity due to which it exhibits remarkable TEC divergence
650–1000 ◦ C. Outstanding toughness and sulfur resistance were and compatible stability with YSZ electrolyte. However, these cathode
observed because of variable molybdenum ion [52]. It has great po materials present some difficulties firstly, at intermediate temperature
tential because of its higher thermal expansion coefficient, redox sta range (500–800 ◦ C) these materials exhibit increased polarization
bility, and electrocatalytic activity. It is also reported in the literature resistance and secondly interaction between LSM and YSZ electrolyte at
that Fe-containing Sr2Mg0.5Fe0.5MoO6-δ anode for methane combustion elevated operating temperature (>1300 ◦ C) result in lower (less than
gives an improved catalytic activity, the highest conductivity 30%) Sr- segregation. LSM act as a semi-conductor and its conductivity
approaching 28 Scm− 1 in hydrogen at a temperature of 800 ◦ C. The can be enhanced by doping a p-type impurity that results in increased
complete substitution of ferric for magnesium (Sr2FeMoO6) exhibited ionic conductivity of oxide ions [77].
higher electronic conductivity (value approaching to 1000 Scm− 1) in 5 The LSCF perovskite is the most studied and illustrative MIEC cath
vol% hydrogen in argon [53]. ode material for IT-SOFCs. It has high electrical and ionic conductivities
Huang et al. [54] studied some more members of the Sr2MMoO6 of 1x102 Scm− 1 and 1x10-2 Scm− 1 respectively. Whereas it exhibits a
series for application as anode materials containing a 3d-block transition good oxygen surface exchange coefficient (k = 6x10-6 Scm− 1) and
9

Table 1
List of different perovskite anode materials by varying fuel at different operating temperatures.
Conductivity (Scm− 1) / PPD (mWcm− 2) EIS
Sr. Anode composition Synthesis routes Temp (◦ C) /Temp(◦ C) (Ω cm2) Fuel Ref
No / Temp used
1 La0.75Sr0.25Cr0.5Mn0.5O3 Solid-state 38/900 ◦ C 470/900 ◦ C 0.2/900 ◦ C 97%H2/ 3%– [57]

reaction H2O
2 La0.75Sr0.25Cr0.3Fe0.2Mn0.5O3− δ Citrate method 1.04/750 ◦ C 550/750 ◦ C 0.48 (H2), 0.55 H2,Dry-CH4 [58]
(CH4) / 750 ◦ C
3 SrFe0.9Ti0.1O3− δ Sol-gel method 2.53/600 ◦ C ——— ——— 5% H2/Ar [59]
4 SrFe0.8Cu0.1Nb0.1O3− δ Sol-gel process, 60/415 ◦ C 423/700 ◦ C 0.25/700 ◦ C 5%H2/Ar [60]
5 La0.5Sr0.5Fe0.9Mo0.1O3− δ Sol–gel method 6.2/800 ◦ C 722(H2), 513(CH4) /800 ◦ C 3.04/800 ◦ C Dry-H2,CH4 [61]
6 Sr0.9Ce0.1Co0.2Fe0.8O3− δ EDTA-citrate 22/600 ◦ C 150/800 ◦ C ~1.80–1.90 H2, air [62]
method /700 ◦ C
7 La0.9Ca0.1Fe0.95Nb0.05O3− δ Citric-acid nitrate 42.55/850 467.1(H2), 375.8(CO), 0.75(H2), H2, CO [63]
method / 750 ◦ C 2.30(CO)
/ 700 ◦ C
8 La0.4Sr0.6TiO3− δ EDTA-citrate 343.902 52/850 ◦ C 4.95/850 ◦ C H2 [64]
method /900 ◦ C
9 La0.3Sr0.7Ti0.8Cr0.2O3 Solid-state 53/800 ◦ C 43.86 ——— 5% H2/Ar [65]
reaction / 900 ◦ C
10 Sr0.4La0.6Ti0.8Mn0.2O3− δ combustion 2.68/800 ◦ C 290(H2), 240(CH4)/800 ◦ C 0.107(H2) H2, CH4 [66]
method 0.209(CH4) /800 ◦ C
11 Sr0.4La0.6(Fe0.75Ti0.25)0.6Ni0.4O3- Solid-state H2(2 2 6), H2(3 1 8), Ethanol(1 4 7), ——— H2, NH3, CH4, [67]
δ reaction Ethanol(1 6 4),NH3(1 1 4), NH3(2 2 6),CH4(1 8 4)/ 600 ◦ C Ethanol, NH3
CH4(89)/600 ◦ C
12 Sr1.8La0.2FeMoO6− δ Solid-state 460 /800 ◦ C 885/800 ◦ C 0.35/800 ◦ C H2 [68]
reaction
13 Sr2Mg0.5Fe0.5MoO6− δ Citric-acid nitrate 28/ 800 ◦ C ——— ——— H2 [69]
method
14 Sr2FeNb0.2Mo0.8O6- δ Solid-state 5.3/800 ◦ C 520 /800 ◦ C 0.057(H2) H2, CH4 [70]
reaction /800 ◦ C
15 Sr1.8Sm0.2Fe1.5Mo0.5O6 Solid-state 25/850 C◦
742 /850 C◦
0.50 /800 ◦ C H2 [71]
reaction
16 Sr1.95Fe1.4Ni0.1Mo0.5O6- δ Combustion 26.6/800 ◦ C 606 /800 ◦ C 0.48/800 ◦ C H2 [72]
method
17 Sr2Fe4/3Mo2/3O6-δ Combustion 16/800 ◦ C 547/800 ◦ C 0.20/800 ◦ C H2 [73]
method (3%H2O)
18 PrBaMn2O5 Pechini method 8.16/800 ◦ C 1700(H2) ——— 5%H2, propane [74]
1300
(propane)
19 PrBaMn1.5Fe0.5O5+δ EDTA-citrate 7.4/800 ◦ C 540/800 ◦ C 0.68 /800 ◦ C 5% H2/Ar [75]
method
20 SDC-NiO/La0.6Sr1.4MnO4- δ EDTA-citrate 0.69/900 ◦ C 108/800 ◦ C 0.1/700 ◦ C H2 [76]
method
oxygen diffusion properties (D*= 5x10-7 S-1cm− 2) at 800 ◦ C, respec first stage can explain this effect. The reactivity trend of La0.6Sr0.2M0.2
tively as compared to LSM materials (i.e., k = 5.62x10-9 Scm− 1, D* Fe0.8O3-δ with YSZ electrolyte is of the order Mn < Cr > Ni > Co which
=4.0x10-15 S-1cm2). It has a TEC of 14–15.2x10-6 K− 1, which is higher can be explained by their respective relative stabilities. The A-site sub
than GDC’s 11.5–11.9x10-6 K− 1, but it can be combined with GDC to stoichiometric, in contrast to LSM, does not affect the activity of
change the thermal-expansion properties and increase the electro (La0.6Sr0.2)zM0.2Fe0.8O3-δ (M = Co, Ni) perovskite with YSZ. The YSZ and
chemical activity [79]. While adding a small amount of doped ceria can perovskite reaction can be written as shown in Equation (10):
improve the surface exchange kinetics and thereby increasing the SrMO3 +ZrO2 = SrZrO3 +MOx +1−2 xO2 Where, x = 1to1.5 (10):
overall LSCF catalytic activity. Murray et al., [78] demonstrated that Previously, Lina Miao et al., have reported high-performance Co-free
adding 50 vol% GDC to LSCF results in a tenfold reduction in polariza cathode material La1⋅2Sr0⋅8Ni0⋅6Fe0⋅4O4+δ(LSNF) with BaZr0.1
tion resistance, with ASR values as low as 0.01 Ωcm2 and 0.33 Ωcm2 at Ce0.7Y0.2O3-δ(BZCY) as an electrolyte. It had low Rp and high conduc
750 ◦ C and 600 ◦ C respectively for the LSCF/GDC cathodes. tivity of 0.078 Ωcm2 and 106 Scm− 1 at 700 ◦ C respectively [82].
LSCF reacts with zirconia-based electrolytes readily, resulting in Rongrong Li et al. (2019a), Fangjun Jin et al. developed a potential
secondary phase formation i.e., SrZrO3 at a lower temperature (800 ◦ C). candidate La1⋅4Ca0⋅6CoMnO5+δ(LCCM) for cathode material with the
In another study, Chen et al., [79] detected the phase formation of highest ionic conductivity of 223 Scm− 1 at 800 ◦ C and electrochemical
SrZrO3 in the mixture of LSCF-YSZ which is sintered at the temperature performance of 0.226 Ωcm2 at 850 ◦ C which was further improved by
of 800 ◦ C for four hours in the air. In contrast to YSZ cubic structure, the addition of Sm0.2Ce0.8O1.9(SDC) [83]. Nowadays Co-free perovskite
SrZrO3 possesses an orthorhombic structure at room temperature. The cathodes are considered to be hot research for intermediate temperature
ionic conductivities of SrZrO3 phase, GDC, and YSZ are reported to be SOFCs. Perovskite containing ferrites has attracted more attention as a
1.87x10-6 Scm− 1, 8.70x10-2 Scm− 1, and 5.40x10-2 Scm− 1 at the same SOFC electrode due to its excellent electrochemical activity. The mate
temperature values. The development of SrZrO3 as a secondary phase at rials such as La,Sr(Fe,Mn)O3-δ(LSFM) and SrFe0.75Mo0.25O3-δ(SFM)
the cathode/electrolyte interface acts as a blocking layer for O2-ions and exhibit high electrochemical properties to be utilized both as cathode
is detrimental to the LSCF cathodes’ electrochemical performance [80]. and anode. It is well known that (La,Sr)(Co,Fe)O3-d oxides (based on
Kindermann et al., [81] explored the (La0.6Sr0.2)zM0.2Fe0.8O3-δ (M = SrCoO3-δ) hold outstanding oxygen transport properties at an operating
Cr, Mn, Co, Ni) and YSZ electrolyte compatibility, demonstrating that temperature as higher as > 700 ◦ C [84]. Considering the high redox
SrZrO3 is formed when all compositions react with YSZ. The creation of capacity of LST, researchers have substituted Ti with Co to improve the
nuclei for the zirconate phase and their consequent rapid growth in the catalytic activity for oxygen reduction, attributing towards the LST
10

