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org/EF Review

Toward Reducing the Operation Temperature of Solid Oxide Fuel

Cells: Our Past 15 Years of Efforts in Cathode Development
Guangming Yang,† Chao Su,† Huangang Shi, Yinlong Zhu, Yufei Song, Wei Zhou, and Zongping Shao*

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ABSTRACT: The development of clean and efficient energy conversion and storage systems is becoming increasingly vital as a
result of accelerated global energy consumption. Solid oxide fuel cells (SOFCs) as one key class of fuel cells have attracted much
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attention, owing to their high energy conversion efficiency and low emissions. However, some serious problems appeared because of
the scorching operating temperatures of SOFCs (800−1000 °C), such as poor thermomechanical stability and difficult sealing,
resulting in a short lifespan and high cost of SOFCs. Therefore, lowering the operating temperature of SOFCs to mid-range and even
low range has become one of the main goals for SOFC development in the recent years. Looking for new cathode materials with
high electrocatalytic activity and robust stability at relatively low temperatures is one of the essential requirements for intermediate-
to-low-temperature SOFCs (ILT-SOFCs). During the past 15 years, we put considerable efforts into the development of alternative
cathode materials for ILT-SOFCs. In this review, we give a summary of our progress from such efforts. We first summarize several
strategies that have been adopted for developing cathode materials with high activity and durability toward reducing operating
temperatures of SOFCs. Then, our new ideas and progress on cathode development with respect to activity and stability are
provided. Both the cathodes of oxygen-ion-conducting SOFCs and protonic-conducting SOFCs are discussed. In the end, we outline
the opportunities, challenges, and future approaches for the development of cathodes for ILT-SOFCs.

1. INTRODUCTION In the early stage of development, SOFCs were mainly

Solid oxide fuel cells (SOFCs), sometimes also called ceramic
fuel cells, are fascinating elevated-temperature electrochemical
energy conversion devices, which transfer the chemical energy
of fuels into electric power through the electrochemical
reaction way, with the advantageous features of high efficiency
and low emissions. A single SOFC is typically composed of an
electronically conductive oxide-based cathode, an oxygen ion
or proton-conducting oxide-based electrolyte, and a nickel
oxide cermet-based anode. An elevated operation temperature
(400−1000 °C) is needed to allow for the electrolyte to have
sufficient ionic conductivity, which distinguishes SOFCs from
low-temperature fuel cells, such as polymer-electrolyte-
membrane fuel cells (from room temperature to 80 °C), by
fuel flexibility and high quality of exhaust heat. In addition to
hydrogen, many other fuels, such as gaseous hydrocarbons
(methane, ethane, etc.),1 liquid hydrocarbons (gasoline, etc.),2
ethanol,3 ammonia,4 carbon monoxide,5 and even solid carbon
(coal),6 can be directly fed into SOFCs for power generation.
In comparison to low-temperature fuel cells that use precious
metal electrocatalysts, the electrode reaction kinetics in SOFCs
is boosted as a result of the elevated operation temperature.
Consequently, cost-effective noble metal-free electrocatalysts
can be used; thus, from the economic aspect of consideration,
SOFCs are more competitive than other fuel cells with the
current matured power generation technologies. The heat in
the hot exhaust gas of SOFCs is in high quality, which can be
further used by integrating with a gas turbine or directly used
as thermal energy.7
operated at a temperature range of 800−1000 °C.8 Such a high
operating temperature was adopted to facilitate the ion
transportation within the electrolyte and fasten the electrode
reaction kinetics. Therefore, a high power output could be
achieved for the cell composed of a typical zirconia-based
electrolyte and La0.8Sr0.2MnO3 (LSM) cathode, which has been
reported to have moderate oxygen ion conductivity and
catalytic activity for the oxygen reduction reaction (ORR) at
intermediate temperature.9,10 However, such a high operating
temperatures also causes several challenges related to sealing,
electrode morphological stability, chemical stability of cell
components, and thermal shock resistance of accessories. All of
these challenges would bring about an increased cell cost and a
reduced cell lifetime. It is now generally believed that the
decrease of the operating temperature for SOFCs from 800−
1000 to 400−800 °C will bring many advantages, such as more
flexible sealing, weaker interfacial reaction between cell
components, and better thermomechanical stability. Hence, a
prolonged cell lifetime and quicker startup can be realized,
while the fuel flexibility can still be maintained.11−13
Special Issue: In Honor of Professor Michael Klein
Received: June 10, 2020
Revised: July 28, 2020
Published: July 29, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.energyfuels.0c01887

15169 Energy Fuels 2020, 34, 15169−15194
Energy & Fuels
With a lower operating temperature, however, the electrode
reaction kinetics becomes sluggish and the oxygen ion
conductivity dropped quickly as a result of the large activation
energy of oxygen activation and the hard transportation of
oxygen ion. Cells with a thick yttria-stabilized zirconia (YSZ)
electrolyte and conventional LSM cathode usually show low
and unaffordable power density at intermediate temperatures, a
result from the substantial increase of polarization resistance
(Rp) of electrodes (mainly cathode) and ohmic resistance (Ro)
of the electrolyte. Because Ro is in direct proportion to the
thickness of the electrolyte, a reduction in electrolyte thickness
is an effective way to reduce the ohmic resistance. By adoption
of state-of-the-art thin-film fabrication techniques, such as tape
casting combined with dip coating or wet powder spraying, a
high-quality anode-supported thin-film electrolyte with a
thickness as low as approximately 10 μm can be fabricated
with mass production capability,14−16 while from the
application of more advanced techniques, such as pulse laser
deposition, the membrane thickness can be further reduced to
1−2 μm, even the nanometer range.17,18 From the application
of a thin-film electrolyte, it was demonstrated the ohmic
resistance of the YSZ and doped ceria electrolytes is still
acceptable for the operation temperature down to 700 and 550
°C, respectively.9 If a thin-film protonic conducting electrolyte
is applied, the operating temperature from the aspect of
electrolyte ohmic resistance may further drop to around 400
°C.19 Therefore, the development of efficient electrodes is the
key to realize the intermediate-to-low-temperature operation of
SOFCs (ILT-SOFCs). In comparison to the fuel electro-
catalytic oxidation at the anode, the ORR over the cathode is
much more sluggish, requiring higher activation energy.
Therefore, a substantial increase in the cathodic polarization
resistance was often confirmed with the drop of the operation
temperature for conventional fuel cells based on a YSZ
electrolyte and LSM cathode. The development of new
cathodes that show high activity and durability at a reduced
temperature is critical to realize ILT-SOFCs. This is one of the
main efforts of our group for SOFC research during the past 15
years.
This review paper will provide a comprehensive summary of
our progress during the past 15 years in the development of
new cathode materials/architecture toward the reduction of
the operating temperature to the intermediate range, in
particular, 500−650 °C. Various aspects will be considered,
such as activity, durability, electronic conductivity, and cost,
with the focus on the first two parameters. Both oxygen-ion-
conducting SOFCs (O2−-SOFCs) and protonic-conducting
SOFCs (PCFCs) will be involved. Finally, the challenges and
perspectives of cathodes for ILT-SOFCs will be discussed.
2. BASIC REQUIREMENTS OF A CATHODE FOR
ILT-SOFCS
As mentioned, to realize the widespread application of SOFCs,
the key is to reduce the operation temperature to the range of
400−800 °C and more preferably to 400−650 °C. To maintain
high-energy conversion efficiency and power output of SOFCs
at such a temperature range, both the electrode polarization
resistance and ohmic resistance of the cell should be kept at an
acceptable level. Because the selection of cathode material
highly depends upon the electrolyte, for the operation
temperature range of 400−650 °C, among the various available
solid oxide electrolyte materials, only doped ceria (such as
samaria- or gadolinium-doped ceria), lanthanum strontium
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gallium magnesium (LSGM) perovskite oxide, and some
proton-conducting perovskite oxides (doped BaZrO3, doped
BaCeO3, and doped SrCeO3), in thin-film configuration, can
meet the requirements of affordable ohmic resistance and
sufficient stability. Therefore, our main efforts are the
development of cathode materials that can work well with
these electrolytes to provide high activity and durability, in
particular, for doped ceria electrolytes and proton-conducting
perovskite electrolytes.
The first essential requirement of a cathode for ILT-SOFCs
is that it should have sufficiently high activity for ORR at this
temperature range. If a peak power density (PPD) of 1.0 W
cm−2 is targeted, then the total area specific resistance of
electrodes should be less than 0.3 Ω cm2 by assuming the
electrolyte ohmic resistance of 0.15 Ω cm2 [it can be reached
for 15 μm thickness of Sm0.2Ce0.8O1.9 (SDC) electrolyte at 500
°C and YSZ electrolyte at 700 °C].20 The challenge is that
oxygen activation is typically much more difficult than
hydrogen activation, and a larger activation energy is required.
The electrode activity is related to both the intrinsic activity of
the electrode material and the number of active sites over the
cathode; thus, both the material composition and the electrode
architecture should be well-tailored/designed.
Apart from the activity, durability is equally significant for a
practical electrode of ILT-SOFCs. Although some materials
show good catalytic activity for ORR at reduced temperature
initially, a progressive increase in area specific resistance (ASR)
with time was observed.21−26 Such deterioration in activity
with time could originate from several aspects, such as the
phase transition (demixing),21 the reaction of the electrode
with impurity, such as CO2/H2O, in the air atmosphere,22 the
phase reaction between the electrode and the electrolyte,23,24
the thermomechanical instability of the electrode as a result of
the mismatch in thermal expansion behavior between the
electrode and the electrolyte,25 and the morphological
instability.26 All of these aspects should be well-considered.
Sufficient electronic conductivity at the operating temper-
ature is also a basic requirement of the electrode. It is
commonly accepted that an electrical conductivity of more
than 100 S cm−1 is needed to ensure no additional
contribution of ohmic drop from the electrode.26,27 However,
it is suggested that, if the electrode morphology can be well-
tailored, an electronic conductivity of only 0.1 S cm−1 is still
affordable.28,29 It should be mentioned that the electrical
conductivity of an electrode could vary under different
cathodic polarization current densities. The cathodic polar-
ization sometimes leads to the partial reduction of the
electrode, which induces the change of the electrical
conduction from p to n type and a decrease in conductivity.
If a phase transition is accompanied by the electrochemical
reduction of the electrode, a sharp decrease in conductivity
could appear.
Cost is also an important concern during the development of
a new cathode for ILT-SOFCs; the use of Earth-abundant raw
materials are always the first choice. The applicability of low-
grade materials with reproducible performance is always
preferred. This brings us the consideration of the effect of
the impurity phase on the performance of cathode materials for
the ORR at ILT.
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Energy & Fuels
Figure 1. Strategies for developing a cathode of ILT-SOFCs.
3. STRATEGIES FOR DEVELOPING A CATHODE OF
ILT-SOFCS
3.1. Cathodes with High Activity. 3.1.1. Intrinsic
Activity. We proposed some strategies for developing cathodes
of ILT-SOFCs according to the main requirements of cathode
materials, i.e., high activity and stability, as shown in Figure 1.
As mentioned, the ORR activity of a cathode is closely related
to the intrinsic activity and number of active sites. With regard
to the conventional LSM perovskite cathode for high-
temperature SOFCs, it is a pure electronic conductor;
therefore, the ORR only happens at the electrode−electro-
lyte−air triple-phase boundary (TPB) region.10 From the
application of a mixed oxygen ion and electronic conductor as
the electrode, the whole exposed electrode surface (air−
electrode two phase boundary) may take part in the oxygen
reduction process because the oxygen ion charge transfer will
take place at the electrode surface and the formed oxygen ions
will transfer through the electrode bulk to the electrolyte and
finally to the anode side.30 The observation of increased
cathodic performance of LSM under a large cathodic
polarization current is partially due to the oxygen vacancies
created inside the perovskite lattice, thus introducing a certain
level of oxygen ion conductivity.10,31 Therefore, introducing
oxygen ion conductivity into the electrode is the most
important strategy toward the development of cathodes for
ILT-SOFCs. In practical SOFCs, the thickness of the cathode
may reach hundreds of micrometers; however, only part of the
electrode that is nearest to the electrolyte layer actually takes
part in the ORR, while the remain part performs only as the
current collector. The effective thickness of the electrode to
take part in the ORR highly depends upon its oxygen ion
conductivity. The higher the conductivity, the thicker the
electrode could be effective and the higher activity is expected.
If the oxygen ion conductivity is sufficiently high, the whole
exposed electrode surface will take part in the ORR. Therefore,
enhancing oxygen ion conductivity in the electrode is crucial to
increase the activity of the electrode for ILT-SOFCs.
There are two main ways for increasing oxygen ion
conductivity of the electrode; one is mixing an electronic
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conducting phase with an oxygen-ion-conducting phase to
form a composite electrode. For example, LSM is often mixed
with YSZ to form a LSM−YSZ composite for SOFCs, to
enhance the cathode performance.32,33 However, as a result of
the different sintering behaviors of both phases before the
physical mixing, the apparent oxygen ion conductivity of the
composite is usually lower than the pure oxygen-ion-
conducting phase, making the improvement in performance
really limited. Another way is the creation of both oxygen ion
conductivity and electronic conductivity in the same phase, i.e.,
the development of single-phase mixed conductors. The most
popular phase that shows mixed conducting capability is
perovskite.34 Perovskite oxide has the formula ABO3, where A
is a large cation of alkaline earth, alkaline, or lanthanum cation,
in 12 coordination with the oxygen anion and the B site is
usually a transition metal element in 6 coordination with the
oxygen ion.35 As mentioned, the state-of-art cathode LSM for
high-temperature SOFC takes the perovskite structure. The
oxygen ion conductivity in perovskite lattice is realized usually
through the diffusion of oxygen ions inside the oxide lattice via
the way of a charge carrier, such as oxygen vacancies.36 Doping
is the main strategy to introduce oxygen vacancies into the
oxide lattice. For typical perovskite oxides (A3+B3+O3 or
A2+B4+O3), doping a cation with a lower oxidation state in the
A site (e.g., A′2+ for A3+B3+O3 and A′+ for A2+B4+O3) or B site
(e.g., B′2+ for A3+B3+O3 and B″2+ or B″3+ for A2+B4+O3), the
increase of the oxidation state of B-site cation(s), the creation
of oxygen vacancies, or both of them will be realized to
maintain the apparent charge neutrality.37,38 The diffusion of
oxygen vacancies within the oxide lattice leads to the
appearance of oxygen ion conductivity, while the hopping of
an electron between B-site cation(s) and O2− is the origin of
electronic conductivity.39 To provide both high oxygen ion
conductivity and electronic conductivity, the easiness of the
oxidation state variation of B-site cation(s) should be well-
tailored, which can be realized by selecting the proper dopant
and/or managing the bond length. For example, cobalt shows
an appropriate band gap between the different species of Co2+,
Co3+, and Co4+; therefore, the cobalt-based perovskites are
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Energy & Fuels
usually easy to achieve high oxygen vacancies and high
electronic conductivity at the same time, while iron is more
prone to keep a high oxidation state of Fe3+/4+; therefore, iron-
rich perovskite oxides usually show lower oxygen vacancy
concentration and conductivity than that of cobalt-rich
perovskites. With regard to Mn and Cr, they usually take a
high oxidation state, such as +4 and +5 for Mn and +5 and +6
for Cr, in the perovskite lattice. For Mn- and/or Cr-doped
perovskite oxides, it is very difficult to achieve a high oxygen
vacancy concentration under an oxidizing atmosphere; there-
fore, these cations were seldom used as the main cations in the
B site of perovskites as efficient cathodes of ILT-SOFCs.
However, under a reducing atmosphere, a high oxidation state
is preferred; thus, Cr- and Mn-based perovskites are widely
applied as anode materials for SOFCs.40−43 The oxygen
vacancy concentration could be variable depending upon the
operation conditions, for example, the temperature, oxygen
partial pressure, and polarization current density. The
oxidation state of the B-site cation can also be tailored
through tuning the cation−oxygen bonding length. For
example, iron is prone to take +4 in perovskite under an
oxidizing atmosphere; however, by substitution of the A-site
cation in perovskite with a large cation, such as Ba2+, to
maintain the perovskite structure, the increase in the distance
between the B-site cation and oxygen forces the iron to take a
lower oxidation state. For example, Ba0.95La0.05FeO3 was found
to be an excellent cobalt-free perovskite for a cathode of IT-
SOFCs.44
In addition to the number of charge carriers (oxygen
vacancies), the oxygen ion conductivity is also closely related
to the oxygen (oxygen vacancies) mobility, which is highly
dependent upon the bond strength of oxygen with a cation, the
cell-free volume, and the lattice symmetry.45 All of these
parameters should be well-tailored to optimize the oxygen ion
conductivity of the electrode. Typically, the lower bond
strength between the oxygen anion and metal cation means the
less confinement of oxygen by the other cations, thus the easier
mobility of the oxygen ions within the oxide lattice.
Consequently, it is beneficial to increase the oxygen ion
conductivity by introducing the cations that have low bond
energy with the oxygen ion, such as Sc3+, Bi3+/5+ and Cox+. The
cations, such as Zr4+, Ti4+, and Cr3+, which have large bond
energy with the oxygen ion, are not preferred with a high
concentration, to realize fast oxygen diffusion within the oxide
lattice at reduced temperatures. In addition, the oxygen
mobility in the oxide lattice is related to the free volume of
the perovskite unit cell, which is defined as the volume
difference between the unit cell and the occupied cation and
anions. The larger the free volume of the unit cell, the higher
freedom of the oxygen anion to diffuse inside the oxide lattice;
thus, a higher conductivity is expected. The larger size of the B-
site cations can result in an increased free volume of the unit
cell for perovskite oxides. Cubic symmetry has the ideal
isotropic three-dimensional diffusion pathway. Because most of
the electrode materials are polycrystalline, it is usually
considered as the optimal structure symmetry for facilitating
the oxygen ion diffusion, which can ensure the shortest
diffusion distance of the oxygen ion within the electrode layer.
Therefore, many of the outstanding perovskite cathode
materials for ILT-SOFCs take a cubic perovskite structure.
The distortion of lattice symmetry may inhibit oxygen ion
diffusion; consequently, a lower oxygen ion mobility is usually
observed/expected. The lattice symmetry of perovskite is
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closely related to the Goldschmidt tolerance factor (t), which
is defined as
t = (RA + R O)/ 2 (RB + R O)
where RA, RB, and RO are the radii of the A-site cation, B-site
cation, and oxygen ion, respectively.46 Typically, the perovskite
structure can be sustained in the t range of 0.71−1.0, while a
value of around 1.0 should be met for the ideal cubic
perovskite.47 According to the equation, the tolerance factor is
determined by the size of the A- and B-site cations, which is
dependent upon the type of cations, their oxidation state, and
the spin state of the electron in the outermost orbital. It is
preferred that t is near unit under the working conditions
(temperature, polarization current, and oxygen partial
pressure). It should also be careful that the large variation in
the tolerance factor may induce a large internal strain of the
perovskite, thus introducing a large thermal expansion
coefficient (TEC) and easy phase transition, which is
detrimental for long-term operation stability.
In some cases, an ordered perovskite structure could provide
special two-dimensional diffusion channels for an oxygen ion
with low activation energy.48,49 For example, for some cation-
ordered double perovskite oxides A′A″B2O5+δ, such as
PrBaCo2O5+δ (PBC), their crystal structure is layered
A′A″B2O6, consisting of consecutive layers [BO2]−[A′Oδ]−
[BO2]−[A″O] stacked along the c axis. The a−b plane (A′Oδ
layer) is believed to be highly easy for oxygen diffusion.48
Indeed, the oxygen exchange kinetics of pulsed laser deposition
(PLD)-derived epitaxial thin films of PBC demonstrated high
electronic conductivity and rapid surface exchange kinetics.49
However, most of the electrode materials in practical fuel cells
are in the polycrystalline phase; thus, the real diffusion route is
actually highly tortuous. As a result, no obvious improvement
in activity for ORR could be observed in real fuel cells.
3.1.2. Apparent Activity. In addition to intrinsic activity, the
apparent ORR activity of the electrode is also closely related to
the number of electrode active sites. As mentioned previously,
from the introduction of oxygen ion conductivity into the
electrode, the active reaction region is extended from the
conventional TPB region to possibly the whole exposed
electrode surface if the oxygen ion conductivity is high enough.
Therefore, the increased surface area of the electrode with
mixed conductivity may result in the increase of activity for the
ORR. As is well-known, the mass specific surface area is
directly related to the particle size of the cathode. Thus, a
reduction in the grain size of the cathode would lead to the
increase of the cathode surface area; consequently, an
enhanced electrode activity may be achieved. Therefore,
nanostructuring is an important strategy to increase the ORR
activity of the electrode. The infiltration method is most
frequently applied to the preparation of nanoparticle-modified
electrodes for SOFCs.50−52 However, as a result of the elevated
temperature operation, the nanostructured electrode is easily
sintered. How to avoid or suppress the sintering of
nanoparticles is crucial to achieve high and stable activity for
the ORR. Another way to increase the number of active sites is
the construction of a three-dimensional (3D) architecture
electrode.53,54
3.2. Cathodes with Good Durability. 3.2.1. Structural
Stability. As mentioned, in addition to activity, stability is
another important concern of a material as a cathode of ILT-
SOFCs. To ensure high durability, the electrode should first
possess high structural stability under operating conditions.
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Energy & Fuels
However, there is a dilemma between activity and stability. To
achieve high activity, the oxygen−metal bond strength should
be low, the oxygen vacancy concentration should be high, and
the free volume of the cell should be large, which inevitably
reduces the stability of the oxide lattice. Thus, the stability and
activity need to be well-balanced. One way to increase the
structural stability of the perovskite oxides while still
maintaining high activity at a reduced temperature is to dope
some elements with fixed oxidation state and relatively high
oxygen−metal bond energy, such as Zr4+ and Ti4+, into the B
site of the perovskite structure at an appropriate concentration
(less than 20% of the B site and typically 5−10%).
One important feature of the cathode in SOFCs is that it will
frequently experience polarization at different current densities.
Such polarization may cause a change in the oxidation state of
the B-site cation with multiple oxidation states, which will
induce a change in the tolerance factor of the perovskite and,
consequently, a transition in the lattice symmetry. If the degree
in loss of oxygen is too large, the collapse of the perovskite
structure may even appear. In addition, the doping of the B site
with an appropriate amount of cation that shows high bonding
energy with oxygen, such as Zr4+ and Ti4+, can greatly increase
the structural stability of the perovskite lattice under different
polarization conditions. However, their amount could not be
high, because it will substantially reduce the oxygen mobility of
perovskite by acting as a trap for the oxygen ion on the one
hand and reducing the oxygen vacancy concentration on the
other hand. From this consideration, we may introduce some
elements with high bonding energy with oxygen and high
oxidation state, such as Cr and Mn, into the B site to improve
the structural stability under polarization. In addition, their
concentration should not be high.
3.2.2. Chemical Stability. To realize high operational
stability, a favorable chemical stability against other cell
components and impurity phase(s) in the air is also highly
important. For the YSZ electrolyte, most of the perovskite
oxides can readily react with the YSZ electrolyte at elevated
temperatures to form some insulating interfacial phase,23,55
although such reaction can be suppressed by reducing the
calcination temperature during the cathode layer fabrication
using nanosized cathode powders,56 while most perovskite
oxides show chemical compatibility with doped ceria, and YSZ
and doped ceria were also found to be chemically
compatible.57 Therefore, if a YSZ electrolyte is applied, a
SDC or Gd0.1Ce0.9O2−δ (GDC) buffer layer can be used to
avoid direct contact between the YSZ electrolyte and the
perovskite cathodes.18,57,58 In comparison to the potential
phase reaction with other cell components, the high chemical
stability of perovskite electrodes against the air impurity is a
major concern. As we know, the SOFCs will operate at
elevated temperatures and are exposed directly to the
surrounding ambient air. In ambient air, they contain a certain
level of impurity, such as CO2 and water vapor. In particular,
from the application of hydrocarbon fuels, the oxidation
product of CO2 at the anode chamber could easily diffuse to
the cathode size via an ambient environment. The reaction of
the cathode with such impurity may cause a block to a certain
intermediate step of the ORR, thus deteriorating or even
ceasing the ORR. If the reaction is so serious, the perovskite
structure may be completely destroyed, leading to the failure of
the cell. For example, the performance of the
Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) cathode was reduced by
approximately 20 times after introducing 10 vol % CO2 into
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the air at 600 °C for 5 min.59 The sensitivity of the electrodes
to CO2 poisoning is due to the adsorption of CO2 or the
formation of carbonate materials on the surface containing
alkaline earth metals, which will destroy the cathode phase
structure and significantly reduce the surface oxygen exchange
kinetics.22,60,61 Even CO2 in air was removed; the catalytic
activity was not able to recover to the initial value. Accordingly,
developing a cathode with good CO2 tolerance will have great
practical value, especially when applied into single-chamber
SOFCs. As we know, BSCF contains alkaline earth cations of
Ba2+ and Sr2+. One effective way to increase the CO2 tolerance
is to develop alternative cathodes, which are alkaline-earth- and
alkaline-cation-free.38 Unfortunately, up to now, the catalytic
activity of such alkaline-earth/alkaline-free electrodes showed
inferior performance. The CO2 tolerance of alkaline-earth-
contained perovskite cathodes may be improved through
doping, forming a composite, and crystal structure engineering.
3.2.3. Thermomechanical Stability. Thermomechanical
stability is also a big concern for long-term operation, although
the decrease of the operating temperature could mediate the
thermal expansion mismatch somewhat between cell compo-
nents. Such a mismatch, however, may introduce large internal
strain/stress, finally leading to delamination of the electrode
and the electrolyte layer. As we know, the ceramic electrolytes
usually have TEC of 10−12 × 10−6 K−1, while the promising
perovskite oxides with high activity for the ORR are usually
cobalt-contained, which show a high TEC value of 18−25 ×
10−6 K−1. Such a high TEC contributes to several parts, the
real thermal excited expansion, the chemical expansion as a
result of the variation in the oxygen content (thus, the
oxidation state) and the spin state, and the possible chemical
expansion as a result of the phase transition. Several strategies
can be taken to increase the thermomechanic compatibility of
the cathode with the electrolyte. One strategy is to develop
electrodes with reduced TEC through doping by suppressing
the oxidation state transition during polarization. The second
is the development of a composite electrode. From the
formation of a composite through physical mixing, the
apparent TEC is a weighted average of the two components.
The electrolyte material is often used as the second phase for
the formation of the composite electrode, which can modify
the oxygen ion conductivity on the one hand and reduce the
apparent TEC on the other hand because the electrolyte
material usually shows a lower TEC than the mixed conducting
perovskite oxides. By adoption of the infiltration technique, the
TEC of the as-prepared composite electrode is determined
mainly by the scaffold.28,62 Therefore, the electrolyte material
is always adopted as the scaffold, and the perovskite mixed
conductor is infiltrated into the scaffold to perform as the
electrocatalyst. This way, which offers both high active sites
and a compatible electrode TEC to the electrolyte, is currently
extensively used to develop high-performance electrodes for
ILT-SOFCs. The creation of an intimate interaction between
two different phases at the nanoscale range and the dynamic
cation exchange between the different phases that may
suppress the oxidation state and the spin state transition result
in improved catalytic activity and reduced TEC simulta-
neously.63
3.2.4. Morphological Stability. As mentioned, the electrode
reaction takes place at the TPB region for the pure electronic
conductor and the bare surface for the mixed conducting
electrode. It suggests that the activity is directly related to the
surface area of the mixed conducting electrode. Because the
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Energy Fuels 2020, 34, 15169−15194
 Table 1. Properties and Performance of Cobalt-Based Perovskites or Related Oxides as the Cathodes of ILT-SOFCs as Developed or Investigated in Our Group
electrical PPD at 600 °C,
space conductivity in air average TEC ASR in air at H2 fuel
cathode phase structure group (S cm−1) (K−1) 600 °C (Ω cm2) (mW cm−2) cell configuration reference
−6
Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) cubic Pm3̅m 27−32 at 21 × 10 at 0.071 1010 BSCF|Sm0.15Ce0.85O2−δ|Ni + Sm0.15Ce0.85O2−δ 65, 69,
Energy & Fuels

