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Applications of all-inorganic perovskites for

energy storage
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Cite this: Mater. Adv., 2023,

4, 79
Ziyang Jia,ab Caipeng Cheng,a Xi Chen,a Lili Liu, a Rui Ding,*b Jilei Ye,a
Jing Wang, a Lijun Fu, a Yuhui Chenga and Yuping Wu *ac

In recent years, electrode materials of perovskite structure with controllable properties and structural
advantages have been widely studied in the field of electrochemical energy storage. In this review, the
research progress and application potential of a series of novel all-inorganic perovskite electrode
Received 30th June 2022, materials in the fields of batteries and supercapacitors are reviewed. Strategies to modulate perovskite
Accepted 9th October 2022 materials are discussed, including tailoring chemical composition and synthesis methods, controlling
DOI: 10.1039/d2ma00779g crystallinity and morphology, surface/interface defect engineering, and elemental doping. In addition,
the correlation between the microscopic properties of the materials and the macroscopic electrode
rsc.li/materials-advances performance is discussed. Furthermore, some directions are pointed out.

1. Introduction clean energy utilization/conversion/storage technologies. Solar

energy and wind energy will be significant pollution-free energy
As the need to address environmental pollution and the energy sources in the upcoming years, but due to their intermittent
crisis becomes more pressing, it is critical to identify new and uneven distribution, they should be combined with efficient
renewable energy materials/resources and to create superior energy storage technology for practical use. Electrochemical energy
storage systems (EES) have attracted significant attention and
a
School of Energy Science and Engineering, Nanjing Tech University, research interest as they can harvest sustainable and renewable
Nanjing 211816, China. E-mail: wuyp@fudan.edu.cn
b
energy for important applications such as electric vehicles, electro-
School of Chemistry, Xiangtan University, Xiangtan 4100XX, China.
E-mail: drm8112@xtu.edu.cn
nic communication devices, and backup power sources for home
c
School of Energy and Environment, Southeast University, Nanjing 210096, China use. They store and release energy by turning chemical energy into
electrical energy and reversing the process, which is associated
with electron and ion transport in electrode materials.1–3 The ideal
Dr Yuping Wu FRSC, is a Distin- EES device should feature high energy density, high power density,
guished Professor of Nanjing Tech long cycling life, environmental friendliness, etc. To achieve this
University and Southeast Univer- goal, a series of new rechargeable energy storage devices and new
sity. He got his PhD degree from electrode materials have emerged and been widely studied.4–6
the Institute of Chemistry, CAS, Every significant advancement in electrochemical energy
in 1997. In 2003, he was storage technology has been linked to the discovery and
promoted to full professor at enhancement of electrode materials. The discovery of LiCoO2
Fudan University, China. In and graphite has led to the marketization of Li-ion batteries;7
2015, he moved to Nanjing Tech the discovery of LiFePO4 marked the arrival of a new era of
University and shifted to Li-ion batteries;8 activated carbon (AC) has facilitated the
Southeast University in 2021. He application of higher power density devices;9 and the concept
has published over 390 papers in of pseudocapacitance was first introduced by the investiga-
Yuping Wu peer-reviewed journals with H- tion of the electrochemical energy storage capacity of RuO2
index 489, was awarded the materials.10 Consequently, finding and creatively designing
World’s Most Influential Minds (2015) by Thomson Reuters, and new electrode materials and tuning their physical, chemical,
Albert Nelson Marquis Lifetime Achievement Award (2019), and is and electrochemical properties are essential to achieve more
one of the Highly Cited Researchers in the world. He has made efficient electrochemical energy storage.
pioneering research work on ARLBs, gel-type and pore-free At the same time, the physical and chemical properties of
separators for lithium batteries with high safety, and hybrid electrode materials mainly affect the energy storage capacity of
capacitors. electrochemical energy storage devices. In practical applications,