utilization as a cathode material. However, cobalt-based perovskite, like [87]. The high concentration of oxygen vacancies may be available due
La0.3Sr0.7Ti1-xCoxO, La0.4Sr0.6Ti1-yCoyO3-δ, and La2xSrxCoTiO6, exhibits to increased ORR surface activity and high diffusivity of O- ions. Ion
high catalytic activity have recently been studied. substitution exhibit some interesting effects on the properties of LnBa
Y and Zr co-doped perovskite (BCFZY0.1) are stable, active, and Co2O5-δ material. For example, it is reported that replacing Pr with Gd
potential cathode for SOFCs working at lower temperatures (≤500 ◦ C). can reduce the electrical conductivity, oxygen defects concentration,
Based on the higher thermal cycling stability, lower activation energy, and performance in a fuel cell. However, the trend of replacing Ba with
and higher ORR activity. BCFZY0.1 is suggested to be an intriguing Sr in the same material is contrary. Researchers have mentioned the
cathode in SOFC applications. To measure its stability, in the long run, synergistic effect of cobalt doping in LnBaCo2O5-δ double-perovskite
cell #1 was operated for>2500 hrs under different operating conditions structure, i.e. Sr on (A-site) while Fe on (B-site). It makes different
and no observable performance degradation was observed. J.Felix et al, channels for fast diffusion of O2 ions, and exchange of oxygen surface
reported Ba0.5Sr0.5(Co0.7Fe0.3)0.6875W0.3125O3-δ(BSCFW) composite while maintaining compatibility with IT-SOFC electrolytes.
consisting of disordered single perovskite and ordered double perovskite Despite the good results, the ASR values of PrBaCo2O5+δ are not
oxide phases. Both of these phases interact and promote both chemical perfectly suitable for cathodic applications when the operating tem
and microstructural stability [85,86]. perature is less than 600 ◦ C. However, the performance can be increased
through Sr doping. A simple perovskite PrBa0.94Co2O5+δ (SPN-A-PBC)
3.2. Praseodymium, Neodymium and Samarium based perovskites and having higher operating stability and electro-catalytic ORR activity was
their composites developed by the in-situ exsolving process. At 6 hrs deposition time, the
SPN-A-PBC electrode is formed (Fig. 6(d)) which shows a lower Rp
Recently, the double perovskite structures mainly LnBaCo2O5- (0.025 Ω cm2) as seen in Fig. 6(c). The single-cell having SPN-A-PBC
δ(whereas Ln = Sm, Pr, and Nd) respectively, have attracted much cathode showed a maximum power density value of 1.1 W cm− 2 at
attention due to faster O2 exchange on the surface, easier diffusion of O2 the temperature of 700 ◦ C (Fig. 6(a-b)). Fig. 6(e) illustrates a possible
ion, and high electrical conductivity than other simple cathode materials mechanism of exsolution. At the synthesis temperature of 1050 ◦ C, the
Fig. 6. Cross-sectional illustration of SEM images for the anode-supported single cells (SPN-A-PBC cathodes) (a). and its peak power density at 600–700 ◦ C (b).
Impedance spectra of symmetric half-cells with the A-PBC and SPN-A-PBC electrodes at 600–700 ◦ C in the air (c). While its SPN-A-PBC electrode was deposited on a
CGO substrate at 950 ◦ C for 6 hrs in the air (d). Schematic for a possible exsolving mechanism of the SPN-A-PBC electrode (e). [88] association between conductivity
and Ca doping contents and the electrical conductivity of PrBa1-xCaxCo2O5+δ and (f, g) [89].
11
segregation of phases occurred. In the electrode deposition process, the behavior in accordance with ASR and conductivity. Electrochemical
perovskite nanoparticles exsolved and transformed into nanorods [88]. performance suffers significantly when doping levels are high. However,
PrBa1-xCaxCo2O5+δ (PBCC) shows the composition of Ca-doped perov by swapping a small quantity of Ni for Co, performance can be
skite which exhibited enhanced electrical conductivity and electro improved. According to the literature, NdBaCo1.6Ni0.4O5+δ is a more
chemical performance with lower thermal expansion. Fig. 6(f) shows the promising compound exhibiting 16.9x10-6 K− 1 TEC value which is less
electrical conductivity of the PBCC as described by the Arrhenius plot than the parent compounds. Liu and coauthors [98] reported that lower
which decreases with the increase in temperature. Fig. 6(g) shows the Cu content causes a decrease in TEC values. However, worsened values
electrical conductivity as a function of the amount of calcium, indicating were observed for conductivity and ASR containing increased Cu con
the hole charge carriers are increased because of higher mobile oxygen tent [95]. Nd0.5Sr0.5Fe0.8Cu0.2O3-δ-Sm0.2Ce0.8O1.9 composite cathode
concentration [89]. with 40 wt% Sm0.2Ce0.8O1.9 component showed the compatibility of
Another potential compound is (PrBa0.5Sr0.5Co2O5+δ), possessing TEC (13.2 × 10-6 K− 1) to Sm0.2Ce0.8O1.9 (12.6 × 10-6 K− 1). At 700 ◦ C
significant conductivity: at the temperature of 600 ◦ C, the conductivity minimum polarization resistance of 0.056 Ωcm2 was found. The per
values were increased in the range of 150–900 Scm− 1 without doping formance of the composite cathode was stable at 700 ◦ C for a time
and up to 600–1400 Scm− 1 with Sr doping. PrBa1-xSrxCo2O5-δ, prepared duration of 370 hrs without any considerable change in the polarization
by Park at al., [90] showed the highest conductivity in the case of Pr- resistance performance.
based perovskites. However, as mentioned in the literature these ma The performance of Sm-doped materials is less studied, but it is found
terials are not suitable for cathodic application when accompanied by to have some interesting results. The Sm0.6Sr0.4FeO3-δ-Ce0.8Sm0.2O2-δ