400−900 °C 25−1000 °C and 70

PrBaCo2O5+δ (PBC) orthorhombic Pmmm 110−200 at 0.4 620 PBC|SDC|Ni + Sm0.2Ce0.8O1.9 (SDC) 48 and
400−900 °C 71
Sm0.5Sr0.5CoO3−δ (SSC5) orthorhombic Pnma 700−1731 at 25.5 × 10−6 at 0.42 690 SSC5|SDC|Ni + SDC 72 and
300−900 °C 500−900 °C 73
BaCo0.75Sc0.25O3−δ (BCSc) cubic Pm3̅m 1.0−3.7 at 400− 0.08 1045 BCSc|SDC|Ni + SDC 74
800 °C
BaCo0.6Fe0.3Sn0.1O3−δ (BCFSn) cubic Pm3̅m 0.9−7.1 at 300− 15.8 × 10−6 at 0.097 1168 BCFSn|SDC|Ni + SDC 75
900 °C 25−800 °C
SrSc0.2Co0.8O3−δ (SScC) cubic Pm3̅m 4.6−25 at 300− 16.9 × 10−6 at 0.09 902 SScC|SDC|Ni + SDC 76 and
900 °C 100 −1000 77
°C
SrNb0.1Co0.9O3−δ (SNC) cubic Pm3̅m 75−135 at 350− 19.1 × 10−6 at 0.094 1008 SNC|SDC|Ni + SDC 78 and
700 °C 200−1000 °C 79
SrSc0.175Nb0.025Co0.8O3−δ (SSNC) cubic Pm3̅m 20−35 at 300− 0.04 910 at 500 °C SSNC|SDC|Ni + SDC 80
800 °C
Sr4Fe4Co2O13 (SFC2) contained two phases cubic (SFC-P) Pm3̅m 30−70 at 600− 0.136 230 SFC2|SDC|YSZ|Ni + 8 mol % Y2O3−ZrO2 81
SrFeyCo1−yO3−δ (SFC-P) + Sr4Fe6−yCoyO13 (SFC- orthorhombic Iba2 900 °C (YSZ)
L) (SFC-L)
SrNb0.1Co0.7Fe0.2O3−δ (SNCF0.2) cubic Pm3̅m 26.0 × 10−6 at 0.052 1587 SNCF0.2|SDC|Ni + SDC 82
25−900 °C

15174
SrCo0.6Fe0.3Sn0.1O3−δ (SCFSn) cubic Pm3̅m 44−121 at 300− 26.4 × 10−6 at 0.10 883 SCFSn|SDC|Ni + SDC 83
900 °C 25−900 °C
SrCo0.8Nb0.1Ta0.1O3−δ (SCNT) cubic Pm3̅m 81−146 at 400− 0.16 at 500 °C 1220 at 500 °C SCNT|GDC|Ni + Gd0.1Ce0.9O2−δ (GDC) 84
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800 °C
SrCo0.7Fe0.2W0.1O3−δ (SCFW) contained two phases cubic (SP) Pm3̅m 90−254 at 400− 18.6 × 10−6 at 0.058 1192 SCFW|SDC|YSZ|Ni + YSZ 85
SrCoxFeyW1−x−yO3−δ (SP) + Sr2CozFe1−zWO6 tetragonal (DP) I4/m 800 °C 200−1000 °C
(DP)
Ba0.6Sr0.4Co0.9Nb0.1O3−δ (BSCN) cubic Pm3̅m 23−40 at 300− 18.2 × 10−6 at 0.1 1150 BSCN|SDC|Ni + SDC 86
900 °C 200−900 °C
Nd0.2Sr0.8Nb0.1Co0.9O3−δ (NSNC) cubic Pm3̅m 156−346 at 300− 0.072 1261 NSNC|SDC|Ni + SDC 87
900 °C
SrCoOx + Sm0.2Ce0.8O1.9 92−208 at 300− 0.18 795 SrCoOx + SDC|SDC|Ni + SDC 88
900 °C
Sm0.3Sr0.7Co0.95Ce0.05O3−δ cubic Pm3̅m 350−500 at 300− 18.6 × 10−6 at 1.02 89
900 °C 200−1000 °C
LaCo0.3Fe0.67Pd0.03O3−δ (LCFPd) orthorhombic Pnma 0.23 132 LCFPd + SDC|SDC|LCFPd + SDC 90
exsolved Sr0.95Ag0.05Nb0.1Co0.9O3−δ (e-SANC) cubic (SANC) Pm3̅m 0.0374 1984 e-SANC|SDC|Ni + SDC 91
tetragonal (e- P4/
SANC) mmm
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Energy & Fuels pubs.acs.org/EF
SOFC is operated at elevated temperatures, the sintering
during operation could lead to the decrease of the electrode
surface area and, consequently, a decrease in the electrode
performance. The aggregation of nanoparticles in nano-
structured electrodes and the sintering of a mesoporous
electrode are big concerns for practical application. Therefore,
high morphological stability is also crucial toward high
durability of the electrode. One strategy for suppressing the
aggregation of nanoparticles is to increase the interaction with
the substrate. Instead of using a nanoparticle-modified
electrode, a thin-film-modified electrode will avoid the
sintering issue of nanoparticles but still afford a high reaction
surface area; it provides another strategy for developing a
highly active and durable electrode for ILT-SOFCs.
4. OUR PROGRESS IN THE DEVELOPMENT OF A
CATHODE FOR ILT-SOFCS
As mentioned, the introduction of oxygen ion conductivity
into the electrode extends the active sites from the TPB region
to the electrode−air two-phase region, thus making it possible
to lower the operating temperature. BSCF was originally
fabricated as a material for the oxygen separation membrane,
which shows superior mixed oxygen ion and electronic
conductivity at high temperatures.64 Such mixed conductivity
resulted from the high oxygen vacancy concentration and the
variable state of Cox+ and Fex+ in the B site. From the
application of BSCF as the cathode, an ASR of 0.055−0.071 Ω
cm2 was achieved at 600 °C. An SOFC with a thin-film SDC
electrolyte and BSCF cathode delivered a benchmark PPD of
1010 mW cm−2 at 600 °C using pure hydrogen as the fuel.65
As a comparison, it usually requires an operating temperature
of higher than 850 °C for a cell with YSZ as the electrolyte and
LSM as the cathode.10 Such pioneering work greatly
accelerates the movement of SOFCs toward intermediate
temperature operation. Although BSCF soon became the
benchmark cathode material for intermediate temperature
SOFCs (IT-SOFCs), the later extensive research works
demonstrated several drawbacks of this material, including
relatively poor structural stability at low to intermediate
temperatures,21 high sensitivity to CO2 poisoning,60,61 and a
large TEC up to 24 × 10−6 K−1 between 400 and 900 °C
(almost doubled that of the SDC electrolyte).66 It suggests that
other electrodes with improved overall performance are still
urgently needed. By adjustment of the mole ratio of Ba/Sr at
the A site and Co/Fe in the B site, the structural stability of
perovskite was improved somewhat and TEC was reduced to a
certain degree; however, the cathode performance was also
found to decrease with an increasing iron content in the B
site.67,68
4.1. Cobalt-Based Perovskite-Type Cathodes.
4.1.1. Cation Stoichiometric Perovskites. Doping was
extensively used during the past few years to tailor the
properties and electrochemical performance of perovskite
mixed conductors as cathode materials for ILT-SOFCs.
Considering the high oxygen vacancy concentration and
electronic conductivity of cobalt-based perovskite oxides,
considerable efforts have been conducted from us with the
development of cobalt-based perovskite or perovskite-related
oxides as cathodes of ILT-SOFCs, mainly through the doping
of BaCoO3−δ and SrCoO3−δ parent oxides. A site, B site,
combined A and B sites, or even the oxygen site doping was
tried. Table 1 listed the properties and performance of various
cobalt-based perovskite or related oxides as the cathode of
15175
Review
oxygen-ion-conducting ILT-SOFCs developed or investigated
in our group.65,69−91 Most of the materials showed promising
activity for the ORR at intermediate temperatures. For
example, through replacing 25 mol % Co with Sc in the B
site of BaCoO3−δ with the formation of BaCo0.75Sc0.25O3−δ
(BCSc), a cubic structure was stabilized, which has the highest
electronic and oxygen ion conductivities among all of the
crystal structures of BaCoO3−δ. The BCSc displayed a
remarkable ORR activity, which was mainly due to the higher
oxygen vacancy concentration compared to BSCF. The SOFC
with the BCSc cathode, SDC electrolyte, and Ni + SDC anode
achieved a PPD of 1045 mW cm−2 at 600 °C.74 Considering
the high price of scandium, we tried to use other cost-effective
dopants to replace it. Sn was also considered as a good dopant
to stabilize the cubic lattice structure of perovskites. We
proposed 10 mol % Sn and 30 mol % Fe co-doped BaCoO3−δ,
i.e., BaCo0.6Fe0.3Sn0.1O3−δ (BCFSn), as a potential cathode of
ILT-SOFC. BCFSn demonstrated a low average TEC of 15.8
× 10−6 K−1 from room temperature to 800 °C, which is close
to that of SDC, implying a good match with the electrolyte in
thermal expansion behavior. Because of the low Sn
concentration and the low bond energy between Sn and
oxygen, a high oxygen vacancy concentration in the lattice was
found, which promoted the oxygen surface exchange and bulk
diffusion. Hence, the BCFSn electrode showed a favorable
ORR activity with the ASR of only 0.097 Ω cm2 at 600 °C in
air, and the cell with the SDC electrolyte and BCFSn cathode
delivered a PPD of 1168 mW cm−2 at 600 °C by operating on
hydrogen fuel.75
As we know, Ba2+ is highly alkaline and easily reacts with
CO2 in the atmosphere, resulting in the poisoning of the
cathode during the fuel cell operation. Because Sr2+ is less basic
than Ba2+, Sr2+ is more suitable as an A-site substitute. We then
introduced a doping strategy to modify the SrCoO3−δ parent
oxide and developed many materials as potential cathodes of
ILT-SOFC with favorable activity. For example, when doping
the B site of SrCoO3−δ with 20 mol % Sc3+, the cubic
perovskite structure with oxygen vacancy disordered was
stabilized and the oxide showed a high oxygen vacancy
concentration and oxygen ion conductivity.76,77 As an oxygen
reduction electrode, a low ASR of 0.09 and 0.52 Ω cm2 was
achieved at 600 and 500 °C, respectively. A single cell with the
Ni + SDC anode, SDC electrolyte, and SrSc0.2Co0.8O3−δ
cathode delivered a PPD of 902 mW cm−2 at 600 °C using
hydrogen as the fuel.77 The high performance is probably due
to the low oxygen−Sc bond energy, low and fixed oxidation
state of Sc3+, and cubic lattice structure, resulting in a high
oxygen vacancy concentration and oxygen mobility. Besides
Sc3+, the B site of SrCoO3 doped with a low concentration of
Nb ion (10 mol %) can also efficiently maintain the cubic
structure of SrCoO3. We demonstrated that SrNb0.1Co0.9O3−δ
(SNC) is a potential oxygen electrode for low temperature
SOFC (<600 °C).78 SNC showed an extremely low polar-
ization resistance of 1.828 Ω cm2 at 450 °C, while that for
BSCF was 2.875 Ω cm2. A single cell with the configuration of
SNC|SDC|Ni + SDC achieved a high PPD of 1008 mW cm−2
at 600 °C. Even at the temperature of 400 °C, it still showed a
PPD of 153 mW cm−2. Such excellent performance was
attributed to high electrical conductivity (>100 S cm−1 below
525 °C) and large oxygen vacancy concentration at the
operated temperatures. When the B site of SrCoO3 was co-
doped with Sc and Nb ions with the formation of
SrSc0.175Nb0.025Co0.8O3−δ (SSNC), the bulk oxygen diffusion
https://dx.doi.org/10.1021/acs.energyfuels.0c01887
Energy Fuels 2020, 34, 15169−15194
Energy & Fuels
Figure 2. (a) ASR of SrCo0.9Nb0.1O3−δ (SCN10), SrCo0.8Nb0.2O3−δ (SCN20), SrCo0.9Ta0.1O3−δ (SCT10), SrCo0.8Ta0.2O3−δ (SCT20), SCNT, and
BSCF at different temperatures. (b) Performance of the SOFC with the configuration of SCNT|GDC (∼14 μm)|Ni + GDC operating on H2.84
rate is very fast below 550 °C, leading to 2 times improvement
in oxygen reduction activity on SSNC compared to BSCF. The
ASR of SSNC is only 0.32 Ω cm2 at 500 °C, and a very high
PPD of 910 mW cm−2 at 500 °C was obtained for the SOFC
[SSNC (cathode)|thin-film SDC|Ni + SDC (anode)] operat-
ing on humidified H2.80 We think a possible synergistic effect
between two highly charged dopants appeared, resulting in a
positive impact on the ORR. Later, Nb and Ta B-site co-doped
SrCoO3−δ perovskite, SrCo0.8Nb0.1Ta0.1O3−δ (SCNT), was
further developed, which showed an extremely high ORR
activity at reduced temperatures.84 As shown in Figure 2a, the
ASR is only 0.16 Ω cm2 at 500 °C, which is 50% of SSNC. The
single cell with the SCNT cathode showed a PPD of 1220 mW
cm−2 at 500 °C (Figure 2b).
On the basis of the experimental results and density
functional theory (DFT) calculations, it was found that a
synergistic effect between Nb and Ta was created, which
accounts for the superior activity for ORR. The synergistic
effect not only occurred on co-doped cations but also between
different phases in one composite. Recently, we developed a
composite with a nominal composition of SrCo0.7Fe0.2W0.1O3−δ
(SCFW) synthesized via a one-pot synthesis as a superior
cathode of ILT-SOFCs.85 According to the refined X-ray
diffraction (XRD) pattern (Figure 3), mixed phases of a single
perovskite (SP) and a double perovskite (DP) were
demonstrated in SCFW. In comparison to SrCo0.7Fe0.3O3−δ
(SCF), this composite possessed enhanced ORR activity and a
lower TEC as a result of the synergistic effect between SP and
Figure 3. Refined XRD pattern of SCFW.85
pubs.acs.org/EF Review
DP phases. Additionally, a long-term stability was also
improved because of the doping of a small amount of W
into the SCF oxide lattice.
In addition to B-site doping, we also designed some
perovskites with combined A and B site co-doping, such as
Ba0.6Sr0.4Co0.9Nb0.1O3−δ (BSCN),86 which showed a little
higher electrochemical performance than SCN. Nd3+ has
been proven to stabilize the perovskite structure.92 Therefore,
we developed Nd0.2Sr0.8Nb0.1Co0.9O3−δ (NSNC) by co-doping
of the A site with Nd3+ and the B site with Nb5+.87 Thanks to
the synergistic effect, the NSNC showed better ORR
electrocatalytic activity than Nd0.2Sr0.8CoO3−δ, SNC, and
SrCoO3−δ. The SOFC with the configuration of NSNC|thin-
film SDC|Ni + SDC obtained a high PPD of 1261 mW cm−2 at
600 °C. Generally, the interfacial reaction between different
components in SOFC should be avoided. However, under
certain circumstances, we found that the interfacial reaction
can benefit the cathode performance.88 For example, the phase
reaction between SDC and SrCoO3 could result in the
formation of Sm and Ce co-doped SrCoO3, accompanied by
the phase transformation from a 2H BaNiO3-type structure to
cubic perovskite. Concurrently, the oxygen mobility and
electrical conductivity of the cathode were increased greatly.
Therefore, SrCoO3, an oxide with poor electronic conductivity
and ionic conductivity, can be developed into a promising
cathode with low ASR of 0.18 Ω cm2 at 600 °C via the phase
reaction with the SDC electrolyte.
4.1.2. Cation Non-stoichiometric Perovskites. In addition
to doping, the creation of A- or B-site cation deficiency was
also found as an effective strategy to increase the oxygen
vacancy concentration or oxygen mobility and, as a result,
improved activity for the ORR at the ILT range.93−97 For a
typical ABO3 oxide, the cation ratio of the A to B site is usually
unit. However, the perovskite structure can tolerate a certain
cation non-stoichiometry while maintaining the perovskite
structure.98 The A-site cation deficiency is more popular
compared to B-site cation deficiency, which is believed to be
energetically less favorable. It was found that the perovskite
structure can still be maintained without the appearance of the
impurity phase under the condition that the A-site cation
deficiency is up to 20%.99 From the introduction of A-site
cation deficiency into the perovskite lattice, the electrical
charge neutrality can be realized through the creation of
additional oxygen vacancies within the oxide lattice, which is
15176 https://dx.doi.org/10.1021/acs.energyfuels.0c01887
Energy Fuels 2020, 34, 15169−15194
 Table 2. Properties and Performance of Non-stoichiometric Perovskite Cathodes for ILT-SOFCs as Developed or Investigated in Our Group
space conductivity in air, ASR in air at 600 °C PPD, H2 fuel at 600 °C
cathode phase structure group 300−800 °C (S cm−1) (Ω cm2) (mW cm−2) cell configuration reference
(Ba0.5Sr0.5)0.97Co0.8Fe0.2O3−δ cubic Pm3̅m 9.6−34.4 0.138 694 (BS)0.97CF|SDC|Ni + Sm0.2Ce0.8O1.9 (SDC) 100
[(BS)0.97CF]
Energy & Fuels