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the key issues that need to be addressed for electrode materials are predicting the stability of oxide and fluoride perovskites. The
specific capacity, kinetic behavior affected by ion and electron higher the electronegativity of the X-site is, the stronger the
transfer, and structural stability in electrochemical reactions.11 bonds in the structure are, making the predictions of the hard-
The preparation and optimization of the materials usually start sphere model more successful.27 The ideal perovskite-type ABX3
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with the selection of elements, structures, and morphologies. In structure has cubic symmetry with the space group Pm3% m. In
terms of element selection, higher energy storage generally bene- addition to the primary perovskite structure ABX3, there are
fits from transition metal elements that can undergo multiple also some structures related to the A2BB 0 O6 double perovskite,
electron transfers.12 For structure, high stability usually is related in which the angles in the crystal structure share BO6 and B 0 O6
to certain structural features, such as dense rows of anionic units in an ordered rock salt-like arrangement, and the B–O–B
skeletons occupied by cations in tetrahedral and octahedral angles and B–O bond lengths in the structure determine the
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sites.13 With respect to the morphological composition, different structural properties. In contrast, anti-perovskites, whose
morphologies change their electron and ion transport ways/ cation and anion components are in opposite positions in the
lengths, interfaces between electrolytes and electrodes, etc.14 Elec- cell structure to normal calcite, have superconductivity.28,29
trode materials such as carbon and carbon derivatives, metal A range of different impressive material characteristics, includ-
oxides/hydroxides/halides, conducting polymers and MXene are ing ferroelectric, pyroelectric, magnetic, catalytic, photovoltaic,
now widely studied as key components in electrochemical energy electronic conduction, ionic conduction, mixed conduction,
storage devices. and superconducting properties, can be generated by tuning
Unlike the common electrode materials with crystal struc- the composition and structure of perovskite compounds.30–34
tures such as layered, spinel, olivine, and calcite,15–17 perovs- Therefore, perovskite materials have a variety of potential
kites have been recognized as a leader among inexpensive and applicability as a result of these features, which is encouraging
highly photochemically and electrochemically active materials their developments for energy storage devices.
for electrochemical energy applications with their robust According to the different types of constituent ions, perovs-
open frame, intersecting tetragonal cavity chains and three- kite materials are mainly divided into organic–inorganic hybrid
dimensional diffusion channels.18 In terms of the physical perovskites and all-inorganic perovskites. Organic–inorganic
properties of the material itself, perovskite materials have high hybrid perovskites have shown promising applications in solar
crystalline quality, facile and controllable preparation technol- cells with the highest certified efficiency, exceeding 25%, but
ogy as well as excellent electron transfer capability, thus exhi- that of all-inorganic perovskites exceeds only 18%.35 Never-
biting excellent electrical conductivity and ion mobility rate, theless, as one of the most important material families in
high charge storage capacity, and notable catalytic performance condensed matter physics and materials science, all-inorganic
in the application of electrochemical energy storage devices.19–22 perovskites have also attracted extensive research interest in
CaTiO3, which features a special structure and properties, the field of electrochemical energy storage in recent years.
was first discovered in 1839 and was named perovskite in honor Based on the improved structural and integrated properties of
of the mineralogist Lev Perovski. With the discovery of more perovskite materials, here recent advances in energy storage
perovskite materials, perovskite refers to all substances that devices based on all-inorganic perovskite materials (organic
have the general molecular formula of ABX3 and have a crystal groups are not included in the composition of perovskite
arrangement similar to CaTiO3.23,24 The structure of ABX3 compounds) are reviewed (Fig. 1), e.g., within the areas of
perovskites is usually based on a cubic array of corner- lithium/sodium/potassium ion batteries, Li–O2 batteries,
sharing BX6 octahedra, where the A-site cations are located zinc–air batteries, zinc ion batteries, and supercapacitors.
within the cubic octahedral cavities. Another way to represent Tailoring tools commonly used in the application of perovskites
the structure is a cubic dense array of AX3, where the B-site in a variety of energy storage devices are also discussed,
cations are located within the octahedral holes. The A-site is a including tuning chemical makeup and processing techniques,
cation or an organic group, usually coordinated to 12 X-site controlling crystallinity and morphology, and engineering sur-
anions, and the B-site cation coordinated to 6 X-site anions has face/interface defects, as well as the exploration of the correla-
a smaller radius. Most of the existing elements can be doped tion between microscopic material properties and macroscopic
into the perovskite structure, resulting in an increasing number device performance.
of compounds with perovskite structures.21
The tolerance factor (t) is an important parameter to mea-
sure the characteristics of perovskites at the structural 2. All-inorganic perovskites for
level.25,26 Currently, the most accepted one is the Goldschmidt lithium-based energy storage devices
tolerance factor t, t = (rA + rX)/O2(rB + rX), where rA, rB and rX are
the cation/anion radii of different sites in the perovskite Li-ion-based energy storage devices typically consist of cathodes
structure, respectively. The calculated value of the tolerance and anodes for ion storage and electrolytes for ion transport.
factor can be used to determine the inter-cavity match between Designing materials suitable for ion storage/transfer is critical
the A-site cation and the cavity in BX3. When the value of t is in for Li-ion batteries.36 Electrode materials are responsible for
the range of 0.8 to 1, a perovskite is usually formed. Likewise, reversibly storing certain forms of lithium, either as ions that
tolerance factors have been very successful in describing and fit into interstitial sites or by intercalation into the crystal