common electrolytes because of their higher TEC. S. Choiel al., have cathode was prepared via co-synthesis technique [99]. It showed higher
reported a highly efficient cathode material i.e., PrBa0.5Sr0.5Co2-xFexO5+ conductivity, enhanced microstructure, and better electrochemical
δ(PBSCF) for LT-SOFC. It was worth notify that when x = 0.5, then the properties as compared to the one prepared via dry-mixing methodol
cathode material (named as PBSCF05), exhibits lower Rp values of 0.33 ogy. The comparison of research publications reveals that the interest of
Ωcm2 and 0.056 Ωcm2 at 500 ◦ C-600 ◦ C respectively which was almost researchers is focused on elements presented above and still more work
half of that of BSCF cathode (0.7 Ωcm2 at 500 ◦ C). Due to a large amount needs to be done to explore the incorporation of elements like Nd, Pr, or
of Fe doping (~50%), the higher oxygen concentration defects in the Ln- Sm in SOFCs application [100].
O (where Ln = Nd and Pr) layer aid to improve its performance and
enhanced oxygen kinetics [91]. Kim et al. synthesized Mn-doped 3.3. Gadolinium, Yttria, and strontium based perovskites and their
perovskite cathode (PrBa0.5Sr0.5Co2-yMnyO5+δ) (y = 0, 0.25, 0.5) and composites
achieved 14.3x106 K− 1 TEC for PrBa0.5Sr0.5Co1.5Mn0.5O5+δ. By using an
anode-supported fuel cell with GDC as an electrolyte, it was found that Compounds having gadolinium in the A site in the form of
the composite PBSCF05-GDC as a cathode exhibit an excellent peak GdBaCo2O5+δ [155] double perovskite were explored by many re
density of 2.90, 2.16, 1.31, and 0.71 Wcm− 2, under H2/(3% H2O) as fuel searchers in the last few years. However, it is seen to be comparatively
at 650–500 ◦ C, respectively as compared to BSCF(1.01 Wcm− 2 at less efficient. At a temperature of 600 ◦ C, the conductivity is found to be
600 ◦ C) cathode. Ni-GDC|GDC|PBSCF05-GDC cell displays good stabil in the range of 100 to 500 Scm− 1 and the ASR value is between 0.3 and
ity without degradation for 150 hrs under an OCV of 0.6 V at 550 ◦ C 22 Ωcm2. By substitution of Sr, a significant improvement is achieved,
[92]. however, only a few researchers have looked into its electrochemical
Doping with Nd on the A-site, NdxSr1-xFe0.8Cu0.2O3-δ, is responsible properties [101,102].
for various factors that affect several electrochemical properties, elec In comparison to SrFeO3-δ (SF), Xiao et al. discovered that Mo-doping
trical and thermal expansion. In addition to this, doping significantly into SF (SrFe1-xMoxO3-δ) can maintain the cubic structure in air,
affects the structure. Compositions Nd0.5Sr0.5Fe0.8Cu0.2O3-δ (x = 0.5) are enhancing the sintering performance On the other hand, the electrical
known as, optimum compositions exhibiting an average TEC of 14.7 × conductivity was reduced in air. Y increasing the doping ratio to x =
10-6 K− 1 over 25–800 ◦ C with the Rp of 0.071 Ωcm2 at 700 ◦ C. Studies 0.25, due to reduction in charged carriers the conductivity value was
suggest that there was not any kind of degradation was being observed reduced to 22 Scm− 1 at a temperature of 800 ◦ C. As indicated in TPR
for the polarization resistance during constant testing for 350 hrs at profiles, Mo-doping has improved the tolerance to the reduction of
700 ◦ C. It was also found that performances of NdxSr1-xFe0.8Cu0.2O3-δ SrFeO3-δ. He et al., studied that tin-doped Sr2Fe1.5Mo0.5-xSn-xO6-
cathodes are greatly dependent on the availability of surface oxygen δ(SFMSn) positively contribute towards better ORR performance
vacancy and composition which in turn are dependent on several crys including the bulk diffusion and surface exchange processes. By
tallographic parameters [93]. increasing the tin content from × = 0 to × = 0.3, the re-equilibration
By Considering Nd as A-site rare earth metal for perovskites, studies time was reduced from 5000 to 600 s, showing that Sn doping can
reported for Pr-based ones are greater. The NdBaCo2O5+δ conductivity significantly enhance the kinetics of oxygen reduction [103-108].
values were found to be in a range of 200 to 1000 S cm− 1 at 600 ◦ C with Mössbauer spectroscopy has revealed that at the larger doping content
variable ASR values from 0.2 to 6 Ω cm2 at the same temperature of Nb, decreasing the Fe4+ to Fe3+ ratio resulted in a reduction in the
(600 ◦ C) by up to two orders of magnitudes at 500 ◦ C [94]. Park et al. average oxidation state of ferric from 3.403 (for SrNb0.05Fe0.95O3-δ) to
improved conductivities and ASRs were achieved from the corre 3.375 (for SrNb0.1Fe0.9O3-δ) and then to 3.291 (for SrNb0.2Fe0.8O3-δ).
sponding un-doped perovskites by comparing the electrochemical Furthermore, the oxygen desorption process and thermal expansion
properties of the perovskite (NdBa0.5Sr0.5Co2O5+δ) with those reported coefficient were also reduced with the increase in Nb content and were
for Pr-based ones. ASR values ranged from 0.1 to 1.2 Ωcm2, whereas explored by Liang and co-workers [108]. Chen et al., has reported a
conductivity values were recorded in the range of 300–2400 Scm− 1 novel cobalt-free Sc-based perovskite cathode having a composition of
[95]. Junyu Chen et al., have developed another perovskite material Nd SrSc0.175Nb0.025Fe0.8O3-δ(SSNF) [109]. It was anticipated that the pres
(Ba0.4Sr0.4Ca0.2)Co1.6Fe0.4O5+δ for proton-conducting SOFC which ence of Nb will enhance the ORR activity and the presence of Sc will
accomplished higher conductivity and low polarization resistance restrain the corresponding TEC value.