(Ba0.5Sr0.5)0.91Co0.8Fe0.2O3−δ cubic Pm3̅m 9.7−26.6 0.220

(Ba0.5Sr0.5)0.85Co0.8Fe0.2O3−δ cubic Pm3̅m 8.4−24.3
(Ba0.5Sr0.5)0.80Co0.8Fe0.2O3−δ cubic Pm3̅m 8.0−29.5 0.265
Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) cubic Pm3̅m 8.7−42.7 0.093 728 BSCF|SDC|Ni + SDC
(Ba0.5Sr0.5)1.03Co0.8Fe0.2O3−δ cubic Pm3̅m 8.2−31.7 0.068 846 (BS)1.03CF|SDC|Ni + SDC 101
[(BS)1.03CF]
(Ba0.5Sr0.5)1.09Co0.8Fe0.2O3−δ cubic Pm3̅m 6.9−25.8 0.295
(Ba0.5Sr0.5)1.15Co0.8Fe0.2O3−δ cubic Pm3̅m 5.3−22.1
(Ba0.5Sr0.5)1.20Co0.8Fe0.2O3−δ cubic Pm3̅m 4.1−9.7 2.083
BaCo0.7Fe0.2Nb0.1O3−δ cubic 2.3−10.9 0.235 93
Ba0.95Co0.7Fe0.2Nb0.1O3−δ cubic 2.2−10.2 0.182
Ba0.9Co0.7Fe0.2Nb0.1O3−δ cubic 2.0−9.6 0.090 711 B0.9CFN|SDC|Ni + SDC
(B0.9CFN)
SrNb0.1Co0.9O3−δ cubic P4mm 266−96 0.086 94 and
95
Sr0.98Nb0.1Co0.9O3−δ cubic P4mm 171−82 0.133
Sr0.95Nb0.1Co0.9O3−δ (S0.95NC) cubic P4/ 276−117 0.044 1566 S0.95NC|SDC|Ni + SDC
mmm
BaCo0.4Fe0.4Zr0.1Y0.1O3−δ cubic Pm3̅m 0.4−2.2 0.043 1035 BCFZY1.0|SDC|Ni + SDC 96

15177
(BCFZY1.0)
Ba(Co0.4Fe0.4Zr0.1Y0.1)0.975O3−δ cubic Pm3̅m 0.011
Ba(Co0.4Fe0.4Zr0.1Y0.1)0.950O3−δ cubic Pm3̅m 0.3−1.8 0.024 1419 BCFZY0.95|SDC|Ni + SDC
pubs.acs.org/EF

(BCFZY0.95)
Ba(Co0.4Fe0.4Zr0.1Y0.1)0.925O3−δ cubic Pm3̅m 0.342
Ba(Co0.4Fe0.4Zr0.1Y0.1)0.900O3−δ cubic Pm3̅m 0.2−1.5 2.051
PrBaCo2O5+δ tetragonal P4/ 887−510 0.256 97
mmm
PrBa0.95Co2O5+δ tetragonal P4/ 993−545 0.222
mmm
PrBa0.90Co2O5+δ tetragonal P4/ 913−598 0.175
mmm
La2NiO4+δ orthorhombic Fmmm 9.207 96 La2NiO4+δ|8 mol % Y2O3−ZrO2(YSZ)|SDC|Ni + SDC 103
La1.98NiO4+δ orthorhombic Fmmm 9.207
La1.95NiO4+δ orthorhombic Fmmm 12.507 81 La1.95NiO4+δ|YSZ|SDC|Ni + SDC
La1.90NiO4+δ orthorhombic Fmmm 13.236 72 La1.90NiO4+δ|YSZ|SDC|Ni + SDC
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Energy & Fuels
the main reason for the increased activity for ORR. In addition,
the presence of cation deficiency means that the free volume of
the perovskite unit cell also increases, which benefits oxygen
mobility. However, sometimes, the defected cation sites may
act as trap sites for immobilizing the oxygen anions, resulting
in a reduction in oxygen diffusion. It suggests that the materials
should be well-designed so that the cation deficiency can
introduce a beneficial effect for catalyzing the ORR. Shown in
Table 2 are the various cation non-stoichiometric perovskites
that were investigated by us, and a comparison was made with
the cation stoichiometric perovskites. Therefore, the introduc-
tion of proper cation deficiency is highly obvious in improving
the cathodic performance.
Considering the high activity of BSCF for the ORR, A- or B-
site cation-deficient (Ba0.5Sr0.5)1−xCo0.8Fe0.2O3−δ [(BS)1−xCF]
were developed as potential cathodes for IT-SOFCs. When the
A-site cation deficiency reached 15%, the phase structure of
(BS)0.85CF can still be maintained as a cubic perovskite.
However, if it further increased to 20%, apart from the main
perovskite phase, a (Fe,Co)3O4 impurity was formed. It was
found that A-site cation deficiency can reduce the TEC of the
material and make it more thermomechanically compatible
with the doped ceria electrolyte. For example, the TEC is 21.4
× 10−6 K−1 for BSCF at 50−750 °C, while it reduced to 18.0 ×
10−6 K−1 for (BS)0.97CF in the same temperature range.
However, the electrochemical performance for the ORR
declined somewhat, from 0.093 Ω cm2 for BSCF to 0.138 Ω
cm2 for (BS)0.97CF at 600 °C. Such deterioration in activity
may suggest the appearance of vacancy association.100 The
introduction of B-site cation deficiency was found to cause
lattice expansion and create more active sites for the ORR as a
result of the reduced valence states of the B-site cation and the
increased oxygen vacancy concentration. The electrochemical
performance of the material first increased and then decreased
with the B-site cation deficiency further increasing. Among
them, (BS)1.03CF showed the best ORR activity at 600 °C with
an ASR of only 0.068 Ω cm2, and BSCF was 0.093 Ω cm2,101
while the TEC did not obviously increase (21.2 × 10−6
K−1).102
The tolerance of cation non-stoichiometry is a universal
phenomenon for perovskite oxides. For example, Ba-
Co0.7Fe0.2Nb0.1O3−δ (BCFN) can tolerate a certain degree of
cation deficiency. From the introduction of 10% deficiency in
the barium site of BCFN, the perovskite phase was maintained
and additional oxygen vacancies were created, as confirmed by
oxygen non-stoichiometry (δ) determination. As a result, the
electrochemical performance was promoted significantly. In
comparison to BCFN, the ASR of B0.9CFN was reduced from
0.230 to 0.090 Ω cm2 at 600 °C.93 The introduction of a small
amount of Sr deficiency in (SNC) was also found to greatly
improve the cathode performance. For example, the ASR at
600 °C was reduced from 0.086 Ω cm2 for SNC to 0.044 Ω
cm2 for Sr0.95Nb0.1Co0.9O3−δ (S0.95NC).94 An anode-sup-
ported fuel cell with a S0.95NC cathode and SDC electrolyte
obtained PPD of 1016 mW cm−2 and a total electrode ASR
(sum of the cathode and Ni−SDC anode) of only 0.052 Ω cm2
at 500 °C.95 Recently, we studied the effect of B-site cation
deficiency on the performance of BaCo0.4Fe0.4Zr0.1Y0.1O3−δ
(BCFZY1.0). If the B-site cation deficiency of Ba-
(Co0.4Fe0.4Zr0.1Y0.1)1−xO3−δ (BCFZY1−x) is under 0.100 (0
< x ≤ 0.100), no phase transition was observed, while the
electrochemical performance was greatly improved at x ≤
0.050, as shown in Figure 4. For example, the ASR was
pubs.acs.org/EF Review
Figure 4. PPDs of cells with BCFZY1.0 and BCFZY0.95 cathodes at
different temperatures.96
decreased from 0.043 Ω cm2 of BCFZY1.0 to 0.024 Ω cm2 of
BCFZY0.95 at 600 °C, and the corresponding PPDs of the
single cells increased from 1035 to 1419 mW cm−2.96
The introduction of Ba deficiency in double perovskite oxide
(PBC) material was also found to improve the cathode
performance for IT-SOFCs, including both the conductivity
and ORR activity. For example, the electrical conductivity of
PrBa0.90Co2O5+δ reached 856 S cm−1 at 600 °C in air, as a
comparison of 744 S cm−1 for PBC, while their ASRs for the
ORR, tested under the same condition based on the
symmetrical cell configuration, are 0.175 and 0.256 Ω cm2,
respectively.97 The cation deficiency in the A site of the
perovskite-related Ruddlesden−Popper-type La2−xNiO4+δ (x =
0−0.1) oxides was studied. However, the A-site cation
deficiency caused the appearance of a high-order La3Ni2O7
phase, and its content increased with the increase of La non-
stoichiometry. In addition, a decreased activity for ORR was
observed for the La-deficient La2−xNiO4+δ electrodes compared
to the cation stoichiometric electrode.103 The different effects
of cation non-stoichiometry on the phase structure and ORR
activity of different perovskites or related oxides suggest that
the cation non-stoichiometry plays a complicated effect on the
properties and performance of perovskite. It is difficult to
optimize the materials by just prediction; instead, experimental
screening is still needed.
4.2. Iron-Based Perovskite Cathodes. Although cobalt-
based perovskites exhibit favorable activity for the ORR at
intermediate temperatures, the disadvantages are also obvious,
including the high price of cobalt and the large TEC of the
related materials. Although the TEC of cobalt-based perovskite
oxides can be reduced by a certain degree through doping, the
materials usually still show a much larger value than SDC or
YSZ electrolyte. This is due to the fact that cobalt is easy to
change its oxidation state and spin state within the perovskite
lattice. The development of cobalt-free cathodes for ILT-
SOFCs is thus highly attractive.44,52,104−128 In comparison to
cobalt, iron is much cheaper in price and more abundant in
resource, while it has similar +2, +3, and +4 oxidation states to
Cox+ but a slightly lager cation size than Cox+. In addition, iron
demonstrates high solubility in the perovskite lattice; the full B
site could be substituted by the Fe ion, thus providing a large
room for the design of iron-based perovskites. During the past
decade, our considerable efforts have been put into the
development of iron-based perovskites as the cathode materials
for ILT-SOFCs. Listed in Table 3 are the properties and
performance of the iron-based perovskite oxides as developed
15178 https://dx.doi.org/10.1021/acs.energyfuels.0c01887
Energy Fuels 2020, 34, 15169−15194
 Table 3. Properties and Performance of Cobalt-Free Cathodes for SOFCs as Developed or Investigated in Our Group
electrical PPD, H2
space conductivity in average TEC fuel
2
cathode phase structure group air (S cm−1) (K−1) ASR in air at 600 °C (Ω cm ) (mW cm−2) cell configuration reference
SrFeO3−δ (SF) orthorhombic Cmmm ∼40−185 at 0.875 ∼500 at SF|Sm0.2Ce0.8O1.9(SDC)|YSZ|Ni + 8 mol % Y2O3−ZrO2 104 and
Energy & Fuels

300−900 °C 700 °C (YSZ) 105

SrFeO2.95−δF0.05 (SFF0.05) cubic Pm3̅m 0.393 ∼750 at SFF0.05|SDC|YSZ|Ni + YSZ
700 °C
SrFeO2.90−δF0.10 (SFF0.1) cubic Pm3̅m 0.491 ∼700 at SFF0.1|SDC|YSZ|Ni + YSZ
700 °C
SrFe0.9Ti0.1O3−δ cubic Pm3̅m 0.310
SrFe0.9Ti0.1O2.95−δF0.05 cubic Pm3̅m 0.180
SrFe0.9Ti0.1O2.90−δF0.10 cubic Pm3̅m 0.200
SrFe0.9Hf0.1O3−δ (SFH) cubic Pm3̅m ∼24−50 at 0.193 1417 at SFH|SDC|YSZ|Ni + YSZ 105
300−900 °C 700 °C
SrFe0.85Ti0.1Ni0.1O3−δ (SFTNi) cubic Pm3̅m 30−130 at 0.17 106
300−900 °C
NiO exsolved cubic Pm3̅m 0.07 1420 at e-SFTNi|SDC|YSZ|Ni + YSZ
SrFe0.85Ti0.1Ni0.1O3−δ (e- 700 °C
SFTNi)
SrNb0.05Fe0.95O3−δ (SFN0.05) cubic Pm3̅m 21−128 at 27.6 × 10−6 at ∼0.36 710 at SFN0.05|SDC|YSZ|Ni + YSZ 107 and
300−900 °C 25−900 °C 700 °C 108
SFN0.1 tetragonal P4mm 12−58 at 22.1 × 10−6 at ∼0.4 810 at SFN0.1|SDC|YSZ|Ni + YSZ
300−900 °C 25−1000 °C 700 °C
SFN0.15 tetragonal P4mm 8−24 at 21.7 × 10−6 at ∼0.39 650 at SFN0.15|SDC|YSZ|Ni + YSZ
300−900 °C 25−1000 °C 700 °C

15179
SFN0.1 3D hierarchical porous ∼0.15 919 at SFN0.1 3D|SDC|Ni + SDC 109
600 °C
SrSc0.075Ta0.025Fe0.9O3−δ (SSTF) cubic Pm3̅m 16−56 at 21.0 × 10−6 at 0.092 110
pubs.acs.org/EF