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of two groups of components, one organic and the other inorganic.

The organic components originate from the decomposition of
solvents in the electrolyte such as esters and ethers.41 Inorganic
substances are derived from the decomposition of salts and
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usually contain fluorides, oxides, and carbonates.42 Inorganic

substances with thermodynamic stability, such as LiF, Li2CO3,
and Li2O, are preferentially formed because they are compatible
with lithium metal or graphite anodes in lithium/lithium-ion
batteries.43 The chemical compatibility between the organic
material and the native electrolyte improves the wettability,
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and in turn, the composition of the SEI will affect the electron
transfer and ion transfer resistance in the cell. The anion in the
lithium salt has a significant effect on the impedance of the SEI.
Organic species are not considered to have a significant effect on
SEI impedance, but their reversibility affects the specific capacity
of the converted anode. In addition to the solute and solvent, the
nature of the electrode material also affects the distribution and
composition of the SEI.

Fig. 1 Modulation methods of all-inorganic perovskite electrode materials 2.1 ABX3 (X = Cl, Br, I) type perovskite halide
and the applied energy storage fields.
Due to the crystal structure characteristics and soft lattice
properties of perovskite materials, they have good defect toler-
ance properties that allow more ions to be doped into the lattice
structure, or undergo conversion reactions with lithium to form without causing destructive damage.44,45 Likewise, perovskite
a series of compounds.37 The electrode material should ensure halides have been used in the anode of lithium batteries
efficient ion and electron transport. During discharge, the because of their superiority in storing multiple lithium ions,
anode releases lithium ions through the electrolyte to the which can migrate to the inside of the perovskite crystal to form
cathode. This causes electrons to flow from the anode to LixABX3.46,47 Hence, they can be used as excellent materials for
the cathode through an external circuit, and the current powers storing Li+. Simultaneously, the doping of Li+ shifts the Fermi
external loads such as cell phones and laptops. During char- energy level of the metal halide perovskite CsPbX3 (CsPbBr3) to
ging, lithium ions move from the cathode to the anode through the conduction band, which suggests that Li+ can act as a
the electrolyte. The voltage is determined by the chemical sender-type impurity in CsPbBr3 materials (Fig. 2a and b).
potential difference between the anode and the cathode.38 CsPbX3 for Li-ion batteries has an unchanged crystal structure
Common anodes for lithium-ion batteries (LIBs) typically of the main body during cycling. This means that the perovskite
rely on graphite, which possesses a theoretical capacity of halide can accept Li+ with topological intercalation without
372 mA h g1. To obtain higher capacities, silicon and its structural distortion (Fig. 2c and d). Of note, perovskite
surface-treated derivatives are used to replace graphite electro- halides with different halogen species have widely diverse
des because silicon has ten times the capacity of graphite. energy storage capacities, e.g., the halogen species affects the
Nevertheless, silicon electrodes dramatically swell after a Li+ storage capacity of CsPbX3. Tufan et al. applied the all-
few cycles, leading to severe degradation of performance. inorganic CsPbBr3 perovskite as an active anode material for
In addition, graphene can also be used as an anode material, lithium-ion batteries, showing first charge/discharge capacities
but has a higher cost and high initial irreversible capacity. of B403 mA h g1 and 376 mA h g1, respectively. Voltage
Cathodes are typically made from lithium-containing materials plateaus at around 0.6–0.72 V for charging and at around 0.72–
such as LiCoO2, LiFePO4, and LiMn2O4, which typically provide 0.98 and 1.59 V for discharging were observed at the current
storage capacities of 150–170 mA h g1. Nickel- and density of 30 mA g1. These plateau voltages for charging–
manganese-based electrodes can be used to improve stability discharging are also consistent with the CV profile of the half-
and reduce costs. Li-ion cathode materials should meet the cells (Fig. 2e and f). The good rate performance suggested that
requirements of being compatible with other components in CsPbBr3 does not present much capacity decay at different
the cell, providing high voltages associated with the Fermi charging and discharging rates, indicating good structural
energy difference between the two electrodes, and avoiding stability of the CsPbBr3 perovskite as the anode for LIB applica-
crystal structure collapse when large amounts of lithium ions tions (Fig. 2g). Likewise, the electrode of CsPbBr3 retained 79%
enter and exit the cathode.39 Therefore, it is important to find of the original specific capacity of the button cell after 100 cycles
new cathode and anode electrode materials. at 60 mA g1, and the Li+ absorption/adsorption process did
In addition, the differences in the chemical activity of not significantly affect the crystal structure of the perovskite
electrode materials and electrolytes lead to the formation (Fig. 2e–h).48 Additionally, a lithium-ion half-cell assembled with a
of the SEI in liquid electrolyte batteries.40 The SEI is composed gel polymer electrolyte and a CsPbCl3 anode by Pulak et al. had a