values of 2500 Scm− 1 at 800 ◦ C and 0.072 Ωcm2 at 750 ◦ C respectively SC’s perovskite structures were typically stabilized/sustained by
[96]. Biao Wang et al., have synthesized Ba0.5Sr0.5Co0.8Fe0.1Ni0.1O3-δ partial substitution of B-site element with higher oxidation-state ele
(BSCFN) cathode material which possesses a low Rp value of 0.033 ments like phosphorous(P)[110], antimony(Sb)[111], molybdenum
Ωcm2 at 800 ◦ C and a maximum conductivity of 35.3 Scm− 1 at 425 ◦ C in (Mo)[112], and niobium (Nb)[113] which contribute to low polariza
air respectively [97] tion resistance (Rp) values at low temperatures. Sun and co-workers
Although Ni doping is responsible for improved thermal expansion [156], reported a new promising perovskite cathode material Ce-doped
12
SC(Sr1-xCexCoO3-δ) which holds good electrochemical performance at an based perovskites i.e., PrBaCo2O5+δ(20.4 × 10-6 K− 1) and Ba0.5Sr0.5
intermediate temperature range. Highly anisotropic displacement fac Co0.8Fe0.2O3-δ (20.44 × 10-6 K− 1) at 30 to 850 ◦ C respectively. In another
tors were observed in Sr0.95Ce0.05CoO3-δ(SCCO) oxygen atoms, sug study conducted by Li, Mengran, et al, the 20% tantalum and niobium
gesting great ionic mobility at 1100 K. Zhou et al., [114] studied an were substituted into strontium cobaltite’s, resulting in SrCo0.8Ta0.2O3-
active perovskite cathode material, in addition to single doped-SCs δ(SCT20) and SrCo0.8Nb0.2O3-δ(SCN20) perovskite oxides, respectively.
perovskite which was characterized by partial substitution of Co-ions The better performance of the SCT20 cathode was observed as compared
with Nb5+ and Sc3+. These dopants result in an exceptionally high to that of SCN20, which is due to the lower electronegativity value of
ORR activity at a temperature range of 550 ◦ C. Till now, few studies Ta5+. The SCT20 was found to show better ORR performance and less
have been reported that co-doping with high-charged dopants may have ASR values as compared to SDN20, implying that SCT20 is better for
a synergistic effect on catalyzing the ORR activity in low-temperature ORR catalyzing. Furthermore, SCT20 cathodes have a lower ORR acti
SOFC (LT-SOFC) cathodes. They investigated the influence of B-site vation energy than SCN20 cathodes such as 104 and 118 kJ/mol
high-charge dopants on the activity of SrCo0.8Nb0.1Ta0.1O3-δ(SCNT) respectively as shown in Fig. 7(d) [117].
perovskite cathode materials at low temperatures. These materials In another study, the cathode made up of a commercial
showed an excellent and stable electrochemical performance below (La0.6Sr0.4)0.95Co0.2Fe0.8O3-δ(LSCF)-Ce0.8Gd0.2O1.9(GDC) composite
500 ◦ C. Symmetric SCNT cathode material displays a low polarization skeleton and the capping layer of a nano-scaled, ORR-active SrCo0.9
resistance value of 0.68 and 0.16 Ωcm2 at 450 and 500 ◦ C respectively. Ta0.1O3-δ(SCT). Fig. 7(e) depicts the production of distinct NPs and a
Fig. 7(a, b) indicate the peak power density values of SCNT cathode constant layer of SCT on LSCF at high and low temperatures. It repre
material i.e., 0.7 Wcm− 2 (at 450 ◦ C) and 1.2 Wcm− 2 (at 500 ◦ C) sents the surface reactions in a Cr-containing environment. In such
respectively. Studies have shown that the substitution of Co for Ta5+ and conditions, the species i.e., CrO3 (g) will react readily with SrO, resulting
Nb5+ will lead to a proper balance of ion mobility, electron transfer, and in the formation of SrCrO4 which is inactive and insulating, thus ORR
oxygen vacancies in the surface, which may be beneficial for ORR ac active sites are blocked. On the other hand, due to SrO-free surface, SCT
tivity in SCNT cathode [115]. It is reported in the literature that the will not react with CrO3(g) [118,119].
cubic perovskite structure of SrFe1-xWxO3-δ has strong compatibility Chuangang Yao et al., reported a novel cobalt-free cathode material
with SDC electrolyte, whereas SrFe0.7W0.3O3-δ has the lowest TEC value SrTa0.1W0.1Fe0.8O3-δ (STWF) which exhibits a lower Rp value of 0.074
and is compatible with SDC electrolyte [116]. The high oxidation state Ωcm2 at 800 ◦ C. However, STWF had lower conductivity of 32.5 Scm− 1
W favors the reduction of Fe4+ at a lower temperature, resulting in a at 450 ◦ C as Ta and W co-doping leads to Fe4+ reduction, thereby
decrease in formation energy associated with oxygen vacancy Fig. 7(c). regulating the charge neutrality of the crystal. In addition, electrical
Also, by increasing the W content, the temperature associated with the transfers in STWF samples can damage the Fe3+–O2-Fe4+ network,
transition from semiconducting to metallic behavior increased. The TEC thereby a drop in the electrical conductivity was observed at high
values of SrNb0.2-xTaxFe0.8O3-δ were closer to that of SDC electrolytes temperatures [120-124]. The performance of cathode material can be
(changed from 13.52 × 10-6 K− 1 to 16.31 × 10-6 K− 1) as compared to Co- improved through surface amendment. Nanoparticles are occasionally
Fig. 7. (a). A diagram showing the minimum energy migration path for oxygen vacancy (VO) in SrCo0.75Nb0.125Ta0.125O3-δ, where dopants are represented by colorful
balls and Co is located within the octahedral along the path. (b). Single-cell performance of anode-supported SCNT | GDC| GDC-Ni at 450–550 ◦ C with air at the
cathode and H2 at the anode. (c). First-principles calculations for the SCNT perovskite oxides, unit cells, single and Co-doped models [117] (d). ORR activation energy
of SCT20 and SCN20 cathodes [118] (e). Schematics of infiltrated and untreated cathode depicting chemical tolerant to Cr-species in the air [119].
13