300−900 °C 25−900 °C
SrSc0.025Nb0.075Fe0.9O3−δ cubic Pm3̅m 0.07 at after CO2 treatment 111
(SSNF)
Sr0.9Ce0.1Fe0.8Ni0.2O3−δ (SCeFN) contained four phases
perovskite SCeFN tetragonal I4/mmm 15.3−28.8 at 16.8 × 10−6 at 0.072 977 at SCeFN|SDC|Ni + SDC 112
RP SCeFN tetragonal I4/mmm 300−800 °C 200−800 °C 600 °C
NiO cubic Fm3m
CeO2 cubic Fm3m
Bi0.5Sr0.5FeO3−δ (BiSF) cubic Pm3̅m 0.4−2.5 at 12.4 × 10−6 at 0.6 1090 at BiSF|SDC|YSZ|Ni + YSZ 113−116
300−900 °C 25−1000 °C 750 °C
Ba0.9Bi0.1FeO3−δ (BBiF) contained three phases
BaFeO3−δ cubic Pm3̅m 7.14 × 10−6 at 0.384 1295 at BBiF|SDC|YSZ|Ni + YSZ 117
BaFe2O4 orthorhombic Bb21m 25−1000 °C 750 °C
BBiF triclinic P1
BaFeO3−δ (BF) contained three phases
BaFeO3 cubic Pm3̅m 0.17 1180 at BF|SDC|YSZ|Ni + YSZ 118
BaFe2O4 orthorhombic Cmc21 750 °C
Ba2Fe2O5 monoclinic P121/c1
Ba0.95La0.05FeO3−δ (BLF) cubic Pm3̅m 4.8−11.0 24.5 × 10−6at 0.211 1125 at BLF|SDC|YSZ|Ni + YSZ 44 and 119
25−1000 °C 700 °C
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 Table 3. continued
electrical PPD, H2
space conductivity in average TEC fuel
2
cathode phase structure group air (S cm−1) (K−1) ASR in air at 600 °C (Ω cm ) (mW cm−2) cell configuration reference
BaNb0.05Fe0.95O3−δ (BNF) contained two phases
Energy & Fuels

BaNbxFe1−xO3−δ cubic Pm3̅m 1.6−9.5 24.6 × 10−6 at 0.147 881 at BNF|SDC|YSZ|Ni + YSZ 120
Ba2NbyFe2−yO5−δ monoclinic P121/c1 25−1000 °C 700 °C
BaFe0.95Sn0.05O3−δ (BFS) cubic Pm3̅m 4.1−7.8 at 0.2 1033 at BFS|SDC|YSZ|Ni + YSZ 121
500−800 °C 700 °C
Ba0.5Sr0.5Fe0.9Cu0.1O3−δ cubic Pm3̅m ∼10−47 at 24.1 × 10−6 at 0.084 122
(BSFCu) 300−800 °C 50−600 °C
Ba0.5Sr0.5Fe0.8Cu0.1Ti0.1O3−δ cubic Pm3̅m ∼7−16 at 19.4 × 10−6 at 0.088 1166 at BSFCuTi|GDC|Ni + Gd0.1Ce0.9O2−δ (GDC)
(BSFCuTi) 300−800 °C 50−600 °C 600 °C
LaBaFe2O5+δ (LBF) cubic Pm3̅m ∼58−190 at 19.4 × 10−6 at ∼7.0 265 at LBF|SDC|YSZ|Ni + YSZ 123
300−900 °C 200−900 °C 700 °C
PrBaFe2O5+δ (PBF) cubic Pm3̅m ∼19−39 at 18.7 × 10−6 at ∼3.9 283 at PBF|SDC|YSZ|Ni + YSZ
300−900 °C 200−900 °C 700 °C
NdBaFe2O5+δ (NBF) orthorhombic Pmmm ∼13−23 at 18.3 × 10−6 at ∼2.5 308 at NBF|SDC|YSZ|Ni + YSZ
300−900 °C 200−900 °C 700 °C
SmBaFe2O5+δ (SBF) orthorhombic Pmmm ∼5.6−9.8 at 16.1 × 10−6 at ∼1.4 462 at SBF|SDC|YSZ|Ni + YSZ
300−900 °C 200−900 °C 700 °C
GaBaFe2O5+δ (GBF) orthorhombic Pmmm ∼2.2−7.2 at 15.6 × 10−6 at ∼1.9 396 at GBF|SDC|YSZ|Ni + YSZ
300−900 °C 200−900 °C 700 °C
YBaFe2O5+δ (YBF) orthorhombic Pmmm ∼0.5−1.1 at 14.6 × 10−6 at ∼8.9 218 at YBF|SDC|YSZ|Ni + YSZ
300−900 °C 200−900 °C 700 °C

15180
La0.6Ca0.4Fe0.8Ni0.2O3−δ orthorhombic Pnma 0.12 507 at LCFN−SDC|SDC|LCFN−SDC 52
(LCFN) 800 °C
La2NiO4 (LN) tetragonal I4/mmm ∼550 at LN−SDC|SDC|LN−SDC 124
800 °C
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La0.6Sr1.4MnO4+δ tetragonal I4/mmm ∼0.5−3.1 at ∼48 67 at LSMO4|SDC|LSMO4 125 and

300−900 °C 800 °C 126
La0.6Sr1.4MnO4+δ−SDC−NiO ∼1.2−4.3 at ∼1 614 at LSMO4−SDC−NiO|SDC|LSMO4−SDC−NiO
(LSMO4−SDC−NiO) 300−900 °C 800 °C
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Energy & Fuels pubs.acs.org/EF Review

Figure 5. (a) Rietveld refinement of the in situ XRD pattern of BF at 700 °C. (b) Schematic diagram of the oxygen surface diffusion and charge
transfer processes for the BF electrode.118

Figure 6. Comparison of different parameters between SF, SFF0.05, and SFF0.10 samples: (a) oxygen non-stoichiometry, (b) O2-TPD curves from
300 to 900 °C, and (c) fitted values of Dchem and (d) kchem from 600 to 800 °C.104

by us as the cathode of ILT-SOFCs.104−123 Very interestingly,
several iron-based perovskite oxides showed comparable ORR
activity to that of the benchmark cobalt-based oxides at
intermediate temperatures.106,109−112
SrFeO3−δ (SF) perovskite is a common parent oxide with its
mixed ionic and electronic conductor (MIEC) characteristics
and low TEC. When the A, B, or oxygen site is doped, the
ORR electrochemical performance of SF can be effectively
improved.104−116 For example, when Bi3+ was doped into the A
site of SF, Bi0.5Sr0.5FeO3−δ (BiSF) was prepared and compared
to the La0.5Sr0.5FeO3−δ (LSF) cathode.113−115 The average
metal−oxygen bond energy (ABE) of BiSF is 209.1 kJ mol−1,
which is smaller than 241.2 kJ mol−1 of LSF, meaning that the
lattice oxygen of BiSF is more easily precipitated to form
oxygen vacancies. At the same time, BiSF has more excellent
oxygen ion diffusion performance than LSF; the bulk diffusion
15181
(Dchem) and surface exchange (kchem) performances of BiSF are
almost 20 times larger than those of LSF. The ASR value of
BiSF at 750 °C is only 0.06 Ω cm2. In addition to its excellent
electrochemical performance for the ORR, BiSF also has a
TEC value that completely matches the electrolyte and anode.
In a temperature range of 25−1000 °C, the TEC value of BiSF
is only 12.4 × 10−6 K−1, which is the same as the SDC
electrolyte (12.4 × 10−6 K−1) and the Ni−YSZ anode (12.3 ×
10−6 K−1). In comparison to the A-site doping, the B-site
doping with transition metal ions has more flexibility. At
present, we have successfully doped one or two elements of
Ti4+, Hf4+, Nb5+, Ni2+/3+, Sc3+, and Ta5+ into SF parent
oxide.104−111 The doping of transition metal ions to the iron
site is beneficial in improving and stabilizing the structure of
SF-based perovskites and increasing the oxygen vacancy
concentration of the cathodes. For example, the
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Energy Fuels 2020, 34, 15169−15194
Energy & Fuels pubs.acs.org/EF
SrNb0.05Fe0.95O3−δ (SFN0.05) cobalt-free cathode as devel-
oped showed a low ASR of 0.36 Ω cm2 at 600 °C.107
Interestingly, it was found that when Fe was replaced by two
different elements at the same time, it could achieve better
ORR performance. For example, we developed a series of Sc
and Ta co-doped SF perovskites, SrSc0.075Ta0.025Fe0.9O3−δ
(SSTF), which showed the lowest ASR of 0.092 Ω cm2 at
600 °C in air. The high performance is mainly due to the
synergetic effect of the co-doping of Sc and Ta.
Cobalt-free BaFeO3−δ (BF) is also an important parent oxide
for many perovskites with different properties, which itself also
has excellent ORR activity.118 On the basis of in situ high-
temperature XRD (HT-XRD), BF was found to be composed
of two phases of BaFeO3 in the cubic structure and BaFe2O4 in
the orthorhombic structure at 700 °C (as shown in Figure 5a).
Among them, BaFeO 3 has a higher oxygen vacancy
concentration, while BaFe2O4 might be implemented for
oxygen surface diffusion. The schematic diagram of the surface
diffusion and charge transfer processes for the BF electrode
was shown in Figure 5b. As a result, BF showed a low
resistance in both processes, and an ASR of the BF cathode is
only ∼0.021 Ω cm2 at 700 °C. When the A or B sites of BF
were doped, the cubic structure of the perovskite could be
stabilized; consequently, its ORR performance was optimized.
For example, we demonstrated that, by doping a small amount
of La into the A site of BaFeO3 (5%), the cubic structure was
formed, which could not be simply explained on the basis of
the tolerance factor because such a small amount of La doping
should not have a big change on the tolerance factor.44,119 It is
likely that the La3+ doping forced Fe to take a lower oxidation
state, making the B-site cation match A-site Ba in size; as a
result, the oxygen-vacancy-disordered perovskite with a high
oxygen vacancy concentration was formed. An ASR of 0.211 Ω
cm2 was obtained at 600 °C. The cobalt-free oxides with the
composition of LnBaFe2O5+δ (Ln = La, Pr, Nd, Sm, Gd, and Y)
were also systematically investigated.123 As the Ln3+ ion radius
decreased, the phase structure of LnBaFe2O5+δ changed from
cubic to orthorhombic, the average valence state of Fe in the B
site decreased from 3.39 to 2.98, the oxygen content decreased
from 0.89 to 0.48, the highest conductivity in the air
atmosphere was reduced from 190 to 1.1 S cm−1, and the
TEC was reduced from 19.4 × 10−6 to 14.6 × 10−6 K−1. The
lower TEC values of LnBaFe2O5+δ oxides can have better
thermal matching with the electrolyte materials. Among all
LnBaFe2O5+δ oxides, SmBaFe2O5+δ and GdBaFe2O5+δ showed
the best ORR electrochemical performance; the ASRs of ∼1.4
and ∼1.9 Ω cm2 were achieved at 600 °C under open circuit
voltage, respectively.
Halogen doping in oxygen site is also a strategy to effectively
improve the oxygen ORR activity of cathode materials.104 As
shown in Figure 6, by doping a small amount of F− in the SF
and SFT perovskites, although F− doping reduced the oxygen
non-stoichiometry and oxygen vacancy concentration of SF
(panels a and b of Figure 6), the Dchem and kchem properties of
the cathode materials can be effectively improved (panels c and
d of Figure 6). For example, the Dchem and kchem values were
4.12 × 10−5 cm2 s−1 and 4.04 × 10−4 cm s−1 for the SF
cathode, while they were 17.28 × 10−5 cm2 s−1 and 17.41 ×
10−4 cm s−1 for SrFeO3−δF0.1 (SFF0.1). Although F− doping
reduced the oxygen non-stoichiometry of SF, as a result of the
fast transport properties, SrFeO3−δF0.05 (SFF0.05) achieved the
best electrochemical performance. At 600 °C, the ASR value of
SFF0.05 is only 0.393 Ω cm2, which is much smaller than that
15182
Review
of SF cathode (0.875 Ω cm2). For cobalt-free cathodes, we can
also tailor the morphology of the electrodes, such as the use of
impregnation52,124−126 or in situ growth technique,106 to
introduce nanoparticles into the electrodes or prepare the
multiphase composite cathodes112,117,118 to further improve
the ORR performance of the cathodes.
4.3. Morphological Control. As mentioned, in addition to
intrinsic activity, the apparent activity is also closely related to
the number of active sites. An increase in the surface area of
the electrode will lead to the increase in the active sites for
ORR; thus, an increased ORR activity is expected. Suppressing
the sintering of the cathode material would result in an
increase of the electrode surface area. On the contrary, an
increase in the sintering of the cathode would reduce the
surface area of the electrode. During the synthesis of BSCF
perovskite by an ethylenediaminetetraacetic acid (EDTA)−
citrate complexing method, it was found the introduction of
nitric acid reduced the crystalline size of the powder. The
smaller crystallite size of the powder lead to a higher sintering
temperature of the cathode and, thus, a decreased electrode
surface area. In addition, nitric acid also had a significant
adverse effect on the oxygen surface exchange kinetics and the
oxygen bulk diffusion rate of the BSCF cathode. As a result, the
BSCF powder synthesized with the introduction of nitric acid
demonstrated reduced ORR activity and, consequently, the
poor performance of the corresponding fuel cell.69
To suppress the sintering of the electrode during cell
fabrication, we then proposed a strategy of using a sintering
inhibitor.127 A small amount of NiO (5 wt %) was found to
suppress the grain growth of BSCF, thus increase the electrode
surface area, and hence, improve the ORR activity. For
example, the ASR of BSCF + 5 wt % NiO is approximately
36.5% lower than that of the BSCF electrode at 600 °C.
Recently, we demonstrated that, through the post-synthesis
CO2-induced activation, the surface area of the cobalt-free
SrSc0.025Nb0.075Fe0.9O3−δ (SSNF) perovskite can be effectively
increased.111 The exposure of the cathode to the CO2-
contained atmosphere can cause the corrosion of the electrode
surface, thus leading to an increased surface area. Once CO2
was removed, the perovskite structure at the surface layer was
restored, while the morphology was maintained. As a
consequence, the electrode surface area was enlarged. After
the CO2-induced activation, the ASR of the electrode at 600
°C was improved from 0.13 to 0.07 Ω cm2. It should be
mentioned that the chemical stability of the perovskite
materials should be well-tailored; otherwise, the perovskite
structure may be destroyed if the chemical stability is not high
enough, and a decreased catalytic activity is likely to occur
because the structure cannot be restored.
In addition to reducing the particle/grain size of the
electrode, another important way to increase the electrode
surface area is the buildup of a mesoporous electrode
architecture. We fabricated a 3D hierarchical porous electrode
directly from a carbon oxide precursor through a versatile,
cost-effective, and simple method.109 As a result of the
expansion of the active areas and the optimized gas
transmission channels, the ORR activity of the porous
electrode was greatly improved. The as-prepared porous
cobalt-free cathode reached an ASR value of only 0.15 Ω
cm2, and the corresponding SOFC showed high power
generation with 919 mW cm−2 at 600 °C.
A high calcination temperature is typically required to
fabricate the cathode layer (typically >950 °C), which
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Energy Fuels 2020, 34, 15169−15194
Energy & Fuels
inevitably leads to the sintering of the electrode with a large
grain size. The infiltration method was then extensively used
for the fabrication of nanoparticle-modified electrodes for
SOFCs, including both the anode and cathode.52,124−126 A
porous scaffold is first fabricated onto the electrolyte surface at
elevated temperatures to act as a substrate, and then the
electrocatalytically active materials are infiltrated into the
scaffold and then calcined at relatively low temperatures. As a
result of the relatively low firing temperature for the second
step, nanoparticles are often formed after calcination, which
cover the scaffold. Typically, the same material of electrolyte is
used as the scaffold, which provides an efficient oxygen ion
transportation channel, while the high surface area of
nanoparticles provides the rich active sites for the ORR. For
example, we applied impregnated LaFe0.67Co0.3Pd0.03O3 perov-
skite as a promising electrocatalyst for “symmetrical” SOFC,
delivering promising performance.90 Again, the sintering of
nanoparticles is a big concern. As well known, nanoparticles
have high surface energy, which are easily aggregated at an
elevated temperature. We then proposed a thin-film-modified
electrode concept for achieving a high electrode surface as well
as good electrode morphology stability, by the in situ beneficial
interfacial reaction. The as-fabricated cathode with a 3D core−
shell architecture (Figure 7) showed a highly efficient and
thermally stable ORR at 700 °C for a tested period of 208 h
with a low ASR of 0.075 Ω cm2.54
Figure 7. TEM images of the core−shell-structured electrode.54
The creation of a strong nanoparticle−substrate interaction
can effectively suppress the aggregation of nanoparticles and,
consequently, increase the thermal stability of the electrode.
For the nanoparticle-modified electrode prepared by infiltra-
tion, the contact between the nanoparticles and the substrate is
usually weak. Exsolution of certain element(s) using the
perovskite lattice as the matrix recently turned out to be a
fascinating technique for the generation of nanoparticle-
modified perovskite with a strong nanoparticle−substrate
interaction.128−133 More attractiveness is that once the
nanoparticles are aggregated, they can be regenerated through
dissolution of the particles into the matrix via chemical
oxidation or electrochemical oxidation (anodic polarization)
and then re-exsolution.106,134 Such a concept was mainly
applied for the research of a metallic nanoparticle-modified
perovskite as the anode for SOFCs.135−137 In 2011, we first
adopted this concept of silver nanoparticle-modified perovskite
pubs.acs.org/EF Review
for the cathode of SOFCs;138 the results showed that the as-
obtained silver nanoparticle-modified LSM perovskite had
stable operation with high activity for ORR, even at 800 °C. By
further development of a cathode with the composition of
silver nanoparticle-modified SCN perovskite based on the
exsolution strategy,91 an ASR as low as 0.214 Ω cm2 at 500 °C
was achieved and the anode-supported cell with the new
cathode delivered a high PPD of 1116 mW cm−2 at 500 °C,
which is much better than BSCF. The strong interaction
between the silver nanoparticles and the SCN substrate
effectively suppressed the aggregation of silver nanoparticles;
in addition, as a result of the special electrode configuration,
the TEC of the electrode is compatible with that of the
electrolyte. As a result, the electrode showed stable perform-
ance within a long test period of 600 h at 500 °C. The further
combination of the infiltration method with nanoparticle
exsolution can lead to the buildup of a hierarchical mesoporous
electrode with different levels of nanoparticles to further
improve the cathode performance.
The formation of a nanocomposite is another way to
suppress the sintering of nanoparticles; in addition, the
dynamic cation exchange at operation conditions can
effectively suppress the oxidation state change of the
compositional element, thus effectively reducing the TEC.
Such a nanoscale interaction also leads to the improved
cathodic performance for the ORR; as a result, both high
activity and durability for the ORR can be achieved.139 For
example, we developed a nanocomposite of a single perovskite
and double perovskite based on one-pot synthesis; the as-
prepared material showed an ASR of 0.058 Ω cm2 at 600 °C;
and good operational stability was observed within a test
period of 225 h. Such a composite showed a TEC of 18.6 ×
10−6 K−1 from 200 to 1000 °C, which is significantly lower
than the other cobalt-based perovskite and double perovskite
oxides.85
4.4. CO2-Tolerant Cathodes. As we know, in practical
SOFCs, the cathode is directly exposed to ambient air that
usually contains a certain level of CO2. Therefore, the chemical
stability of the electrode against CO2 poisoning is also an
important concern. Considerable efforts have been directed
from our group to improve the stability of the electrode
operated in an atmosphere containing CO2. Many excellent
cathodes with good CO2 tolerance have been developed, such
as LN/BSCF,59 NSNC,87 Ag/Sr0.95Nb0.1Co0.9O3−δ (Ag/
S0.95NC),91 (SSTF),110 SrNb0.1Co0.9−xFexO3−δ (SNCF),140
SSNC,141 GDC/SCNT,142 Bi2Sr2Nb2MnO12−δ (BSNM).143
For clarity, these advanced cathodes in our work were designed
from three main strategies, i.e., doping, introducing a second
phase, and crystal structure engineering.
An important point of view of the reaction between the
cathode and CO2 is based on the theory of Lewis acids and
bases, where the metal oxide on the surface of the cathode and
CO2 act as the base and acid, respectively.141 On the basis of
this theory, decreasing the basicity of cathode materials could
improve the resistivity to CO2. SrCoO3−δ-based perovskite
cathodes with high mixed conductivities show promising
electroactivity for the ORR at intermediate temperatures but
are susceptible to CO2 poisoning.144 To address this issue, we
doped some high-valence cations with relatively high acidity
into a parent SrCoO3−δ oxide lattice to stabilize the crystal
structure and enhance the CO2 tolerance. Examples include
partial doping in the B site with Sc3+, Nb5+, and/or Ta5+ and in
the A site with Nd3+.87,110,140,141 It is proposed to increase the
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Energy & Fuels
Figure 8. (a) Schematic of the exsolution process. (b) Time-dependent ASR values of three cathodes in air with different CO2 concentrations at
600 °C.91 (c) Schematic diagram of the Aurivillius crystal structure of BSNM. (d) Comparison of the ASR values of the BSNM cathode to other
reported manganese-containing cathodes. (e) Impedance spectra of the BSNM cathode in air and 10 vol % CO2/air atmospheres at 700 °C.143
acidity and thermodynamic stability of these perovskite oxides
to illustrate the enhanced CO2 resistance. Moreover, we also
found that the low oxygen vacancy concentration in SNCF
perovskite can reduce the basicity and, thus, increase the CO2
tolerance ability, and the ABE can be applied as a useful CO2
tolerance prediction index.140
Another effective strategy to improve CO2 tolerance is to
introduce a second phase with forming composite cath-
odes.59,91,142 One attracting advantage of composite cathodes
is that they exhibit combined advantages from different
compositions. Therefore, the resistance of the cathode to
CO2 can be improved by introducing an additional phase with
high CO2 resistance. For example, the CO2 resistance of the
BSCF cathode could be improved by a 3D hierarchical shell of
CO2-resistant La2NiO4−δ (LN), which was prepared by
infiltration and microwave plasma treatment.59 Such a
composite cathode shows both enhanced ORR activity and
resistance against CO2. With regard to high oxygen ion
conductivity and good stability against CO2, the GDC
electrolyte can also be used as a protective layer.142 For
instance, the GDC/SCNT composite cathode shows slightly
lower electrochemical performance but higher resistance to
CO2 than the SCNT cathode.142 Furthermore, we also
reported a facile exsolution method to develop the Ag
nanoparticle-decorated surface of Sr0.95Ag0.05Nb0.1Co0.9O3−δ
(SANC) perovskite oxide (Figure 8a), as a highly active
cathode with good CO2 tolerance for IT-SOFCs.91 As depicted
in Figure 8b, the increase in the ASR of the exsolved SANC (e-
SANC) cathode is obviously more moderate than that of the
S0.95NC and BSCF cathodes, indicating that the Ag nano-
particles decorated on the surface could protect the oxide from
CO2 attack. These results make the heterostructured
composites as highly promising CO2-tolerant cathodes.
Although strategies of doping and forming composite oxides
for the development of CO2-tolerant cathodes have been
proposed, all developed cathodes cannot completely resist CO2
poisoning. To solve this issue, a new oxide with a unique
pubs.acs.org/EF Review
Aurivillius structure (Figure 8c), BSNM, was supplied as a
cathode for IT-SOFCs.143 The BSNM cathode not only shows
excellent ORR activity at intermediate temperatures (Figure
8d) but also, more importantly, possesses complete CO2
tolerance (Figure 8e), which is one of the few cathode
materials containing alkaline earth metal with this property.
The excellent CO2 tolerance of the BSNM cathode should be
attributed to its unique structure and composition, containing
high acidity elements of Bi3+, Nb5+, and Mn3+/4+ as well as
strong ABE.
To summarize, the susceptibility to CO2 of cathode
materials will adversely affect the electrochemical performance
of SOFC for a long time. At lower temperatures, the tolerance
to CO2 of cathodes becomes lower, which is attributed to the
basic nature of the contained alkaline earth elements. Strategies
are explored to improve the CO2 tolerance, such as doping
acidic cations to increase the overall acidity of the oxide,
forming composite cathodes by introducing a CO2-resistant
protective layer, or engineering a special crystal structure.
However, in most cases, these approaches must sacrifice the
performance of the cathodes. For cathodes containing alkaline
earth elements, there is a trade-off between high ORR activity
and good CO2 tolerance. Up to now, although some advances
have been achieved, the studies about the development of
CO2-tolerant cathodes for ILT-SOFCs are still very limited.
Therefore, more work is required to understand the
mechanism of CO2 poisoning in a cathode, so that more
effective methods can be developed to further improve CO2
tolerance while maintaining high ORR activity of the cathode.
In addition, the ABE can be considered as an effective
quantitative parameter to forecast the CO2 tolerance when
designing cathode materials. The stronger the ABE, the higher
the resistance toward CO2.
4.5. Cathodes of PCFCs. In principle, the proton-
conducting electrolytes are superior to oxygen-ion-conducting
electrolytes for lower operating temperatures as a result of the
lower activation energy associated with the proton diffusion.
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Energy Fuels 2020, 34, 15169−15194
 Table 4. Performance of SOFCs Based on O2−- or H+-Conducting Electrolytes with Different Cathodes
PPDs at 600 °C PPDs at 500 °C ASRs in air at 600 °C for ASRs in wet air at 600 °C for
cathode (mW cm−2) (mW cm−2) O2−-SOFCs (Ω cm2) PCFCs (Ω cm2) cell configuration reference
Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) 1010 402 0.071 BSCF|Sm0.15Ce0.85O2−δ|Ni + Sm0.15Ce0.85O2−δ 65
BSCF 356 183 0.189 at 700 °C (dry air) BSCF|BZCY721|Ni + BaZr0.2Ce0.7Y0.1O3−δ (BZCY721) 145
Energy & Fuels