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Fig. 2 TDOS of CsPbBr3 without (a) and with Li+ (b). Side views (c and d). CV curves (e), GCD curves (f), specific discharge capacity (g), and cycling
diagram (h) of CsPbBr3.48 Copyright r 2021 American Chemical Society.

specific capacity of 612.3 mA h g1 at a current density of of more than 99%. Nonetheless, the poor performance of Cs2Na-
50 mA g1, with a Coulomb efficiency of 88%.49 Similarly, BiCl6-based batteries, especially the poor cycling stability, limits
Nahid et al. prepared CsPbI3 as an anode material for lithium- their practical applications.56 Yang et al., for the first time,
ion batteries using a simple solution approach. The capacity of synthesized a rare-earth-based double perovskite Cs2NaErCl6:Li+
CsPbI3 decreased from 151 mA h g1 to 149.8 mA h g1 in the doped with a high concentration of lithium ions for LIBs by
first six charge/discharge cycles and subsequently increased to adjusting the elements doped at the B-site. Embedding of differ-
235 mA h g1 in the 100th cycle at 40 mA g1.50 The CsPbCl3 ent concentrations of Li+ did not affect the crystal structure of the
compound features a greater Li+ storage capacity. material (Fig. 3a and b). Benefiting from its excellent structural
Generally speaking, hydrophobic carbon nanotubes (CNTs) stability, Cs2NaErCl6 possessed relatively good cycling stability
can protect water-sensitive perovskite materials from the effects with a specific capacity of 120 mA h g1 at 300 mA g1 after
of moisture, thus improving the overall material stability under 500 cycles, with a coulombic efficiency close to 100% (Fig. 3c–f).
environmental conditions.51 More importantly, CNTs are regarded However, it can be seen that the decay of the specific capacity was
as an excellent conductive material and have been shown to severe in the first 20 cycles (Fig. 3c and e). The irreversible capacity
decrease the charge transfer resistance of perovskites through of the first few cycles was mainly caused by irreversible side
doping.52 Liu et al. synthesized CsPbBr3@CNTs composites for reactions and the formation of a solid electrolyte interface (SEI)
lithium-ion batteries using a simple co-precipitation method. The film. Furthermore, the too high doping concentration of Li+ also
electroactive materials with pseudocapacitance-controlled behavior changed the crystal structure, thereby limiting the Li+ migration
exhibited high reversible capacity (644.6 mA h g1 at 100 mA g1), and affecting the electrochemical performance. The addition of
long cycle stability (470.2 mA h g1 after 200 cycles at 100 mA g1), rare earth elements into the lead-free double perovskite opens up
and excellent rate capacity in LIBs.53 a way for the exploration of new promising anode materials for
Nevertheless, the toxicity of lead-based peroxides may have a lithium storage applications.57
negative effect on further expansion of applications in energy
storage. Materials with a double-perovskite structure, as a 2.2 ABF3 type perovskite fluoride
derivative based on the 113-type perovskite, have been widely Unlike the above-mentioned perovskite halides, perovskite
used in recent years as an effective means to develop lead-free fluorides (ABF3) showed high redox potential, high energy
perovskite materials based on the replacement of Pb with density and good cycling stability due to the highly ionic nature
monovalent and trivalent cations.54,55 The double-perovskite of the M–F bond and the presence of the strongest electro-
structure offers higher tunability and a wider range of elemental negative F element. In recent years, ABF3 (A = K, Na, NH4+, etc.;
incorporation possibilities than the ‘‘113’’ perovskite structure. B = Fe, Co, Ni, Mn, Zn, Cu, etc.) has drawn extensive research
Therefore, lead-free double-perovskite materials doped with interest as an electrode material in the area of electrochemical
different elements at the B-site show a promising application energy storage.58–60 The structural advantages of perovskites
prospect. Wu et al. showed the possibility of double-perovskite can address some of the disadvantages of traditional transition
materials in lithium storage by synthesizing all-inorganic double metal-based materials in energy storage. For example, the
perovskite Cs2NaBiCl6 as a new electrode material with a channel size of the FeF3 backbone hindered ion diffusion, thus
specific capacity of about 300 mA h g1 and a coulombic efficiency making long term storage of larger ions (e.g., sodium and