considered to be very effective for enhancing surface-exchange kinetics. can be indisputably got poisoned by H2S [6]. Experimental studies
However, due to the high surface energy of nanoparticles, poor thermal supported by X-ray diffraction suggest that the structure of PBFO ma
stability is a significant problem. Further modifications will help to terials differs from single to double phase perovskites [7]. Sc and Ru
improve the efficiency of cathode materials. The parameters of various components specified for LSSM and SSFR electrodes are overpriced due
perovskite cathode materials at various operating temperatures are which inclusively raises the price of production for SSOFC. Thus, there is
shown in Table 2. a need to develop new symmetric materials having an effective cost of
The conductivities and CTE of cobalt-free and cobalt-based materials production. Liu et al. have reported a new type of symmetrical perov
from distinct references are compared in Fig. 8(a-b) for different oper skite electrode material Sr2Fe1.5Mo0.5O6-δ (SFM) with good redox sta
ating temperatures. bility, high electronic conductivity in H2, and air atmosphere for SSOFC.
The OCV of the symmetric cell was 1.07 V, using LSGM as an electrolyte
4. Recent advancement in symmetric perovskite materials and under humidified H2, while the cells OCV ranges to 0.90 V under 3 vol%
their composites H2O(CH4) as fuel at 900 ◦ C respectively. The PPD of the symmetric SFM
were 230 and 835 mWcm− 2 under CH4 and H2 as a fuel at 900 ◦ C. Zhang
In previous years, the focus of various studies was performed on et al studies revealed that SFHf cathode material exhibit polarization
different types of materials and it was suggested that there are only a few area with low specific resistance value of 0.193 Ωcm2 at 600 ◦ C for a
materials that have been reported as symmetric SOFC electrodes SFHf|Sm0.2Ce0.8O1.9(SDC)|SFHf symmetric cell with highest power
including La0.75Sr0.25Cr0.5Mn0.5O3-δ (LSCM) [1], Sr2Fe1.5Mo0.5O6–δ density values of 1.94 Wcm− 2 at 700 ◦ C in anode assisted fuel cell (Ni+
(SFMO) [2], PrBaFe2O5+δ (PBFO) [3], La0.8Sr0.2Sc0.2Mn0.8O3-δ (LSSM) (ZrO2)0.92(Y2O3)0.08(YSZ)| YSZ|SDC|SFHf) [148].
[4], Sm0.9Sr0.1Fe0.9Ru0.1O3-δ (SSFR) [5] and La0.5Sr0.5Co0.5Ti0.5O3-δ In another piece of research, Sm0.95Ce0.05FeO3–δ (SCFO) perovskite-
(LSCT). These materials are characterized as SOFC but due to various type oxide was evaluated against its potential application as a material
reasons possess limited applications. LSCM exhibits remarkable chemi of electrode in symmetrical SOFCs. The SCFO was found to have good
cal stability as an anode material in fuel supporting atmosphere with redox stability when the sample was calcined in 5% H2/N2 at a tem
relatively lower electronic conductivity. In addition, LSCM is charac perature of 850 ◦ C for a total time of 10 hrs. The peak power density
terized by poor oxygen reduction activity. These materials show when humidified hydrogen was used as fuel at a temperature of 800 ◦ C
enhanced electrochemical performance at ≥ 900 ◦ C used in SSOFC but was as high as 130 mWcm− 2 [8]. Moreover, SrFe0.75Zr0.25O3–δ
Table 2
Variation in operating temperatures influences the properties of different perovskite cathode materials.
Conductivity (S cm− 1) / Temp Activation energy EIS TEC ×
Sr. Cathode composition Synthesis routes (◦ C) Ea (eV) (Ω cm2) 10− 6 Ref
No / Temp (k− 1)
1 La0.7Sr0.3MnO3 Combustion method 4.5/1000 ◦ C 0.58 ——— 11.7 [125]