BSCF 276 184 BSCF|BZCY442|Ni + BaZr0.4Ce0.4Y0.2O3−δ (BZCY442) 146

BSCF 508 202 BSCF|BZCY305515|Ni + BaZr0.3Ce0.55Y0.15O3−δ (BZCY305515) 147
BSCF 380 225 ∼0.5 BSCF|BCY|Ni + BaCe0.9Y0.1O3−δ (BCY) 148
BSCF−Ag 245 0.25 (dry air) BSCF−Ag|BZCY811|Ni + BaZr0.1Ce0.8Y0.1O3−δ (BZCY811) 149
BaCo0.4Fe0.4Zr0.1Y0.1O3−δ 970 ∼0.26 BCFZY|GDC|Ni + Gd0.1Ce0.9O2−δ (GDC) 150
(BCFZY)
BCFZY 405 ∼0.1 BCFZY|BZCYYb + NiO (1 wt %)|Ni + BaZr0.1Ce0.7Y0.1Yb0.1O3−δ 151
(BZCYYb)
PrBaCo2O5+δ (PBC) 620 285 0.4 PBC|SDC|Ni + Sm0.2Ce0.8O1.9 (SDC) 48
PBC 305 125 0.73 PBC|BZCY721|Ni + BZCY721 152
BaCo0.7Fe0.2Nb0.1O3−δ (BCFNb) 800 0.096 BCFNb|GDC|Ni + GDC 153
BCFNb 280 115 0.1 BCFNb|BZCY721|Ni + BZCY721 154
Ba0.9Co0.7Fe0.2Nb0.1O3−δ 1062 ∼400 0.046 B0.9CFNb|GDC|Ni + GDC 153
(B0.9CFNb)
SrSc0.175Nb0.025Co0.8O3−δ (SSNC) 910 0.04 SSNC|SDC|Ni + SDC 80
SSNC 260 145 0.26 SSNC|BZCY721|Ni + BZCY721 155
PrBa0.5Sr0.5Co1.5Fe0.5O5+δ 2160 710 0.056 PBSCF|GDC|Ni + GDC 156
(PBSCF)
PBSCF 880 400 PBSCF|BZCYYb4411|Ni + BaZr0.4Ce0.4Y0.1Yb0.1O3−δ 157

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(BZCYYb4411)
BaCo0.7(Ce0.8Y0.2)O3−δ (BCCY) 399 251 BCCY|BZCY442|Ni + BZCY442 159
BCCY 743 319 0.034 0.25 BCCY|BZCYYb|Ni + BZCYYb 159
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Ba0.6Sr0.4Co0.9Nb0.1O3−δ (BSCN) 1150 565 0.1 BSCN|SDC|Ni + SDC 86