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Fig. 3 XRD patterns of Cs2NaErCl6 with various Li+ compositions (a). 3D structure patterns of Cs2NaErCl6 (b). Specific capacity (c) and EIS (d) of
Cs2NaErCl6 anodes with different Li+ concentrations. Cycling performance of Cs2NaErCl6:8Li+ anodes in the initial 150 cycles at different charging
current densities of 75, 150, and 300 mA g1 (e) and the following 150–500 cycles at a charging current density of 300 mA g1 (f).57 Copyright r 2022
American Chemical Society.

potassium) difficult or impossible.61 AFeF3 (A = K, Na, NH4+, of KFeF3 was far from ideal (Fig. 4g). NH4FeF3, as the cathode
etc.) allows the direct insertion of lithium in the structure material, was observed to have a significant decrease in crystal-
(after the first delocalization of the alkali metal and/or the linity during the initial decomposition of NH4+ ions (Fig. 4c).
NH4+ cation) and enables its circulation in larger alkali metal Fig. 4d displays galvanostatic charge and discharge cycles of
ions (e.g. sodium and potassium). For LIBs, perovskite LiFeF3 NH4FeF3 toward Li. The first step was the deinsertion of the
would be a suitable candidate, but it has not been synthesized ammonium cations from the crystalline framework represented
due to its thermodynamic instability, decomposing into LiF by a slopped plateau between 3.3 and 4.5 V versus Li/Li+. The
and FeF2.62,63 Different elemental substitution at the A-site theoretical capacity (Cth (NH4FeF3) = 206 mA h g1)) was
directly affects the tolerance factor of the perovskite structure, achieved at a current rate of C/2 with a relatively well-defined
and in fact, NaFeF3 was shown to distort to an orthogonal plateau around 3 V and a capacity retention of 94% after
symmetric structure.62,64 The major difference was also reflected 100 cycles (Fig. 4f). However, the cubic structure was retained
in the application of Li+ storage. in the next cycles. The low crystallinity of NH4FeF3 cannot store
The NaFeF3//Li half-cell constructed by Andréa et al. ions like KFeF3 (only 50% of the theoretical capacity was
retained a capacity higher than 200 mA h g1 after 50 cycles retained at 5 C (Fig. 4g)). After the first insertion of Li+, its
at C/3 and higher than 180 mA h g1 after 100 cycles at 1 C.59 crystallinity was essentially unchanged and had spectacular
The 3D stabilized channels are favorable to increase the migra- capacity retention during cycling.65
tion rate of alkali metal ions in the framework of the perovskite A-site elements play a supporting role in the crystal structure,
structure. In addition, Martin et al. used a fluorinated sol–gel whereas B-site elements affect the reactivity and catalytic
process to synthesize perovskite materials with different activity of perovskite-type compounds. Therefore, the modula-
cations at the A-site (Fig. 4a). For example, KFeF3 is in the tion of B-site elements is necessary for electrochemical perfor-
Pnma conformation after the insertion of Na+ and in the cubic mance improvement for application in Li-ion batteries. Ying
conformation after the insertion of Li+, and the volume of its et al. synthesized a new cost-competitive KZnF3 (KZF) material
device remained nearly constant during a long charge/ and constructed an advanced Li-DIB. KZF displayed a conversion/
discharge period (Fig. 4b). This change in structure can explain alloying hybrid mechanism with pseudocapacitance-dominated
the excellent rate performance (maintaining 70% of the theo- kinetics for Li-ion storage, which differed from the previously
retical capacity at 5 C), still with a capacity of 132 mA h g1. The described conversion/insertion hybrid process with pseudocapa-
GCD curves of KFeF3, when cycled toward lithium, are shown in citive characterization for Na0.85Ni0.45Co0.55F3.56.60 Due to the high
Fig. 3e. After deinsertion of the potassium ions characterized by natural reserves of Zn, KZF not only had the advantage of being
a first slopped curve, a single clear plateau can be observed inexpensive but also exhibited fast pseudocapacitive kinetic beha-
between 3.5 and 2.8 V. Unfortunately, the cycling performance vior and good cycling stability. Specifically, the KZF electrode can