2 Pr0.6Sr0.4MnO3 ± δ Combustion method 214/600 ◦ C ——— ——— 12 [126]
3 Sm0.5Sr0.5CoO3-La0.6Sr0.4FeO3 Pechini method ——— ——— 0.64/700 ◦
C 17.7 [127]
1
4 Sm0.5Sr0.5MnO3 Sol-gel method 138/800 ◦ C 13.93 kJmol− 0.50/800 ◦
C 10.7 [128]
5 La0.6Sr0.4Fe0.8Ni0.2O3− δ Sol–gel method 130/500 ◦ C ——— 0.142/ 11.9 [129]
800 ◦ C
6 La0.8Sr0.2Co0.2Fe0.8O3-δ Solid-state reaction 41/800 ◦ C 1.684 0.92/800 ◦
C 18 [130]
7 Ba0.5Sr0.5Co0.8Fe0.2O3 Citric-acid nitrate 37.6/800 ◦ C 0.08/600 ◦
C 20 [131]
method
1
8 Sr0.9Ce0.1Fe0.8Ni0.2O3–δ Smart self-assembly 21.5/650 ◦ C 152.2 kJmol− 0.028/ 16.8 [132]
800 ◦ C
9 BaFe0.8Zn0.1Bi0.1O3− δ Citrate combustion ——— ——— ——— 9.27 [133]
method
10 La0.6Sr0.4Fe0.9Nb0.1O3 Solid-state reaction ——— ——— 0.16/800 C ◦
—— [134]
11 LaBaFe1.925Nb0.075O6-δ Sol–gel method 101 / 450 ◦ C 0.95 0.056 19.2 [135]
/800 ◦ C
12 LaBa0.5Sr0.5Fe2O6-δ Sol–gel method 164.2 /450 ◦ C 1.36 0.152/ 18.2 [136]
750 ◦ C
13 Ba0.95La0.05Fe0.8Zn0.2O3-δ Sol–gel method 1.9/450 ◦ C ——— 2.072/ 20.1 [137]
750 ◦ C
14 La0.6Sr0.4Fe0.9Ni0.1O3-δ Citric-acid nitrate 160/400 C ◦
——— 0.14/700 ◦ C ——— [138]
method
15 Ba0.5Sr0.5Co0.8Fe0.2O3-δ - Pechini method ——— ——— 0.10/700 ◦ C ——— [139]
BaZr0.1Ce0.7Y0.2O3-δ
16 Ba0.5Sr0.5Co0.75Fe0.2Nb0.05O3-δ Citric-acid nitrate 48/450 ◦ C ——— 0.14/700 ◦ C 19.67 [140]
method
17 Ba0.95La0.05Fe0.85Cu0.15O3-δ Solid-state reaction 28.25/450 ◦ C ——— 0.091/ ——— [141]
700 ◦ C
18 La0.6Sr0.4Fe0.8Cu0.2O3-δ EDTA-citrate process, 238/575 C ◦
0.11 0.070/ 14.6 [142]
800 ◦ C
19 LaFe0.8Cu0.2O3-δ EDTA citrate process, 41.2/800 ◦ C 1.65 0.090/ 12.0 [143]
800 ◦ C
20 BaFe0.8Cu0.2O3-δ EDTA citrate process, ~9/600 ◦ C ——— ——— ——— [144]
21 NdBaCo2O5+δ Sol-gel method 1000/100 ◦ C ——— 0.035/ ——— [144]
700 ◦ C
22 Sr2Fe1.3Ti0.1Mo0.6O6-δ Solid state reaction 220/500 ◦ C ——— 0.18/900 ◦ C 13.5 [145]
method
23 SrCo0.8Nb0.1Ta0.1O33-δ Solid state reaction ~147/400 ◦ C 103.1 ± 0.8 kJ 0.059/ ——— [146]
method mol− 1 550 ◦ C
24 PrBa0.5Sr0.5Co1.5Fe0.5O5-δ glycine-nitrate process 10–103/700 ◦ C 94.75 ± 2.01 0.056/ ——— [147]
600 ◦ C
14
Fig. 8. The best conductivities and CTE values of the cobalt-free and cobalt-based oxides materials evaluated in this review are compared (a, b).
compounds were also assessed about their performance as electrode electrochemical performance in terms of lower polarization resistance.
material in SOFCs. At a temperature of 750 ◦ C, area-specific resistance Peak power densities of 531.49 and 364.93 mWcm− 2 at 800 and 750 ◦ C
values as low as 0.17 and 0.1 Ω cm2 were found in air and 5%H2-Ar, were achieved in a single symmetrical cell having Sr2Fe1.4Nb0.1Mo0.5O6-
respectively. A single cell having La0.8Sr0.2Ga0.8Mg0.2O3-δ (LSGM) elec δ electrode, representing great redox stability [150-154].
trolyte with 400 µm thickness was used to test the performance of these Among electrode materials, substances containing nickel and iron
chemicals as both anode and cathode materials, a maximum PPD value are very common and usually have comparable performance.
of 425 mWcm− 2 was achieved at a temperature of 800 ◦ C [149]. The Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) [14], La0.8Sr0.2Cr0.5Fe0.5O3-δ (LSCrF)
results of x-ray photoelectron spectrometry revealed that niobium [15], La0.3Sr0.7Ti0.3Fe0.7O3-δ [153], LaNi0.6Fe0.4O3-δ [19], La0.6Sr0.4
doping has significantly increased the Fe-O-Fe (Nb) bind strength as a Fe0.9Sc0.1O3-δ [20], Ni-Ce0.8Sm0.2O1.9(Ni-SDC) [23], La0.3Sr0.7Fe0.7
result after reduction Fe ions can maintain more stabilized oxidation Cr0.3O3-δ [24] and SrFe0.75Mo0.25O3-δ [27], as well as the double
states. The conductivity was also increased from 11.11 Scm− 1-15.86 perovskite structured Sr2Fe1.5Mo0.5O6-δ [28] and Sr2Co1+xMo1− xO6 [29]
Scm− 1 in wet-hydrogen and from 17.62 to 27.61 Scm− 1 in the air showed good performance as compared to LSCF. But their poor stability
because of niobium doping at 600 ◦ C. Moreover, Sr2Fe1.4Nb0.1Mo0.5O6-δ under the reducing and oxidizing atmosphere is the key problem with
also displayed under both reducing-oxidizing conditions, better these materials. Therefore, by changing the shortcomings of different
Table 3
List of novel symmetric electrode materials by varying fuel at different processing temperatures.
Conductivity (S cm− 1) PPD (mWcm− 2) EIS
Sr. Symmetric electrode material Synthesis routes /Temp (◦ C) /Temp(◦ C) (Ω cm2) Fuel Ref
No composition / Temp used
1 La0.8Sr0.2Sc0.2Mn0.8O3-δ EDTA-citrate method 45 / 850 ◦ C 310, 130 at 6.5/850 ◦ C wet H2, wet [5]
900 ◦ C CH4
2 La0.75Sr0.25Cr0.5Mn0.5O3-δ Solid-state reaction ——— 546, 347 0.29/950 C ◦
H2, CH4 [30]
/ 950 ◦ C
3 La0.4Sr0.6Co0.2Fe0.7Nb0.1O3-δ Solid-state reaction ——— 500 / 850 ◦ C 0.22/850 ◦ C H2 [151]
4 Sr2Fe1.5Mo0.5O6-δ microwave-assisted 310 / 780 ◦ C 835, 230 0.21/850 ◦ C wet H2, wet [3]
combustion method at 850 ◦ C CH4
5 SmBaMn2O5+δ Citric-acid nitrate method 10.7/900 ◦ C 782/900 ◦ C 0.313/ H2 [75]
900 ◦ C
6 La2NiO4-infiltrated LSGM Solid-state reaction ——— 520/800 C ◦
——— H2 [43]
7 La0.3Sr0.7Ti0.3Fe0.7O3-δ Solid-state reaction ——— 74/900 ◦ C 0.04/900 ◦
C H2 [44]
8 La0.2Cu0.4Sr0.4 Sol-gel method ~4.70/650 ◦ C ~782/600 ◦ C ——— H2 [103]
9 La0.7Sr0.3Ti0.1Fe0.6Ni0.3O3-δ Pechni method ~1.1 / 700 ◦ C ~402/800 ◦ C 0.201/ Dry H2 [104,152]
800 ◦ C
10 LaSr2Fe2CrO9-δ Citric-acid Sol-gel method 0.16/800 ◦ C 224/800 ◦ C 0.454/ H2 [105]
800 ◦ C
11 La0.6Sr1.4MnO4 Citric-acid nitrate method 0.4/800 C ◦
59/800 C◦
2.07/800 ◦
C H2 [106]
12 La0.5Sr0.5Co0.5Ti0.5O3-δ Citric-acid nitrate method 0.11/900 ◦ C 500/850 ◦ C ——— H2 [107]
13 SrFe0.8W0.2O3-δ Pechini method 1.16/850 ◦ C 931/850 ◦ C 0.20/800 ◦
C H2 [120]
14 Sr2TiFe0.9Mo0.1O6–δ EDTA-citrate method 1.2/500 ◦ C 573, 361 0.237 / H2, H2S [121]
/850 ◦ C 850 ◦ C
15 Pr0.6Sr0.4Fe0.7Ni0.2Mo0.1O3-δ EDTA-citrate method 70.1/700 ◦ C / air 500/800 ◦ C 0.07/800 ◦
C H2 [122]
16 Sm0.5Sr0.5FeO3-δ EDTA-citrate method 0.19/750 ◦ C 109.09 4.32/750 ◦
C H2 [103]
/750 ◦ C
17 Sm0.5Sr0.5FeO3-δ- Gd0.1Ce0.9O2-δ EDTA-citrate method ——— 201.74 0.91/750 ◦ C H2 [123]
/750 ◦ C
18 BaZr0.1Co0.4Fe0.4Y0.1O3-SDC sol–gel method ——— 114.8 0.32 / H2 [124]
/750 ◦ C 750 ◦ C
19 Pr0.4Sr0.6Co0.3 Fe0.6Nb0.1O3-δ Solid-state reaction 258.9/ ~600 ◦ C / air 891 / 900 ◦ C 0.077 / H2 [3]
900 ◦ C
15