BSCN 305 0.27 at 650 °C BSCN|BZCY721|Ni + BZCY721 160
Ba0.5Sr0.5Sc0.175Nb0.025Co0.8O3−δ 413 0.64 BSSNC|BZCY721|Ni + BZCY721 161
(BSSNC)
SrCo0.8Fe0.15Zr0.05O3−δ (SCFZ) 458 234 0.38 SCFZ|BZCYYb|Ni + BZCYYb 162
Sr2Sc0.1Nb0.1Co1.5Fe0.3O6−δ 732 405 0.35 SSNCF|BZCYYb|Ni + BZCYYb 163
(SSNCF)
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Energy & Fuels pubs.acs.org/EF
However, as listed in Table 4, up to now, O2−-SOFCs still
show much higher power output than PCFCs at a reduced
temperature (<650 °C).48,65,80,145−157 This is mainly due to
the fact that ideal cathodes specifically designed for PCFCs is
not available. For example, the Ni-BaZr0.4Ce0.4Y0.2O3-δ (Ni-
BZCY442) anode-supported single cell with a BSCF cathode
exhibited a PPD of 276 mW cm−2 at 600 °C, which is much
lower than that of the Ni−SDC anode-supported single cell
with a BSCF cathode (1010 mW cm−2 at 600 °C) at the same
conditions.65,146 We further modified BSCF via infiltrating Ag
nanoparticles to improve the ORR activity of BSCF; the
infiltrated Ag nanoparticles improved both the surface
adsorption of O2 and the charge transfer process, thus leading
to an improved ORR activity. However, the performance of
SOFC with a BSCF−Ag cathode is still not satisfied.149
Figure 9 shows a comparison of the ORR process over the
different types of cathodes of PCFCs and O2−-SOFCs. The
Figure 9. Schematic diagrams of the ORR process for (a) O2−-SOFC
and (b) PCFC with a mixed oxygen-ion- and electron-conducting
electrode.159
main difference is that water is generated at the cathode of the
PCFC, while it is produced at the anode of the O2−-SOFC. As
shown in Figure 9a, if a MIEC is used as the cathode of O2−-
SOFCs, the whole electrode surface may take part in the
electrode reaction. Instead, if the same MIEC is applied as the
cathode of PCFCs, the water is only formed at the electrolyte−
air−electrode TPB. The electrode surface mainly acts as the
active sites for the reduction of oxygen to oxygen ions that can
then diffuse through the surface or the electrode bulk to the
TPB to meet with protons for the formation of water (Figure
9b). It suggests that the quick removal of water from TPB is of
significant importance for ensuring the continuous electrode
reaction, thus leading to high electrode performance. From the
introduction of proton conductivity into the electrode with the
development of an oxygen ion−proton−electron triple
conductor, both the oxygen reduction with the formation of
oxygen ions and the water formation can occur over the whole
electrode surface; an improvement in electrode performance is
then expected. On the basis of multiscale and physical models
for PCFCs with oxygen ion−proton−electron mixed conduct-
ing properties, we demonstrated that the electrode perform-
ance could be effectively improved through introducing proton
conductivity into the electrode.158 It thus suggests that the
development of a mixed oxygen ion, proton, and electronic
conductor is key to achieve high ORR activity at a reduced
temperature for PCFCs. In addition, water in the cathode
should be well-managed to make sure that it will not cause
inhibition for the electrode reaction.
During the early stage, we applied some mixed conducting
perovskite materials that showed promising cathodic perform-
ance in O2−-SOFCs at a reduced temperature as cathodes of
PCFCs, such as BSCF,148 PBC,152 BCFN,154 SSNC,155
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Review
BSCN,160 Ba0.5Sr0.5Sc0.175Nb0.025Co0.8O3−δ (BSSNC),161 and
SrCo0.8Fe0.15Zr0.05O3−δ (SCFZ).162 As mentioned above,
introducing proton conductivity into the electrode could
improve the cathode performance of PCFCs. For single-phase
cathode materials, proton conductivity could be in situ
generated as a result of the formation of H2O in the PCFC
cathode, which could react with oxygen vacancy (V•• O ) and
oxide ions (OxO) to generate hydroxyl ions (OH•O). For
example, the ohmic and polarization resistance of the
symmetrical cell (SSNC|BaZr0.2Ce0.7Y0.1O3−δ (BZCY721)|
SSNC) decreased after introducing 3% H2O into air,155 and
similar phenomenon also occurred in the symmetrical cell with
BSSNC and BCFN cathodes.154,161 However, the interfacial
reactions between these cathodes and proton-conducting
electrolytes always occurred as a result of the cation diffusion
between the electrode and electrolyte. For example, after
calcination of SSNC and BZCY721 at 900 °C, the Ba2+
diffusion promoted the formation of Ba2+-doped SSNC and
Ba2+-deficient BZCY721, and a similar diffusion phenomenon
between BaCe0.9Y0.1O3−δ (BCY) and BSCF was also confirmed
by Lin et al., leading to a blocking effect on the proton
transfer.148 Therefore, we investigated an appreciating
calcination temperature between the electrolyte and cathode
to ensure good contact and limit the interfacial reaction.
More recently, we used an oxygen ion−proton−electron
triple conductor as the electrode of PCFC; an improved
performance was indeed achieved, for example, on the basis of
an in situ formation of a 3D core−shell and triple-conducting
oxygen electrode for PCFCs after infiltrating Co(NO3)2 into
the BZCY442 scaffold and calcined at an appropriate
temperature (900 °C). Carefully controlled temperature
calcination leads to the formation of nanocomposites
composed of a triple conductor Ba(Zr0.4Ce0.4Y0.2)1−xCoxO3−δ,
an oxygen ion conductor (Ce, Zr, Y)O2, and an electronic
conductor Co3O4, thus leading to a sufficient triple-conducting
capability of the composite cathode. When the core−shell
composite was applied as a cathode for a single cell with Ni-
BZCY442 anode supported, a PPD of 330 mW cm−2 was
achieved at 650 °C.29
If we further introduce partial oxygen ion conductivity into
the electrolyte, i.e., the adoption of an O2−/H+ dual-ion
conducting electrolyte, an attractive PPD could be obtained by
applying a triple-conducting cathode. For example, we
developed a novel triple-conducting
Sr2Sc0.1Nb0.1Co1.5Fe0.3O6−δ (SSNCF) perovskite oxide as a
cathode material. As a result of the single-phase nature of the
SSNCF perovskite, the triple conduction capability is achieved
at the molecular level, thereby maximizing the conductivity of
the different charges and extending the active sites of the
electrode to the entire cathode surface. A Ni-
BaZr0.1Ce0.7Y0.1Yb0.1O3−δ (Ni-BZCYYb) anode-supported cell
exhibited a high PPD of 732 mW cm−2 operating on H2 fuel at
600 °C and had an operational stability of 400 h at 500 °C.
The dual-ion conducting capability of the BZCYYb electrolyte
was also experimentally confirmed by the water generation
phenomenon on both sides of the single cell.163
As we know, the proton conductivity and oxygen ion
conductivity largely depend upon the operating conditions. It
is difficult to precisely control the ratio of oxygen ion
conductivity to proton conductivity in a single-phase perov-
skite. For the mixture of MIEC and proton conductors
prepared by physical mixing, the apparent oxygen ion
conductivity and proton conductivity are usually low as a
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Energy Fuels 2020, 34, 15169−15194
Energy & Fuels
Figure 10. Schematic diagrams of the (a) preparation process of the Pd|BCFZY|Pd membrane, (b) H2 permeation test device, and (c) H2
permeation membrane of Pd|BCFZY|Pd. The enlarged part of the feed surface illustrates what happened in that part and the species involved.164
result of the poor diffusion pathway. Very recently, we further
introduced a proton conductor into a BaCoO3−δ-based
electrode to develop an oxygen ion−proton−electron triple-
conducting oxide, BaCo0.7(Ce0.8Y0.2)0.3O3−δ (BCCY), as a
high-performance PCFC cathode.159 A high-temperature
calcination process resulted in the formation of a self-
assembled nanocomposite electrode composited of a H+/e−-
conducting phase (BaCexYyCozO3−δ denoted as P-BCCY) and
two O2−/e−-conducting phases (BaCoxCeyYzO3−δ denoted as
M-BCCY and BaCoO3−δ phases). The P-BCCY phase
facilitates the proton diffusion; the M-BCCY phase promotes
the oxygen ion diffusion; and the BaCoO3−δ phase enhances
the electronic conduction of the electrode. The interplay
between these phases improved their thermomechanical
compatibility by alleviating the mismatch in TEC. When
tested as a cathode in anode-supported PCFCs, a PPD of 743
mW cm−2 was obtained at 650 °C and an operating stability of
812 h can be maintained at 550 °C. As listed in Table 4, the
cathode showed almost one of the best performances among
all of the reported electrodes for PCFCs up to now.
Considering that the proton conductivity is a critical
parameter of the PCFC cathode, it is difficult to directly
evaluate the proton conduction capability of cathode materials
via an experimental method. We innovatively used the
hydrogen permeation test to realize the direct evaluation of
the proton conduction capability of cathode materials and
provided a detailed calculation method of proton conductiv-
ity.163,164 In the hydrogen permeation test, a dense pellet of
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cathode is needed and a dense palladium film is also
introduced into both sides of the cathode pellet via sputtering
to prevent the structure damage to the membrane (Figure
10a). Panels b and c of Figure 10 display the schematic
diagrams of the H2 permeation test and H2 permeation process
through a Pd|BCFZY|Pd membrane. The enlarged part of Pd
on the feed surface indicates that the H2 molecule dissociates
to 2H through the solution-diffusion mechanism. Once these
H atoms reach the perovskite region, they will interact with
electrons and attach themselves to lattice oxygen according to
eq 1. The proton conductivity (σH+) can be obtained from H2
permeation flux (JH2) by eq 2. We successfully evaluated the
proton conduction capability of the conventional BSCF and
the state-of-the-art BCFZY, SSNCF, and BCCY cathodes,
suggesting the practicality of this method, which can provide
useful guidance for the development of triple-conducting
cathode materials163,164
H + OOx + h• ↔ OH•O (1)
4F 2L PH ,supp
σH+ = JH /ln 2
2 RT PH2,perm
(2)
where F is the Faraday constant (96 485.3329 C mol−1), R is
the universal gas constant (8.314 J mol−1 K−1), L is the
thickness, T is the operation temperature (K), PH2,supp is the
hydrogen partial pressure on the hydrogen supply side, and
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Energy & Fuels
Figure 11. Timeline for some typical ILT-SOFC cathode materials that we have developed over the past 15 years.
PH2,perm is the hydrogen partial pressure on the hydrogen
permeable side.
Considering that the SOFC cathode operates in ambient air,
which contains a certain level of CO2, the PCFC cathode
material should also possess good structural stability in CO2-
contained air to ensure the long-term ORR activity. Partial
substitution of the B-site ions of perovskites with high valent
transition metals can improve the phase structure stability and
reduce the basicity, therefore enhancing CO2 tolerance. We
introduced 5 mol % ZrO2 into the B site of SrCo0.8Fe0.2O3−δ to
enhance its structural stability and CO2 tolerance. Finally, the
Ni−BZCYYb anode-supported single cell with a SCFZ
cathode exhibited a high power output of 712 mW cm−2 at
700 °C in H2 fuel and an excellent operational stability of 300
h.162
For the synthesis of cathode materials, typically analytical
reagents were applied to avoid the introduction of impurity.
However, from the cost consideration, the use of low-grade
raw material may effectively reduce the material cost. Using
BSCF as an example, we deliberately introduced various
impurity elements into BSCF at different concentrations.165
Encouragingly, such impurities were found to have only a small
negative effect on the ORR activity, which may be correlated
with the high flexibility of the perovskite structure, with more
than 90% of elements in the periodic table being doped into
the perovskite lattice; therefore, the impurity is dissolved into
the oxide bulk, instead of staying at the grain boundary or
surface, and the negative effect is minimized. It suggests for
practical application that lower grade chemicals can be applied
in the synthesis.
5. CONCLUSION, CHALLENGES, AND PERSPECTIVES
To realize the decrease of the working temperature of SOFCs
to the intermediate-to-low temperature range (400−800 °C),
intensive efforts have been conducted from researchers
worldwide, while the development of a high-performance
cathode is the key. After 15 years of efforts, we have achieved
some promising progress in the development of cathode
materials for ILT-SOFCs. As shown in Figure 11, we list some
typical cathode materials that we developed. From the aspect
of ASR, according to the symmetric cell test, a low value of
only 0.16 Ω cm2 was reached at 500 °C in air.84 Introducing
oxygen ion conductivity into the cathode can effectively extend
the active sites from a conventional TPB region to the entire
electrode surface; thus, a substantial increase in the ORR
activity at a reduced temperature is expected. Cobalt-based
perovskite oxides are the most promising electrodes to achieve
high activity at a reduced temperature, because a high
concentration of oxygen vacancy that is the charge carrier for
oxygen ions could be easily created in these oxides. We have
pubs.acs.org/EF Review
conducted intensive research activities to develop cobalt-based
perovskites as the cathode of SOFC through a doping strategy.
Increasing the oxygen vacancy concentration and oxygen
mobility are two important strategies to enhance the ORR
activity of perovskite oxides at reduced temperatures, which
can be realized via doping the cation with a lower oxidation
state into the A or B site of perovskite, increasing the cell free
volume, reducing the cation−oxygen bond energy, and forming
a cubic lattice structure. The creation of appropriate cation
non-stoichiometry may also lead to an increased oxygen
vacancy concentration. Several A-site cation-deficient perov-
skites were then exploited, which showed promising activity for
the ORR at intermediate temperatures, superior to their cation
stoichiometric counterparts.
The apparent activity of cathode materials is directly
correlated with the number of active sites. Building a
hierarchical porous electrode and nanostructured electrode
could effectively increase the electrode surface area; thus, an
improved electrode performance is expected. However,
electrode sintering is a big concern. Using an exsolution
strategy, we successfully developed some silver nanoparticle-
modified perovskite electrodes, which showed high activity at
intermediate temperatures and favorable durability. A core−
shell-structured thin-film-modified 3D mesoporous electrode
was also developed, which can effectively avoid the sintering
issue of nanoparticles but also sustain the high surface area,
high activity, and favorable durability at an intermediate
temperature for the ORR activity. Through building a
nanocomposite, the dynamic exchange between two different
phases in the electrode could help to increase the electrode
activity and suppress the thermal expansion; as a result,
increased activity and durability was achieved.
In addition to O2−-SOFCs, during the past few years, great
efforts have also been made in developing cathode materials for
PCFCs. Several cobalt-based perovskite oxides that performed
well in O2−-SOFCs also showed favorable activity in PCFCs,
for instance, BSCF, PBC, BCFNb, BSCN, SSNC, and PBSCF
cathodes. From the introduction of proton conductivity into
the materials to form BCFZY, SSNCF, and BCCY cathodes,
further improvement in cathodic performance was observed. In
particular, if the electrolyte exhibits mixed proton and oxygen
ion conductivity, the cathodic performance of the oxygen ion−
proton−electron triple-conducting electrode was further
improved. For example, from the application of a self-
assembled triple-conducting nanocomposite of BCCY, a
breakthrough cell power output of 319 mW cm−2 at 500 °C
was achieved.
Although favorable activity was achieved for some materials
as developed, the use of these materials in practical cells is still
not reached. Currently, all of the tests were made on lab-scale
button cells; their performance in commercial size cells is to be
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Energy & Fuels
urgently confirmed. As a practical cathode for ILT-SOFCs, we
should take comprehensive consideration from multiple
aspects, including activity, durability, conductivity, and cost.
Each of these aspects is determined by many parameters. For
example, durability is closely related to structural stability,
chemical stability, thermomechanical stability, and morpho-
logical stability. During the past, the developed cathode
materials can meet one or two requirements, while very few of
them can meet three requirements simultaneously. Unfortu-
nately, all available materials cannot meet all requirements at
the same time. For example, BSCF shows very high activity for
the ORR at intermediate temperatures but suffers from high
TEC and high sensitivity to CO2 in an air atmosphere.
Nanoparticle-modified electrodes prepared from the infiltra-
tion method show favorable activity at a reduced temperature
but may suffer from the durability problem because of the easy
aggregation/sintering of the nanoparticles. It seems a big
challenge to reach all of the requirements based on a single
strategy; instead, the combination of several strategies, such as
doping, nanostructuring, compositing, and electrode morphol-
ogy control, is more promising, which requires more attention
for future SOFC cathode research.
For SOFCs, there are different types of electrolytes based on
the various conducting species, such as oxygen ion, proton, and
mixed oxygen ion and proton. During the past, most
researchers simply transferred the cathode materials that
performed well in one type of electrolyte to the other type
of electrolyte. However, simple transferring does not
necessarily bring the most favorable results because of the
different reaction mechanisms. In future research, a specific
design of the electrode material for a particular type of
electrolyte should be emphasized. For example, for the PCFCs,
the impact of water on the electrode performance was largely
ignored, which requires particular consideration during the
development of alternative cathode materials. Because the
adsorption of water on the surface of the electrode will inhibit
the further reaction of H+ and O2−, a hydrophobic electrode
surface is preferred; however, the perovskite should have the
water dissolution capability, which is required for the creation
of proton conductivity. Thus, in the future study, the electrode
should be well-tailored to obtain the best balance between
these two effects. During the past, single-phase perovskite or
related oxides have been intensively exploited as a cathode of
SOFCs. However, it is a big challenge to achieve all of the
requirements in a single phase. Instead, two- or multiple-phase
composites are more promising, requiring more attention. In
particular, nanocomposites with an intimate interaction
between the different phases in the composite can bring
some unusual effects on the physicochemical properties;
consequently, the electrode performance is highly attractive.
This type of composite needs to be further explored in detail.
■
AUTHOR INFORMATION
Corresponding Author
Zongping Shao − State Key Laboratory of Materials-Oriented
Chemical Engineering, College of Chemical Engineering,
Nanjing Tech University, Nanjing, Jiangsu 211816, People’s
Republic of China; WA School of Mines: Minerals, Energy and
Chemical Engineering, Curtin University, Perth, Western
Australia 6102, Australia; orcid.org/0000-0002-4538-
4218; Email: shaozp@njtech.edu.cn
pubs.acs.org/EF Review
Authors
Guangming Yang − State Key Laboratory of Materials-Oriented
Chemical Engineering, College of Chemical Engineering,
Nanjing Tech University, Nanjing, Jiangsu 211816, People’s
Republic of China; orcid.org/0000-0003-3792-5018
Chao Su − WA School of Mines: Minerals, Energy and Chemical
Engineering, Curtin University, Perth, Western Australia 6102,
Australia; School of Energy and Power Engineering, Jiangsu
University of Science and Technology, Zhenjiang, Jiangsu
212003, People’s Republic of China
Huangang Shi − WA School of Mines: Minerals, Energy and
Chemical Engineering, Curtin University, Perth, Western
Australia 6102, Australia; School of Environmental
Engineering, Nanjing Institute of Technology, Nanjing, Jiangsu
211167, People’s Republic of China
Yinlong Zhu − Department of Chemical Engineering, Monash
University, Clayton, Victoria 3800, Australia; orcid.org/
0000-0002-9207-2452
Yufei Song − State Key Laboratory of Materials-Oriented
Chemical Engineering, College of Chemical Engineering,
Nanjing Tech University, Nanjing, Jiangsu 211816, People’s
Republic of China
Wei Zhou − State Key Laboratory of Materials-Oriented
Chemical Engineering, College of Chemical Engineering,
Nanjing Tech University, Nanjing, Jiangsu 211816, People’s
Republic of China; orcid.org/0000-0003-0322-095X
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.energyfuels.0c01887
Author Contributions
†
Guangming Yang and Chao Su contributed equally to this
work.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The research was partially supported by Australian Research
Council (ARC) Discovery Project Grants DP150104365 and
DP160104835. Dr. Chao Su acknowledges ARC Discovery
Early Career Researcher Award DE180100773.
■ REFERENCES
(1) Wang, W.; Su, C.; Wu, Y.; Ran, R.; Shao, Z. Progress in solid
oxide fuel cells with nickel-based anodes operating on methane and
related fuels. Chem. Rev. 2013, 113 (10), 8104−8151.
(2) Wang, W.; Qu, J.; Julião, P. S. B.; Shao, Z. Recent advances in
the development of anode materials for solid oxide fuel cells utilizing
liquid oxygenated hydrocarbon fuels: A mini review. Energy Technol.
2019, 7 (1), 33−44.
(3) Wang, W.; Su, C.; Ran, R.; Zhao, B.; Shao, Z.; Tade, M. O.; Liu,
S. Nickel-based anode with water storage capability to mitigate carbon
deposition for direct ethanol solid oxide fuel cells. ChemSusChem
2014, 7 (6), 1719−1728.
(4) Song, Y.; Li, H.; Xu, M.; Yang, G.; Wang, W.; Ran, R.; Zhou, W.;
Shao, Z. Infiltrated NiCo alloy nanoparticles decorated perovskite
oxide: A highly active, stable and anti-sintering anode for direct-
ammonia solid oxide fuel cells. Small 2020, 16, 2001859.
(5) Su, C.; Wu, Y.; Wang, W.; Zheng, Y.; Ran, R.; Shao, Z.
Assessment of nickel cermets and La0.8Sr0.2Sc0.2Mn0.8O3 as solid-oxide
fuel cell anodes operating on carbon monoxide fuel. J. Power Sources
2010, 195 (5), 1333−1343.
(6) Wu, Y.; Su, C.; Zhang, C.; Ran, R.; Shao, Z. A new carbon fuel
cell with high power output by integrating with in situ catalytic reverse
Boudouard reaction. Electrochem. Commun. 2009, 11 (6), 1265−1268.
15189 https://dx.doi.org/10.1021/acs.energyfuels.0c01887
Energy Fuels 2020, 34, 15169−15194
Energy & Fuels pubs.acs.org/EF
(7) Azizi, M. A.; Brouwer, J. Progress in solid oxide fuel cell-gas
turbine hybrid power systems: System design and analysis, transient
operation, controls and optimization. Appl. Energy 2018, 215, 237−
289.
(8) Minh, N. Q. Ceramic fuel cells. J. Am. Ceram. Soc. 1993, 76 (3),
563−588.
(9) Jacobson, A. J. Materials for solid oxide fuel cells. Chem. Mater.
2010, 22 (3), 660−674.
(10) Jiang, S. P. Development of lanthanum strontium Manganite
perovskite cathode materials of solid oxide fuel cells: A review. J.
Mater. Sci. 2008, 43 (21), 6799−6833.
(11) Wachsman, E. D.; Lee, K. T. Lowering the temperature of solid
oxide fuel cells. Science 2011, 334 (6058), 935−939.
(12) Brett, D. J. L.; Atkinson, A.; Brandon, N. P.; Skinner, S. J.
Intermediate temperature solid oxide fuel cells. Chem. Soc. Rev. 2008,
37 (8), 1568−1578.
(13) Kilner, J. A.; Burriel, M. Materials for intermediate-temperature
solid-oxide fuel cells. Annu. Rev. Mater. Res. 2014, 44 (1), 365−393.
(14) Song, J. H.; Park, S. I.; Lee, J. H.; Kim, H. S. Fabrication
characteristics of an anode-supported thin-film electrolyte fabricated
by the tape casting method for IT-SOFC. J. Mater. Process. Technol.
2008, 198 (1−3), 414−418.
(15) Ding, J.; Liu, J. A novel design and performance of cone-shaped
tubular anode-supported segmented-in-series solid oxide fuel cell
stack. J. Power Sources 2009, 193 (2), 769−773.
(16) Shi, H.; Su, C.; Yang, G.; Ran, R.; Hao, Y.; Tade, M. O.; Shao,
Z. Fabrication and operation of flow-through tubular SOFCs for
electric power and synthesis gas cogeneration from methane. AIChE J.
2014, 60 (3), 1036−1044.
(17) Beckel, D.; Bieberle-Hütter, A.; Harvey, A.; Infortuna, A.;
Muecke, U. P.; Prestat, M.; Rupp, J. L. M.; Gauckler, L. J. Thin films
for micro solid oxide fuel cells. J. Power Sources 2007, 173 (1), 325−
345.
(18) Chen, D.; Yang, G.; Shao, Z.; Ciucci, F. Nanoscaled Sm-doped
CeO2 buffer layers for intermediate-temperature solid oxide fuel cells.
Electrochem. Commun. 2013, 35, 131−134.
(19) Fabbri, E.; Bi, L.; Pergolesi, D.; Traversa, E. Towards the next
generation of solid oxide fuel cells operating below 600 °C with
chemically stable proton-conducting electrolytes. Adv. Mater. 2012,
24 (2), 195−208.
(20) Steele, B. C. H.; Heinzel, A. Materials for fuel-cell technologies.
Nature 2001, 414 (6861), 345−352.
(21) Efimov, K.; Xu, Q.; Feldhoff, A. Transmission electron
microscopy study of Ba0.5Sr0.5Co0.8Fe0.2O3−δ perovskite decomposi-
tion at intermediate temperatures. Chem. Mater. 2010, 22 (21),
5866−5875.
(22) Yang, Z.; Guo, M.; Wang, N.; Ma, C.; Wang, J.; Han, M. A
short review of cathode poisoning and corrosion in solid oxide fuel
cell. Int. J. Hydrogen Energy 2017, 42 (39), 24948−24959.
(23) Jiang, S. P. Development of lanthanum strontium cobalt ferrite
perovskite electrodes of solid oxide fuel cells − A review. Int. J.
Hydrogen Energy 2019, 44 (14), 7448−7493.
(24) Giannici, F.; Chiara, A.; Canu, G.; Longo, A.; Martorana, A.
Interface solid-state reactions in La0.8Sr0.2MnO3/Ce0.8Sm0.2O2 and
La0.8Sr0.2MnO3/BaCe0.9Y0.1O3 disclosed by X-ray microspectroscopy.
ACS Appl. Energy Mater. 2019, 2 (5), 3204−3210.
(25) Nakajo, A.; Wuillemin, Z.; Van herle, J.; Favrat, D. Simulation
of thermal stresses in anode-supported solid oxide fuel cell stacks. Part
I: Probability of failure of the cells. J. Power Sources 2009, 193 (1),
203−215.
(26) Gao, Z.; Mogni, L. V.; Miller, E. C.; Railsback, J. G.; Barnett, S.
A. A perspective on low-temperature solid oxide fuel cells. Energy
Environ. Sci. 2016, 9 (5), 1602−1644.
(27) Sun, C.; Hui, R.; Roller, J. Cathode materials for solid oxide fuel
cells: A review. J. Solid State Electrochem. 2010, 14 (7), 1125−1144.
(28) Vohs, J. M.; Gorte, R. J. High-performance SOFC cathodes
prepared by infiltration. Adv. Mater. 2009, 21 (9), 943−956.
(29) Zhang, Z.; Wang, J.; Chen, Y.; Tan, S.; Shao, Z.; Chen, D. In
situ formation of a 3D core-shell and triple-conducting oxygen
15190
Review
reduction reaction electrode for proton-conducting SOFCs. J. Power
Sources 2018, 385, 76−83.
(30) Fleig, J. Solid oxide fuel cell cathodes: Polarization mechanisms
and modeling of the electrochemical performance. Annu. Rev. Mater.
Res. 2003, 33 (1), 361−382.
(31) Horita, T.; Yamaji, K.; Ishikawa, M.; Sakai, N.; Yokokawa, H.
Active sites imaging for oxygen reduction at the La0.9Sr0.1MnO3−x/
yttria-stabilized zirconia interface by secondary-ion mass spectrome-
try. J. Electrochem. Soc. 1998, 145 (9), 3196−3202.
(32) Tsai, T.; Barnett, S. A. Effect of LSM−YSZ cathode on thin-
electrolyte solid oxide fuel cell performance. Solid State Ionics 1997,
93 (3−4), 207−217.