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Fig. 4 Synthesis roadmap and model diagram of K/NH4+FeF3 (a). Ex situ XRD of KFeF3 during charging and discharging (b). Comparison of ex situ XRD of
NH4FeF3 and KFeF3 (c). GCD of NH4FeF3 at C/10 (d) and KFeF3 at C/2 (e) toward Li. Cycling performance of NH4+FeF3 (f) and KFeF3 (g).65 Copyright r
2019 American Chemical Society.

achieve a high capacity of 134 mA h g1 at a current density of KNCMF-111 underwent conversion reactions and showed a
100 mA g1 and also maintain 136% of the initial capacity after pseudocapacitive kinetic behavior, exhibiting good kinetics and
1000 cycles.66 Similarly, given the finite and high cost of nickel/ specific capacity, reaching a maximum capacity of 343 mA h g1
cobalt resources, Huang et al. synthesized a tetragonal KCuF3 at 100 mA g1.69 Ying et al. synthesized KZMF(1-3)(K1.1Zn0.17-
(KCF) material with lower cost as an advanced anode for Li+ Mn0.83F3.03) demonstrating pseudocapacitance-diffusion hybrid
storage devices, demonstrating the conversion mechanism and control kinetics with the conversion–alloying hybrid mechanism
pseudo-capacitance kinetic properties. The KCF electrode had (Fig. 5a and b), which contributed to significantly improved rate
a specific capacity of 65.6 mA h g1 at a current density of performance and cycling stability, especially at high current
100 mA g1 and an excellent stability of 191% of the initial densities (Fig. 5c and d). The KZMF(1-3) electrode exhibited a
capacity after 1000 cycles.67 It can be seen that the different higher reversible capacity of 111–47 mA h1 at 0.1–3.2 A g1
B-site elements in the perovskite structure had a significant effect and an excellent retention of 334% at 2 A g1 for 1000 cycles.
on cost control, the lithium storage mechanism and management Therefore, KZMF(1-3) electrodes are expected to be promising
of electrochemical properties. low-cost candidates for lithium-ion and dual-ion energy storage
Generally, polymetallic candidates exhibited better behavior because Zn and Mn elements are much more abundant than Ni
than the corresponding monometallic candidates, mainly due and Co species.70
to the synergetic effects of polymetallic redox substances. For To further promote the application of perovskite fluoride
redox substances containing Ni, Co, Zn and Mn, Ni-containing electrode materials in energy storage fields, the construction
substances can enhance the electrochemical activity, whereas of composite materials in combination with other materials
Co-/Mn-based materials can contribute to electrical conduc- with complementary properties is also an effective means. For
tivity and structural stability, respectively. Accordingly, depend- example, graphene has been widely used for electrochemical
ing on the characteristics of the various elements, a compound energy storage due to its excellent electrical conductivity,
composed of polymetallic elements would contribute to the stability and flexibility. Ying et al. constructed electrode materials
overall performance of the material. Xu et al. optimized the (KCMF(3 : 2)/rGO) consisting of Co and Mn element-doped
performance as LIC and DIB anode for dual-ion batteries via perovskite fluoride anchored on graphene with robust hetero-
tuning the Ni/Co ratio in the perovskite K–Ni–Co–F (denoted as geneous nanostructures that exhibited fast kinetics of pseudo-
KNCF). The optimal material, KNi0.1Co0.9F3, had a bulk nano- capacitive behavior in the storage of Li+.71 The electrochemical
crystalline morphology with a hierarchical porous structure, performance of the KCMF(3 : 2)/rGO electrode was better com-
thus showing the surface conversion mechanism for Li+ energy pared to that of KCMF(3 : 2) electrodes. And the KCMF(3 : 2)/
storage, in which Ni and Co electroactive substances had a rGO electrode had a reversible capacity of 288–106 mA h g1 at
synergistic effect on Li-ion storage.68 In addition, Yan et al. a current density of 0.1–3.2 A g1, which was twice that of bare
synthesized ABF3 materials (K0.97Ni0.31C0.34Mn0.35F2.97, KNCMF-111) KCMF(3 : 2) electrodes. With the introduction of rGO, the
doped by three elements of metal Ni, Co and Mn at the B-site particle size and specific surface area of KCMF(3 : 2) become
and explored their electrochemical properties and energy sto- smaller and larger, respectively, contributing to the increase in
rage characteristics in a Li+ storage device. During cycling, electrode/electrolyte contact area. Second, rGO in KCMF(3 : 2)/rGO