electrode materials, researchers have synthesized a new type of sym site, as this may encourage partial reduction to a lower oxidation state
metric electrode material in the future. Table 3 shows the novel sym when exposed to fuel gas, resulting in lattice expansion. Therefore, oxide
metric electrode materials with variable fuels at different operating electrodes might be able to experience several lattice expansions in
temperatures. different environments (cathode and anode) resulting in the induction of
large internal strain during redox cycling [5,30,31]. Hence, the criteria
5. Future perspective and concluding remarks of single and stable phase structure under both reducing and oxidizing
atmospheres would not be a better criterion for further advancement
Perovskite materials fall under the category of a most important class and development of electrode materials for symmetrical SOFCs. Elec
of materials and attracted the attention of enormous researchers as trode performance for SOFC is determined by considering the intrinsic
functional materials in the fields of energy conversion and storage. Their properties, microstructure, morphology, and design of the electrode. In
use has been extensively exploited in the fields of oxy-fuel combustors, most cases, morphology is considered as a prominent parameter for the
fuel cells, batteries, and solar cells. However, on a commercial scale determination of electro-catalytic activity for ORR and a proper un
perovskite-based energy storage and conversion devices still not avail derstanding of the operational activity of fuel cells. It has been observed
able. Although, in various energy-related fields perovskite materials can that the scientific community has been focusing on 3D microstructural
find widespread applications in commercially available devices by reconstruction and optimization of electrode materials. Observations
improving critical performance parameters to some extent. In the past revealed that the symmetrical cell configuration of SOFC can play an
few years, doping strategies encompassing the A-site, B-site, or com important role in the minimization of synthesis cost for cells. So, there is
bined A and B-site doping have remarkably increased the O2 permeation a need to maintain a balance between cell performance and the cost
fluxes of oxide-based perovskite materials. Therefore, offering a big concerned with the fabrication process. However, coking and sulfur
challenge for the development of perovskite materials possessing poisoning can be eliminated by flowing gas between both electrodes
favorable mechanical strength, chemical stability, and permeability [39,40]. A very few studies have been reported highlighting the issues of
concurrently [120-124]. For instance, cobalt-based perovskite oxides poisoning behavior of Sulphur redox, carbon deposition, and revers
are characterized for higher values of oxygen permeability corre ibility towards symmetric electrodes. So, more attention should be
sponding to ease of reduction of cobalt ions under reduced atmospheric devoted to this issue in the future. Symmetric SOFC comprising of two or
conditions [84]. Moreover, the A-site of the perovskite structure is multiple phases capable to perform various functions could be more
doped by the huge amount of alkaline earth metal elements for the promising cells for energy storage devices. By adopting an optimal
introduction of high oxygen permeation flux. However, rare earth ele approach for the selection of materials being used in the fabrication of
ments are receptive towards CO2 poisoning therefore, a rapid degrada both electrodes (cathode and anode) overall electrochemical perfor
tion occurs for oxygen permeation within the time as briefly mentioned mance of SOFC can be improved. Regardless of all these reported issues,
in Fig. 9 [57-76,125-147]. Symmetric electrodes are still falling under the category of high-
Cathode plays an essential role to define the electrochemical per performance SOFCs cells for various advanced applications and their
formance of SOFC. Operational temperature can be minimized by commercialization in emerging energy fields [120-122].
adopting MICE electrodes in SOFC which facilitate the staggering in The selection of the electrode material for the fabrication of SOFCs is
crease in the length of three-phase boundary length which further another challenging feature as the overall performance of the fuel cell is
correspond to increased active sites. Literature survey suggests that the evaluated by reactions occurring at the anode site. The anode should be
development of cathode materials with elevated properties for a wider of higher electronic conductivity for the evaluation of transported
range of temperatures is one of the much-concerned issues [87]. Alka electrons through a channel or reduced resistance. It must be resistant to
line earth metals are susceptible to poisoning which is a major reported carburization and sulfide, inert towards electrolytes, and capable of
issue in the commercialization of SOFCs so, the introduction of several retaining enhanced- catalytic activity. However, the question of low
strategies for the formation of alkaline metal-free perovskite material is electronic conductivity for the anode in composite electrodes becomes
another emerging challenge now. Significant conductivity values have more conventional. Perovskite materials are associated with several
been reported for cobalt-based materials but only a few comparative cons corresponding to lower electronic conductivity at room tempera
studies have been conducted between cobalt-based and cobalt-free ture and show brittleness under acidic conditions. Hence, their elec
materials. According to high priority needs, cobalt-free particles must tronic conductivities can be improved by loading a sufficient amount of
be developed to enhance the performance of SOFC with enhanced metals or composites exhibiting higher values of electrical conductance
conductive character. Several parameters (selection of dopant, tuned e.g by employing CNT and graphene electrical conductance can be
conditions) must be high priority conditions for the development of remarkably enhanced. The electronic configuration of perovskite oxides
highly conductive materials [109]. Mixed conductivities correspond to can be tuned for transiting the metal charges to the surface of nano
electronic, protonic, and oxygen-ionic conductivities that can remark particles during spin-state change through the application of the
ably affect the triple-phase boundary (TPB) length therefore, they downsizing technique. Low-valence cation doping is considered as one
represent a consequential R&D handling in the future. Literature survey of the promising techniques to transit the structural configuration of
revealed that mechanical properties of cathode materials have not been metals within the crystal structure due to this reason an increased
studied well, whereas these properties have a significant role as well in metal–oxygen covalence and decrease in d-band energy have been
the fabrication route of SOFCs. The fuel-testing parameter is considered observed in several reported studies. In addition, adequate filling of
as one of the versatile parameters to check the durability and stability of orbitals leads to increased tensile strength that results in enhanced
materials. Deep understanding regarding the properties and structure catalytic activity. It is a big challenge for researchers to develop several
relations is necessary for the development of materials, and design strategies for controllable and reliable approaches for the production of
strategies with tailored properties for breakthrough applications of pe nanostructured perovskite oxides. Effective industrial implementation
rovskites in energy storage and conversion domains in near future. There of oxygen electrocatalysts in various electro-chemical energy storage
is a need to yield a cost-effective metal rather than high-priced metals to and conversion devices is necessary for their proper understanding. For
develop a promising cost-effective symmetrical cathode material [104- further future advancement in this attractive area, further multidisci
107]. plinary approaches including conventional electrochemistry, physics,
In addition to this precedence, symmetrical SOFCs are susceptible to experimental solid-state chemistry, and advanced characterization with
sulphur poisoning and mediated coking and the scientific community is multiscale computing would be important perspectives.
addressing these issues with high priority. Furthermore, oxide-based
symmetrical electrodes must have a variable oxidation state at their B-
16
Fig. 9. Summary of Electrode materials for solid oxide fuel cells.
17
CRediT authorship contribution statement [18] S. Gupta, Y. Zhong, Mahapatra, P. Singh, Processing and electrochemical
performance of manganese-doped lanthanum-strontium chromite in oxidizing
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ware, Writing - review & editing, Supervision, Visualization. Martin LaNi0.6Fe0.4O3-δ-carbon nanotube hybrids as anodes for direct-methane solid
Motola: Validation, Investigation. Sana qayyum: Writing - review & oxide fuel cells, J. Power Sources 299 (2015) 472–479.
[20] X. Liu, D. Han, Y. Zhou, X. Meng, H. Wu, J. Li, Z. Zhan, Sc-substituted
editing. Sajid Rauf: Validation, Investigation. Azqa khalid: Validation, La0.6Sr0.4FeO3-δ mixed conducting oxides as promising electrodes for symmetrical
Investigation. Chang-Jiu Li: Project administration. Cheng-Xin Li: solid oxide fuel cells, J. Power Sources 246 (2014) 457–463.
Supervision, Visualization. [21] J.C. Ruiz-Morales, D. Marrero-López, M. Gálvez-Sánchez, J. Canales-Vázquez,
C. Savaniu, S.N. Savvin, Engineering of materials for solid oxide fuel cells and
other energy and environmental applications, Energy Environ. Sci. 3 (2010)
Declaration of Competing Interest 670–1681.
[22] C. Duan, R.J. Kee, H. Zhu, C. Karakaya, Y. Chen, S. Ricote, R. O’Hayre, Highly
durable, coking and sulfur tolerant, fuel-flexible protonic ceramic fuel cells,
The authors declare that they have no known competing financial Nature 557 (2018) 217–222.
interests or personal relationships that could have appeared to influence [23] J. Canales-Vázquez, J.C. Ruiz-Morales, D. Marrero-López, J. Peña-Martínez,
P. Núñez, P. Gómez-Romero, Fe-substituted (La, Sr) TiO3 as potential electrodes
the work reported in this paper. for symmetrical fuel cells (SFCs), J. Power Sources 171 (2007) 552–557.
[24] M. Chen, S. Paulson, V. Thangadurai, V. Birss, Sr-rich chromium ferrites as
Acknowledgment symmetrical solid oxide fuel cell electrodes, J. Power Sources 236 (2013) 68–79.
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Program of China (China-USA Intergovernmental Cooperation Project, Carbon deposition and sulfur poisoning in SrFe0.75Mo0.25O3-δ and
Grant NO. 2017YFE0105900) and supported by 111 Project 2.0 SrFe0.5Mn0.25Mo0.25O3-δ electrode materials for symmetrical SOFCs,
J. Electrochem. Soc. 162 (2015) F1078.
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20
transition from coherent to incoherent static Jahn-Teller distortions, J. Phys.: Professor Dr. Cheng-Xin Li obtained his Ph.D. degree in Mate
Condens. Matter 22 (2010), 445401. rials Science & Engineering at Xi’an Jiao-tong University, China
in 2005. He became a professor at Xian Jiao-tong University in
2012, where he leads a research group focused on Solid Oxide
Fuel Cells (Materials, Single Cells, Stack, and System). He has
Muhammad Bilal Hanif has joined Xi’an Jiaotong University worked as a visiting scholar in the University of Technology of
(XJTU), China for his MS under a Chinese government schol Belfort-Montbéliard, Belfort, France in 2015 and Georgia
arship. Now He is working as a research scholar at XJTU with a Institute of Technology, Atlanta, the USA from 2017-2019. He
collaborative projects of Prof. Dr. Cheng-Xin Li. His research has 350 SCI papers publications in international academic
mainly focuses on solid oxide fuel cells, super capacitors, and journals and more than 50 invention patents with 10,000
solid oxide electrolysis cells for energy conversion. He has citations.
published well renowned international journal papers on en
ergy storage applications.
Prof. Dr. Chang-Jiu Li completed his Masters and Doctoral de