(33) Tanner, C. W.; Fung, K. Z.; Virkar, A. V. The effect of porous
composite electrode structure on solid oxide fuel cell performance. J.
Electrochem. Soc. 1997, 144 (1), 21−30.
(34) Sunarso, J.; Baumann, S.; Serra, J. M.; Meulenberg, W. A.; Liu,
S.; Lin, Y. S.; Diniz da Costa, J. C. Mixed ionic-electronic conducting
(MIEC) ceramic-based membranes for oxygen separation. J. Membr.
Sci. 2008, 320 (1−2), 13−41.
(35) Peña, M. A.; Fierro, J. L. G. Chemical structures and
performances of perovskite oxides. Chem. Rev. 2001, 101 (7),
1981−2018.
(36) Wang, L.; Merkle, R.; Mastrikov, Y. A.; Kotomin, E. A.; Maier,
J. Oxygen exchange kinetics on solid oxide fuel cell cathode
materialsgeneral trends and their mechanistic interpretation. J.
Mater. Res. 2012, 27 (15), 2000−2008.
(37) Gellings, P. J.; Bouwmeester, H. J. M. Ion and mixed
conducting oxides as catalysts. Catal. Today 1992, 12 (1), 1−101.
(38) Chen, Y.; Zhou, W.; Ding, D.; Liu, M.; Ciucci, F.; Tade, M.;
Shao, Z. Advances in cathode materials for solid oxide fuel cells:
Complex oxides without alkaline earth metal elements. Adv. Energy
Mater. 2015, 5 (18), 1500537.
(39) Zener, C. Interaction between the d-shells in the transition
metals. II. Ferromagnetic compounds of manganese with perovskite
structure. Phys. Rev. 1951, 82 (3), 403−405.
(40) Boukamp, B. A. The amazing perovskite anode. Nat. Mater.
2003, 2 (5), 294−296.
(41) Tao, S.; Irvine, J. T. S. A redox-stable efficient anode for solid-
oxide fuel cells. Nat. Mater. 2003, 2 (5), 320−323.
(42) Huang, Y.-H.; Dass, R. I.; Xing, Z.-L.; Goodenough, J. B.
Double perovskites as anode materials for solid-oxide fuel cells. Science
2006, 312 (5771), 254−257.
(43) Sengodan, S.; Choi, S.; Jun, A.; Shin, T. H.; Ju, Y. W.; Jeong, H.
Y.; Shin, J.; Irvine, J. T. S.; Kim, G. Layered oxygen-deficient double
perovskite as an efficient and stable anode for direct hydrocarbon
solid oxide fuel cells. Nat. Mater. 2015, 14 (2), 205−209.
(44) Dong, F.; Chen, D.; Chen, Y.; Zhao, Q.; Shao, Z. La-doped
BaFeO3−δ perovskite as a cobalt-free oxygen reduction electrode for
solid oxide fuel cells with oxygen-ion conducting electrolyte. J. Mater.
Chem. 2012, 22 (30), 15071−15079.
(45) Zhang, K.; Sunarso, J.; Shao, Z.; Zhou, W.; Sun, C.; Wang, S.;
Liu, S. Research progress and materials selection guidelines on mixed
conducting perovskite-type ceramic membranes for oxygen produc-
tion. RSC Adv. 2011, 1 (9), 1661−1676.
(46) Goldschmidt, V. M. Die gesetze der krystallochemie (The laws
of crystal chemistry). Naturwissenschaften 1926, 14, 477−485.
(47) Li, Z.; Yang, M.; Park, J. S.; Wei, S. H.; Berry, J. J.; Zhu, K.
Stabilizing perovskite structures by tuning tolerance factor: Formation
of formamidinium and cesium lead iodide solid-state alloys. Chem.
Mater. 2016, 28 (1), 284−292.
(48) Chen, D.; Ran, R.; Zhang, K.; Wang, J.; Shao, Z. Intermediate-
temperature electrochemical performance of a polycrystalline
PrBaCo2O5+δ cathode on samarium-doped ceria electrolyte. J. Power
Sources 2009, 188 (1), 96−105.
(49) Kim, G.; Wang, S.; Jacobson, A. J.; Yuan, Z.; Donner, W.;
Chen, C. L.; Reimus, L.; Brodersen, P.; Mims, C. A. Oxygen exchange
kinetics of epitaxial PrBaCo2O5+δ thin films. Appl. Phys. Lett. 2006, 88
(2), 024103.
https://dx.doi.org/10.1021/acs.energyfuels.0c01887
Energy Fuels 2020, 34, 15169−15194
Energy & Fuels
(50) Fan, L.; Zhu, B.; Su, P. C.; He, C. Nanomaterials and
technologies for low temperature solid oxide fuel cells: Recent
advances, challenges and opportunities. Nano Energy 2018, 45, 148−
176.
(51) Ding, D.; Li, X.; Lai, S. Y.; Gerdes, K.; Liu, M. Enhancing
SOFC cathode performance by surface modification through
infiltration. Energy Environ. Sci. 2014, 7 (2), 552−575.
(52) Yang, G.; Su, C.; Chen, Y.; Tadé, M. O.; Shao, Z. Nano
La0.6Ca0.4Fe0.8Ni0.2O3−δ decorated porous doped ceria as a novel
cobalt-free electrode for “symmetrical” solid oxide fuel cells. J. Mater.
Chem. A 2014, 2 (45), 19526−19535.
(53) Almar, L.; Morata, A.; Torrell, M.; Gong, M.; Liu, M.; Andreu,
T.; Tarancón , A. Synthesis and characterization of robust,
mesoporous electrodes for solid oxide fuel cells. J. Mater. Chem. A
2016, 4 (20), 7650−7657.
(54) Chen, D.; Yang, G.; Ciucci, F.; Tadé, M. O.; Shao, Z. 3D core-
shell architecture from infiltration and beneficial reactive sintering as
highly efficient and thermally stable oxygen reduction electrode. J.
Mater. Chem. A 2014, 2 (5), 1284−1293.
(55) Mitterdorfer, A.; Gauckler, L. J. La2Zr2O7 formation and oxygen
reduction kinetics of the La0.85Sr0.15MnyO3, O2(g)|YSZ system. Solid
State Ionics 1998, 111 (3−4), 185−218.
(56) Su, C.; Xu, X.; Chen, Y.; Liu, Y.; Tadé, M. O.; Shao, Z. A top-
down strategy for the synthesis of mesoporous Ba0.5Sr0.5Co0.8Fe0.2O3−δ
as a cathode precursor for buffer layer-free deposition on stabilized
zirconia electrolyte with a superior electrochemical performance. J.
Power Sources 2015, 274, 1024−1033.
(57) Duan, Z.; Yang, M.; Yan, A.; Hou, Z.; Dong, Y.; Chong, Y.;
Cheng, M.; Yang, W. Ba0.5Sr0.5Co0.8Fe0.2O3−δ as a cathode for IT-
SOFCs with a GDC interlayer. J. Power Sources 2006, 160 (1), 57−64.
(58) Shimura, K.; Nishino, H.; Kakinuma, K.; Brito, M. E.; Uchida,
H. Effect of samaria-doped ceria (SDC) interlayer on the performance
of La0.6Sr0.4Co0.2Fe0.8O3−δ/SDC composite oxygen electrode for
reversible solid oxide fuel cells. Electrochim. Acta 2017, 225, 114−120.
(59) Zhou, W.; Liang, F.; Shao, Z.; Zhu, Z. Hierarchical CO2-
protective shell for highly efficient oxygen reduction reaction. Sci. Rep.
2012, 2 (1), 327.
(60) Bucher, E.; Egger, A.; Caraman, G. B.; Sitte, W. Stability of the
SOFC cathode material (Ba,Sr)(Co,Fe)O3−δ in CO2-containing
atmospheres. J. Electrochem. Soc. 2008, 155 (11), B1218−B1224.
(61) Yan, A.; Maragou, V.; Arico, A.; Cheng, M.; Tsiakaras, P.
Investigation of a Ba0.5Sr0.5Co0.8Fe0.2O3−δ based cathode SOFC: II.
The effect of CO2 on the chemical stability. Appl. Catal. B Environ.
2007, 76 (3−4), 320−327.
(62) Wang, F.; Chen, D.; Shao, Z. Sm0.5Sr0.5CoO3−δ-infiltrated
cathodes for solid oxide fuel cells with improved oxygen reduction
activity and stability. J. Power Sources 2012, 216, 208−215.
(63) Shin, J. F.; Xu, W.; Zanella, M.; Dawson, K.; Savvin, S. N.;
Claridge, J. B.; Rosseinsky, M. J. Self-assembled dynamic perovskite
composite cathodes for intermediate temperature solid oxide fuel
cells. Nat. Energy 2017, 2 (3), 16214.
(64) Shao, Z.; Yang, W.; Cong, Y.; Dong, H.; Tong, J.; Xiong, G.
Investigation of the permeation behavior and stability of a
Ba0.5Sr0.5Co0.8Fe0.2O3−δ oxygen membrane. J. Membr. Sci. 2000, 172
(1−2), 177−188.
(65) Shao, Z.; Haile, S. M. A high-performance cathode for the next
generation of solid-oxide fuel cells. Nature 2004, 431 (7005), 170−
173.
(66) Wei, B.; Lü, Z.; Li, S.; Liu, Y.; Liu, K.; Su, W. Thermal and
electrical properties of new cathode material Ba0.5Sr0.5Co0.8Fe0.2O3−δ
for solid oxide fuel cells. Electrochem. Solid-State Lett. 2005, 8 (8),
A428−A431.
(67) Shao, Z.; Xiong, G.; Dong, H.; Tong, J.; Cong, Y.; Yang, W.
Effect of Fe content on properties of Ba0.5Sr0.5CoxFe1−xO3−δ mixed
conducting membranes. Chin. J. Catal. 2000, 21 (5), 500−504.
(68) Shao, Z.; Xiong, G.; Tong, J.; Dong, H.; Yang, W. Ba effect in
doped Sr(Co0.8Fe0.2)O3−δ on the phase structure and oxygen
permeation properties of the dense ceramic membranes. Sep. Purif.
Technol. 2001, 25 (1−3), 419−429.
pubs.acs.org/EF Review
(69) Zhou, W.; Ran, R.; Shao, Z. P.; Gu, H. X.; Jin, W. Q.; Xu, N. P.
Significant impact of nitric acid treatment on the cathode perform-
ance of Ba0.5Sr0.5Co0.8Fe0.2O3−δ perovskite oxide via combined EDTA-
citric complexing process. J. Power Sources 2007, 174 (1), 237−245.
(70) Zeng, P.; Chen, Z.; Zhou, W.; Gu, H.; Shao, Z.; Liu, S. Re-
evaluation of Ba0.5Sr0.5Co0.8Fe0.2O3−δ perovskite as oxygen semi-
permeable membrane. J. Membr. Sci. 2007, 291 (1−2), 148−156.
(71) Zhang, K.; Ge, L.; Ran, R.; Shao, Z.; Liu, S. Synthesis,
characterization and evaluation of cation-ordered LnBaCo2O5+δ as
materials of oxygen permeation membranes and cathodes of SOFCs.
Acta Mater. 2008, 56 (17), 4876−4889.
(72) Guo, Y.; Chen, D.; Shi, H.; Ran, R.; Shao, Z. Effect of Sm3+
content on the properties and electrochemical performance of
SmxSr1−xCoO3−3 (0.2 ≤ x ≤ 0.8) as an oxygen reduction electrodes
on doped ceria electrolytes. Electrochim. Acta 2011, 56 (7), 2870−
2876.
(73) Dong, F.; Chen, D.; Ran, R.; Park, H.; Kwak, C.; Shao, Z. A
comparative study of Sm0.5Sr0.5MO3−δ (M = Co and Mn) as oxygen
reduction electrodes for solid oxide fuel cells. Int. J. Hydrogen Energy
2012, 37 (5), 4377−4387.
(74) Liu, B.; Sunarso, J.; Zhang, Y.; Yang, G.; Zhou, W.; Shao, Z.
Highly oxygen non-stoichiometric BaSc0.25Co0.75O3−δ as a high-
performance cathode for intermediate-temperature solid oxide fuel
cells. ChemElectroChem 2018, 5 (5), 785−792.
(75) Qian, B.; Chen, Y.; Tade, M. O.; Shao, Z. BaCo0.6Fe0.3Sn0.1O3
perovskite as a new superior oxygen reduction electrode for low-to-
intermediate temperature solid oxide fuel cells. J. Mater. Chem. A
2014, 2 (36), 15078−15086.
(76) Zeng, P.; Ran, R.; Chen, Z.; Zhou, W.; Gu, H.; Shao, Z.; Liu, S.
Efficient stabilization of cubic perovskite SrCoO3−δ by B-site low
concentration scandium doping combined with sol−gel synthesis. J.
Alloys Compd. 2008, 455 (1−2), 465−470.
(77) Zhou, W.; Shao, Z.; Ran, R.; Cai, R. Novel SrSc0.2Co0.8O3−δ as a
cathode material for low temperature solid-oxide fuel cell. Electrochem.
Commun. 2008, 10 (10), 1647−1651.
(78) Zhou, W.; Shao, Z.; Ran, R.; Jin, W.; Xu, N. A novel efficient
oxide electrode for electrocatalytic oxygen reduction at 400−600 °C.
Chem. Commun. 2008, 44, 5791−5793.
(79) Zhou, W.; Jin, W.; Zhu, Z.; Shao, Z. Structural, electrical and
electrochemical characterizations of SrNb0.1Co0.9O3−3 as a cathode of
solid-oxide fuel cells operating below 600 °C. Int. J. Hydrogen Energy
2010, 35 (3), 1356−1366.
(80) Zhou, W.; Sunarso, J.; Zhao, M.; Liang, F.; Klande, T.;
Feldhoff, A. A highly active perovskite electrode for the oxygen
reduction reaction below 600 °C. Angew. Chem., Int. Ed. 2013, 52
(52), 14036−14040.
(81) Jiang, S.; Sunarso, J.; Zhou, W.; Shao, Z. The significant effect
of the phase composition on oxygen reduction reaction activity on a
layered oxide cathode. J. Mater. Chem. A 2013, 1 (36), 11026−11032.
(82) Zhu, Y.; Sunarso, J.; Zhou, W.; Jiang, S.; Shao, Z. High
performance SrNb0.1Co0.9−xFexO3−3 perovskite cathodes for low
temperature solid oxide fuel cells. J. Mater. Chem. A 2014, 2 (37),
15454−15462.
(83) Chen, Y.; Qian, B.; Shao, Z. Tin and iron co-doping strategy for
developing active and stable oxygen reduction catalysts from
SrCoO3−δ for operating below 800 °C. J. Power Sources 2015, 294,
339−346.
(84) Li, M.; Zhao, M.; Li, F.; Zhou, W.; Peterson, V. K.; Xu, X.;
Shao, Z.; Gentle, I.; Zhu, Z. A niobium and tantalum co-doped
perovskite cathode for solid oxide fuel cells operating below 500 °C.
Nat. Commun. 2017, 8 (1), 13990.
(85) Chen, Y.; Shen, J.; Zhou, W.; Yang, G.; Shao, Z. A single-/
double-perovskite composite with an overwhelming single-perovskite
phase for the oxygen reduction reaction at intermediate temperatures.
J. Mater. Chem. A 2017, 5 (47), 24842−24849.
(86) Huang, C.; Chen, D.; Lin, Y.; Ran, R.; Shao, Z. Evaluation of
Ba0.6Sr0.4Co0.9Nb0.1O3−δ mixed conductor as a cathode for inter-
mediate- temperature oxygen-ionic solid oxide fuel cells. J. Power
Sources 2010, 195 (16), 5176−5184.
15191 https://dx.doi.org/10.1021/acs.energyfuels.0c01887
Energy Fuels 2020, 34, 15169−15194
Energy & Fuels
(87) Zhang, J.; Li, X.; Zhang, Z.; Xu, X.; Chen, Y.; Song, Y.; Dai, J.;
Yang, G.; Ran, R.; Zhou, W.; Shao, Z. A new highly active and CO2-
stable perovskite-type cathode material for solid oxide fuel cells
developed from A- and B-site cation synergy. J. Power Sources 2020,
457, 227995.
(88) Zhou, Y.; An, B.; Guo, Y.; Ran, R.; Shao, Z. Development of
high-performance cathodes for IT-SOFCs through beneficial
interfacial reactions. Electrochem. Commun. 2009, 11 (11), 2216−
2219.
(89) Zhang, G.; Dong, X.; Liu, Z.; Zhou, W.; Shao, Z.; Jin, W.
Cobalt-site cerium doped SmxSr1−xCoO3−δ oxides as potential
cathode materials for solid oxide fuel cells. J. Power Sources 2010,
195 (11), 3386−3393.
(90) Shen, J.; Chen, Y.; Yang, G.; Zhou, W.; Tadé, M. O.; Shao, Z.
Impregnated LaFe0.67Co0.3Pd0.03O3 as a promising electrocatalyst for
“symmetrical” intermediate-temperature solid oxide fuel cells. J. Power
Sources 2016, 306, 92−99.
(91) Zhu, Y.; Zhou, W.; Ran, R.; Chen, Y.; Shao, Z.; Liu, M.
Promotion of oxygen reduction by exsolved silver nanoparticles on a
perovskite scaffold for low-temperature solid oxide fuel cells. Nano
Lett. 2016, 16 (1), 512−518.
(92) Dogdibegovic, E.; Wright, C. J.; Zhou, X. D. Stability and
activity of (Pr1−xNdx)2NiO4 as cathodes for solid oxide fuel cells: I.
Quantification of phase evolution in Pr2NiO4. J. Am. Ceram. Soc.
2016, 99 (8), 2737−2741.
(93) Wang, F.; Chen, D.; Shao, Z. Composition and microstructure
optimization and operation stability of barium deficient
Ba1−xCo0.7Fe0.2Nb0.1O3−δ perovskite oxide electrodes. Electrochim.
Acta 2013, 103, 23−31.
(94) Zhu, Y.; Lin, Y.; Shen, X.; Sunarso, J.; Zhou, W.; Jiang, S.; Su,
D.; Chen, F.; Shao, Z. Influence of crystal structure on the
electrochemical performance of A-site-deficient Sr1‑sNb0.1Co0.9O3−δ
perovskite cathodes. RSC Adv. 2014, 4 (77), 40865−40872.
(95) Zhu, Y.; Chen, Z.; Zhou, W.; Jiang, S.; Zou, J.; Shao, Z. An A-
site-deficient perovskite offers high activity and stability for low-
temperature solid-oxide fuel cells. ChemSusChem 2013, 6 (12), 2249−
2254.
(96) Kuai, X.; Yang, G.; Chen, Y.; Sun, H.; Dai, J.; Song, Y.; Ran, R.;
Wang, W.; Zhou, W.; Shao, Z. Boosting the activity of
BaCo0.4Fe0.4Zr0.1Y0.1O3−δ perovskite for oxygen reduction reactions
at low-to-intermediate temperatures through tuning B-site cation
deficiency. Adv. Energy Mater. 2019, 9 (38), 1902384.
(97) Dong, F.; Ni, M.; Chen, Y.; Chen, D.; Tade, M. O.; Shao, Z.
Structural and oxygen-transport studies of double perovskites
PrBa1−xCo2O5+δ (x = 0.00, 0.05, and 0.10) toward their application
as superior oxygen reduction electrodes. J. Mater. Chem. A 2014, 2
(48), 20520−20529.
(98) Striker, T.; Ruud, J.; Gao, Y.; Heward, W.; Steinbruchel, C. A-
site deficiency, phase purity and crystal structure in lanthanum
strontium ferrite powders. Solid State Ionics 2007, 178 (21−22),
1326−1336.
(99) Kostogloudis, G.; Ftikos, C. Properties of A-site-deficient
La0.6Sr0.4Co0.2Fe0.8O3−δ-based perovskite oxides. Solid State Ionics
1999, 126 (1−2), 143−151.
(100) Zhou, W.; Ran, R.; Shao, Z.; Jin, W.; Xu, N. Evaluation of A-
site cation-deficient (Ba0.5Sr0.5)1−xCo0.8Fe0.2O3−δ (x > 0) perovskite as
a solid-oxide fuel cell cathode. J. Power Sources 2008, 182 (1), 24−31.
(101) Zhou, W.; Ran, R.; Shao, Z.; Zhuang, W.; Jia, J.; Gu, H.; Jin,
W.; Xu, N. Barium- and strontium-enriched
(Ba0.5Sr0.5)1+xCo0.8Fe0.2O3−δ oxides as high-performance cathodes for
intermediate-temperature solid-oxide fuel cells. Acta Mater. 2008, 56
(12), 2687−2698.
(102) Ge, L.; Ran, R.; Zhang, K.; Liu, S.; Shao, Z. Oxygen selective
membranes based on B-site cation-deficient (Ba 0.5 Sr 0.5 )-
(Co0.8Fe0.2)yO3−δ perovskite with improved operational stability. J.
Membr. Sci. 2008, 318 (1−2), 182−190.
(103) Chen, Y.; Qian, B.; Yang, G.; Chen, D.; Shao, Z. Insight into
an unusual lanthanum effect on the oxygen reduction reaction activity
pubs.acs.org/EF Review
of Ruddlesden-Popper-type cation-nonstoichiometric La2−xNiO4+δ (x
= 0−0.1) oxides. J. Mater. Chem. A 2015, 3 (12), 6501−6508.
(104) Zhang, Z.; Zhu, Y.; Zhong, Y.; Zhou, W.; Shao, Z. Anion
doping: A new strategy for developing high-performance perovskite-
type cathode materials of solid oxide fuel cells. Adv. Energy Mater.
2017, 7 (17), 1700242.
(105) Zhang, Z.; Chen, D.; Wang, J.; Tan, T.; Yu, X.; Shao, Z.
Highly active and stable cobalt-free hafnium-doped SrFe0.9Hf0.1O3−δ
perovskite cathode for solid oxide fuel cells. ACS Appl. Energy Mater.
2018, 1 (5), 2134−2142.
(106) Yang, G.; Zhou, W.; Liu, M.; Shao, Z. Enhancing electrode
performance by exsolved nanoparticles: A superior cobalt-free
perovskite electrocatalyst for solid oxide fuel cells. ACS Appl. Mater.
Interfaces 2016, 8 (51), 35308−35314.
(107) Jiang, S.; Sunarso, J.; Zhou, W.; Shen, J.; Ran, R.; Shao, Z.
Cobalt-free SrNbxFe1−xO3−δ (x = 0.05, 0.1 and 0.2) perovskite
cathodes for intermediate temperature solid oxide fuel cells. J. Power
Sources 2015, 298, 209−216.
(108) Jiang, S.; Zhou, W.; Niu, Y.; Zhu, Z.; Shao, Z. Phase transition
of a cobalt-free perovskite as a high-performance cathode for
intermediate-temperature solid oxide fuel cells. ChemSusChem 2012,
5 (10), 2023−2031.
(109) Jiang, S.; Liang, F.; Zhou, W.; Shao, Z. Hierarchical porous
cobalt-free perovskite electrode for highly efficient oxygen reduction.
J. Mater. Chem. 2012, 22 (32), 16214−16218.
(110) Zhang, Y.; Gao, X.; Sunarso, J.; Liu, B.; Zhou, W.; Ni, M.;
Shao, Z. Significantly improving the durability of single-chamber solid
oxide fuel cells: A highly active CO2-resistant perovskite cathode. ACS
Appl. Energy Mater. 2018, 1 (3), 1337−1343.
(111) Gu, H.; Sunarso, J.; Yang, G.; Zhou, C.; Song, Y.; Zhang, Y.;
Wang, W.; Ran, R.; Zhou, W.; Shao, Z. Turning detrimental effect
into benefits: Enhanced oxygen reduction reaction activity of cobalt-
free perovskites at intermediate temperature via CO2-induced surface
activation. ACS Appl. Mater. Interfaces 2020, 12 (14), 16417−16425.
(112) Song, Y.; Chen, Y.; Xu, M.; Wang, W.; Zhang, Y.; Yang, G.;
Ran, R.; Zhou, W.; Shao, Z. A cobalt-free multi-phase nanocomposite
as near-ideal cathode of intermediate-temperature solid oxide fuel
cells developed by smart self-assembly. Adv. Mater. 2020, 32 (8),
1906979.
(113) Niu, Y.; Zhou, W.; Sunarso, J.; Ge, L.; Zhu, Z.; Shao, Z. High
performance cobalt-free perovskite cathode for intermediate temper-
ature solid oxide fuel cells. J. Mater. Chem. 2010, 20 (43), 9619−9622.
(114) Niu, Y.; Sunarso, J.; Liang, F.; Zhou, W.; Zhu, Z.; Shao, Z. A
comparative study of oxygen reduction reaction on Bi-and La-doped
SrFeO3−δ perovskite cathodes. J. Electrochem. Soc. 2011, 158 (2),
B132−B138.
(115) Niu, Y.; Sunarso, J.; Zhou, W.; Liang, F.; Ge, L.; Zhu, Z.;
Shao, Z. Evaluation and optimization of Bi1−xSrxFeO3−δ perovskites as
cathodes of solid oxide fuel cells. Int. J. Hydrogen Energy 2011, 36 (4),
3179−3186.
(116) Niu, Y.; Liang, F.; Zhou, W.; Sunarso, J.; Zhu, Z.; Shao, Z. A
three-dimensional highly interconnected composite oxygen reduction
reaction electrocatalyst prepared from a core-shell precursor.
ChemSusChem 2011, 4 (11), 1582−1586.
(117) Niu, Y.; Zhou, W.; Sunarso, J.; Liang, F.; Zhu, Z.; Shao, Z. A
single-step synthesized cobalt-free barium ferrites-based composite
cathode for intermediate temperature solid oxide fuel cells. Electro-
chem. Commun. 2011, 13 (12), 1340−1343.
(118) Dong, F.; Chen, Y.; Chen, D.; Shao, Z. Surprisingly high
activity for oxygen reduction reaction of selected oxides lacking long
oxygen-ion diffusion paths at intermediate temperatures: A case study
of cobalt-free BaFeO3−δ. ACS Appl. Mater. Interfaces 2014, 6 (14),
11180−11189.
(119) Chen, C.; Chen, D.; Gao, Y.; Shao, Z.; Ciucci, F.
Computational and experimental analysis of Ba0.95La0.05FeO3−δ as a
cathode material for solid oxide fuel cells. J. Mater. Chem. A 2014, 2
(34), 14154−14163.
(120) Dong, F.; Chen, Y.; Ran, R.; Chen, D.; Tadé, M. O.; Liu, S.;
Shao, Z. BaNb0.05Fe0.95O3−δ as a new oxygen reduction electrocatalyst
15192 https://dx.doi.org/10.1021/acs.energyfuels.0c01887
Energy Fuels 2020, 34, 15169−15194
Energy & Fuels pubs.acs.org/EF
for intermediate temperature solid oxide fuel cells. J. Mater. Chem. A
2013, 1 (34), 9781−9791.
(121) Dong, F.; Ni, M.; He, W.; Chen, Y.; Yang, G.; Chen, D.; Shao,
Z. An efficient electrocatalyst as cathode material for solid oxide fuel
cells: BaFe0.95Sn0.05O3−δ. J. Power Sources 2016, 326, 459−465.
(122) Yang, G.; Shen, J.; Chen, Y.; Tadé, M. O.; Shao, Z. Cobalt-free
Ba0.5Sr0.5Fe0.8Cu0.1Ti0.1O3−δ as a bi-functional electrode material for
solid oxide fuel cells. J. Power Sources 2015, 298, 184−192.
(123) Chen, D.; Wang, F.; Shi, H.; Ran, R.; Shao, Z. Systematic
evaluation of Co-free LnBaFe2O5+δ (Ln = Lanthanides or Y) oxides
towards the application as cathodes for intermediate-temperature
solid oxide fuel cells. Electrochim. Acta 2012, 78, 466−474.
(124) Yang, G.; Su, C.; Ran, R.; Tadé, M. O.; Shao, Z. Advanced
symmetric solid oxide fuel cell with an infiltrated K2NiF4-type
La2NiO4 electrode. Energy Fuels 2014, 28 (1), 356−362.
(125) Shen, J.; Yang, G.; Zhang, Z.; Zhou, W.; Wang, W.; Shao, Z.
Tuning layer-structured La0.6Sr1.4MnO4+δ into a promising electrode
for intermediate temperature symmetrical solid oxide fuel cells
through surface modification. J. Mater. Chem. A 2016, 4 (27),
10641−10649.
(126) Shen, J.; Yang, G.; Zhang, Z.; Tadé, M. O.; Zhou, W.; Shao, Z.
Improved performance of a symmetrical solid oxide fuel cell by
swapping the roles of doped ceria and La0.6Sr1.4MnO4+δ in the
electrode. J. Power Sources 2017, 342, 644−651.
(127) Chen, Y.; Chen, D.; Ran, R.; Park, H. J.; Kwak, C.; Ahn, S. J.;
Moon, K. S.; Shao, Z. A new way to increase performance of oxide
electrode for oxygen reduction using grain growth inhibitor.
Electrochem. Commun. 2012, 14 (1), 36−38.
(128) Neagu, D.; Tsekouras, G.; Miller, D. N.; Ménard, H.; Irvine, J.
T. S. In situ growth of nanoparticles through control of non-
stoichiometry. Nat. Chem. 2013, 5 (11), 916−923.
(129) Myung, J.; Neagu, D.; Miller, D. N.; Irvine, J. T. S. Switching
on electrocatalytic activity in solid oxide cells. Nature 2016, 537
(7621), 528−531.
(130) Zhu, T.; Troiani, H. E.; Mogni, L. V.; Han, M.; Barnett, S. A.
Ni-substituted Sr(Ti,Fe)O3 SOFC anodes: Achieving high perform-
ance via metal alloy nanoparticle exsolution. Joule 2018, 2 (3), 478−
496.
(131) Sun, Y. F.; Zhang, Y. Q.; Chen, J.; Li, J. H.; Zhu, Y. T.; Zeng,
Y. M.; Amirkhiz, B. S.; Li, J.; Hua, B.; Luo, J. L. New opportunity for
in situ exsolution of metallic nanoparticles on perovskite parent. Nano
Lett. 2016, 16 (8), 5303−5309.
(132) Kwon, O.; Sengodan, S.; Kim, K.; Kim, G.; Jeong, H. Y.; Shin,
J.; Ju, Y.-W.; Han, J. W.; Kim, G. Exsolution trends and co-segregation
aspects of self-grown catalyst nanoparticles in perovskites. Nat.
Commun. 2017, 8, 15967.
(133) Yu, S.; Yoon, D.; Lee, Y.; Yoon, H.; Han, H.; Kim, N.; Kim, C.
J.; Ihm, K.; Oh, T. S.; Son, J. Metal nanoparticle exsolution on a
perovskite stannate support with high electrical conductivity. Nano
Lett. 2020, 20 (5), 3538−3544.
(134) Hussain, A. M.; Huang, Y. L.; Pan, K. J.; Robinson, I. A.;
Wang, X.; Wachsman, E. D. A redox-robust ceramic anode supported
low-temperature solid oxide fuel cell. ACS Appl. Mater. Interfaces
2020, 12 (16), 18526−18532.
(135) Park, S. D.; Vohs, J. M.; Gorte, R. J. Direct oxidation of
hydrocarbons in a solid-oxide fuel cell. Nature 2000, 404 (6775),
265−267.
(136) Madsen, B. D.; Kobsiriphat, W.; Wang, Y.; Marks, L. D.;
Barnett, S. A. Nucleation of nanometer-scale electrocatalyst particles
in solid oxide fuel cell anodes. J. Power Sources 2007, 166 (1), 64−67.
(137) Adijanto, L.; Padmanabhan, V. B.; Küngas, R.; Gorte, R. J.;
Vohs, J. M. Transition metal-doped rare earth vanadates: A
regenerable catalytic material for SOFC anodes. J. Mater. Chem.
2012, 22 (22), 11396−11402.
(138) Zhou, W.; Shao, Z.; Liang, F.; Chen, Z. G.; Zhu, Z.; Jin, W.;
Xu, N. A new cathode for solid oxide fuel cells capable of in situ
electrochemical regeneration. J. Mater. Chem. 2011, 21 (39), 15343−
15351.
15193
Review
(139) Xu, X.; Wang, W.; Zhou, W.; Shao, Z. Recent advances in
novel nanostructuring methods of perovskite electrocatalysts for
energy-related applications. Small Methods 2018, 2 (7), 1800071.
(140) Zhu, Y.; Sunarso, J.; Zhou, W.; Shao, Z. Probing CO2 reaction
mechanisms and effects on the SrNb0.1Co0.9−xFexO3−δ cathodes for
solid oxide fuel cells. Appl. Catal. B Environ. 2015, 172, 52−57.
(141) Zhang, Y.; Yang, G.; Chen, G.; Ran, R.; Zhou, W.; Shao, Z.
Evaluation of the CO2 poisoning effect on a highly active cathode
SrSc0.175Nb0.025Co0.8O3−δ in the oxygen reduction reaction. ACS Appl.
Mater. Interfaces 2016, 8 (5), 3003−3011.
(142) Gu, B.; Sunarso, J.; Zhang, Y.; Song, Y.; Yang, G.; Zhou, W.;
Shao, Z. A high performance composite cathode with enhanced CO2
resistance for low and intermediate-temperature solid oxide fuel cells.
J. Power Sources 2018, 405, 124−131.
(143) Zhu, Y.; Zhou, W.; Chen, Y.; Shao, Z. An aurivillius oxide
based cathode with excellent CO2 tolerance for intermediate-
temperature solid oxide fuel cells. Angew. Chem., Int. Ed. 2016, 55
(31), 8988−8993.
(144) Li, M.; Zhou, W.; Zhu, Z. Recent development on perovskite-
type cathode materials based on SrCoO3−δ parent oxide for
intermediate-temperature solid oxide fuel cells. Asia-Pac. J. Chem.
Eng. 2016, 11 (3), 370−381.
(145) Wan, T.; Zhu, A.; Li, H.; Wang, C.; Guo, Y.; Shao, Z.;
Savadogo, O. Performance variability of Ba0.5Sr0.5Co0.8Fe0.2O3−δ
cathode on proton-conducting electrolyte SOFCs with Ag and Au
current collectors. Rare Metals 2018, 37 (8), 633−641.
(146) Liu, Y.; Guo, Y.; Ran, R.; Shao, Z. A novel approach for
substantially improving the sinterability of BaZr0.4Ce0.4Y0.2O3−δ
electrolyte for fuel cells by impregnating the green membrane with
zinc nitrate as a sintering aid. J. Membr. Sci. 2013, 437, 189−195.
(147) Bae, K.; Noh, H. S.; Jang, D. Y.; Hong, J.; Kim, H.; Yoon, K.
J.; Lee, J. H.; Kim, B. K.; Shim, J. H.; Son, J. W. High-performance
thin-film protonic ceramic fuel cells fabricated on anode supports with
a non-proton-conducting ceramic matrix. J. Mater. Chem. A 2016, 4
(17), 6395−6403.
(148) Lin, Y.; Ran, R.; Zheng, Y.; Shao, Z.; Jin, W.; Xu, N.; Ahn, J.
Evaluation of Ba0.5Sr0.5Co0.8Fe0.2O3−δ as a potential cathode for an
anode-supported proton-conducting solid-oxide fuel cell. J. Power
Sources 2008, 180 (1), 15−22.
(149) Lin, Y.; Ran, R.; Shao, Z. Silver-modified
Ba0.5Sr0.5Co0.8Fe0.2O3−δ as cathodes for a proton conducting solid-
oxide fuel cell. Int. J. Hydrogen Energy 2010, 35 (15), 8281−8288.
(150) Duan, C.; Hook, D.; Chen, Y.; Tong, J.; O’Hayre, R. Zr and Y
co-doped perovskite as a stable, high performance cathode for solid
oxide fuel cells operating below 500 °C. Energy Environ. Sci. 2017, 10
(1), 176−182.
(151) Duan, C.; Tong, J.; Shang, M.; Nikodemski, S.; Sanders, M.;
Ricote, S.; Almansoori, A.; O’Hayre, R. Readily processed protonic
ceramic fuel cells with high performance at low temperatures. Science
2015, 349 (6254), 1321−1326.
(152) Lin, Y.; Ran, R.; Zhang, C.; Cai, R.; Shao, Z. Performance of
PrBaCo2O5+δ as a proton-conducting solid-oxide fuel cell cathode. J.
Phys. Chem. A 2010, 114 (11), 3764−3772.
(153) Liu, Z.; Cheng, L. Z.; Han, M. F. A-site deficient
Ba1−xCo0.7Fe0.2Ni0.1O3−δ cathode for intermediate temperature
SOFC. J. Power Sources 2011, 196 (2), 868−871.
(154) Lin, Y.; Zhou, W.; Sunarso, J.; Ran, R.; Shao, Z.
Chacterization and evaluation of BaCo0.7Fe0.2Nb0.1O3−δ as a cathode
material for proton-conducting solid oxide fuel cells. Int. J. Hydrogen
Energy 2012, 37 (1), 484−497.
(155) Zhu, A.; Zhang, G.; Wan, T.; Shi, T.; Wang, H.; Wu, M.;
Wang, C.; Huang, S.; Guo, Y.; Yu, H.; Shao, Z. Evaluation of
SrSc0.175Nb0.025Co0.8O3−δ perovskite as a cathode for proton-
conducting solid oxide fuel cells: The possibility of in situ creating
protonic conductivity and electrochemical performance. Electrochim.
Acta 2018, 259, 559−565.
(156) Choi, S.; Yoo, S.; Kim, J.; Park, S.; Jun, A.; Sengodan, S.; Kim,
J.; Shin, J.; Jeong, H. Y.; Choi, Y.; Kim, G.; Liu, M. Highly efficient
https://dx.doi.org/10.1021/acs.energyfuels.0c01887
Energy Fuels 2020, 34, 15169−15194
Energy & Fuels pubs.acs.org/EF Review