gree in 1986 and 1989 respectively from Osaka University,
Japan. He has expertise in diverse fields of research including
mechanisms of thermal spray coatings, the coating structure
and property characterization, application of thermal spraying
technology, and Solid Oxide Fuel Cells. He has 456 publications
in international academic journals, more than 150 research
papers in domestic and over 190 articles in proceedings of In
ternational conferences with more than 10,000 citations.
21

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Chemical Engineering Journal 428 (2022) 132603

Contents lists available at ScienceDirect

Chemical Engineering Journal

Recent advancements, doping strategies and the future perspective of

Fig. 1. Working principle of SOFC.

doping of Ru and Pd at B-site. For instance, as shown in Fig. 3(a-d) at a

1 La0.75Sr0.25Cr0.5Mn0.5O3 Solid-state 38/900 ◦ C 470/900 ◦ C 0.2/900 ◦ C 97%H2/ 3%– [57]

1 La0.7Sr0.3MnO3 Combustion method 4.5/1000 ◦ C 0.58 ——— 11.7 [125]

Fig. 9. Summary of Electrode materials for solid oxide fuel cells.

Prof. Dr. Chang-Jiu Li completed his Masters and Doctoral de

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1 s2.0 S1385894721041814 Main

Uploaded by

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Copyright

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1 s2.0 S1385894721041814 Main

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Copyright:

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Chemical Engineering Journal 428 (2022) 132603

Contents lists available at ScienceDirect

Chemical Engineering Journal

Recent advancements, doping strategies and the future perspective of

Fig. 1. Working principle of SOFC.

doping of Ru and Pd at B-site. For instance, as shown in Fig. 3(a-d) at a

1 La0.75Sr0.25Cr0.5Mn0.5O3 Solid-state 38/900 ◦ C 470/900 ◦ C 0.2/900 ◦ C 97%H2/ 3%– [57]

1 La0.7Sr0.3MnO3 Combustion method 4.5/1000 ◦ C 0.58 ——— 11.7 [125]

Fig. 9. Summary of Electrode materials for solid oxide fuel cells.

Prof. Dr. Chang-Jiu Li completed his Masters and Doctoral de­

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Prof. Dr. Chang-Jiu Li completed his Masters and Doctoral de