and robust cathode materials for low-temperature solid oxide fuel

cells: PrBa0.5Sr0.5Co2−xFexO5+δ. Sci. Rep. 2013, 3 (1), 2426.
(157) Choi, S.; Kucharczyk, C. J.; Liang, Y.; Zhang, X.; Takeuchi, I.;
Ji, H. I.; Haile, S. M. Exceptional power density and stability at
intermediate temperatures in protonic ceramic fuel cells. Nat. Energy
2018, 3 (3), 202−210.
(158) Chen, D.; Zhang, Q.; Lu, L.; Periasamy, V.; Tade, M. O.;
Shao, Z. Multi scale and physics models for intermediate and low
temperatures H+-solid oxide fuel cells with H+/e−/O2‑ mixed
conducting properties: Part A, generalized percolation theory for
LSCF−SDC−BZCY 3-component cathodes. J. Power Sources 2016,
303, 305−316.
(159) Song, Y.; Chen, Y.; Wang, W.; Zhou, C.; Zhong, Y.; Yang, G.;
Zhou, W.; Liu, M.; Shao, Z. Self-assembled triple-conducting
nanocomposite as a superior protonic ceramic fuel cell cathode.
Joule 2019, 3 (11), 2842−2853.
(160) Lin, Y.; Ran, R.; Chen, D.; Shao, Z. A novel
Ba0.6Sr0.4Co0.9Nb0.1O3−δ cathode for protonic solid oxide fuel cells.
J. Power Sources 2010, 195 (15), 4700−4703.
(161) Zhang, Y.; Zhu, A.; Guo, Y.; Wang, C.; Ni, M.; Yu, H.; Zhang,
C.; Shao, Z. Electrochemical performance and effect of moisture on
Ba0.5Sr0.5Sc0.175Nb0.025Co0.8O3−δ oxide as a promising electrode for
proton-conducting solid oxide fuel cells. Appl. Energy 2019, 238, 344−
350.
(162) Lv, X.; Chen, H.; Zhou, W.; Li, S. D.; Shao, Z. CO2-tolerant
SrCo0.8Fe0.15Zr0.05O3−δ cathode for proton-conducting solid oxide fuel
cells. J. Mater. Chem. A 2020, 8, 11292−11301.
(163) Zhou, C.; Sunarso, J.; Song, Y.; Dai, J.; Zhang, J.; Gu, B.;
Zhou, W.; Shao, Z. New reduced-temperature ceramic fuel cells with
dual-ion conducting electrolyte and triple conducting double
perovskite cathode. J. Mater. Chem. A 2019, 7 (21), 13265−13274.
(164) Zhou, C.; Sunarso, J.; Dai, J.; Ran, R.; Song, Y.; He, F.; Zhou,
W.; Shao, Z. Realizing stable high hydrogen permeation flux through
BaCo0.4Fe0.4Zr0.1Y0.1O3−δ membrane using a thin Pd film protection
strategy. J. Membr. Sci. 2020, 596, 117709.
(165) Chen, Y.; Qian, B.; Li, S.; Jiao, Y.; Tade, M. O.; Shao, Z. The
influence of impurity ions on the permeation and oxygen reduction
properties of Ba0.5Sr0.5Co0.8Fe0.2O3−δ perovskite. J. Membr. Sci. 2014,
449, 86−96.

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Energy Fuels 2020, 34, 15169−15194