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Fig. 5 Reaction mechanism of the KZMF electrode (a). Schematic diagram of potential applications of KZMF for Li+ storage (b). Specific capacity of KZMF
(c) and cycling performance (d).70 Copyright r 2020 Elsevier.

is also an active material that can store Li+. The introduction Huang et al. also explored a perovskite anode for LIBs
of particles at the nanoscale level can prevent aggregation (K1.00Ni0.06Co0.14Mn0.80F2.92, KNCMF-3#) with an F vacancy
between graphene sheets, which can expose more active surface and a different Ni/Co/Mn doping ratio than before. The
area, which is beneficial to increase the overall capacity of presence of the F vacancy led to an increase in activity and
KCMF(3 : 2)/rGO. The presence of rGO builds a conductive net- conductivity. The change of the elemental doping ratio altered
work in the composite, ensuring higher electron conductivity,72 the synergistic effect and electrode cost. KNCMF-3# showed
reducing the internal resistance of the LIBs, thus resulting in a conversion-type charge storage mechanism with excellent
higher reversible capacity and better rate capability.73 overall electrochemical performance.77
The introduction of defects in the material is another
strategy. The resulting increases in active sites, specific surface 2.3 ABO3 type perovskite fluoride
area and conductivity all contribute to the improved specific As a metal oxide, perovskite oxides have been studied by many
capacity.74 Cation vacancies have unique advantages for elec- researchers due to their high electrical conductivity and acces-
trode materials in that they allow reversible embedding/ sible oxygen vacancies.78 In the case of ABO3-type perovskite
de-embedding of ions in the crystal structure with little effect oxides, their characteristics are that the B-site transition
on the crystal structure, thus maintaining excellent perfor- element can change its valence and improve the electrical
mance at high rate and long cycling life.75 The vacancies of conductivity. Mahata et al. found a significant increase in
F are new active sites that favor strong adsorption of Li ions conductivity during the reduction of Mn4+ to Mn3+ in La(1x)-
and enhanced electrical conductivity.76 Shi et al. successfully CaxMnO3, which is suitable as an electrode material.79 The
synthesized Na0.85Ni0.45Co0.55F3.56 (NNCF) anode materials materials with ordered structures in the A-site generally have
with sodium ion vacancies, and due to the presence of Na outstanding thermal and chemical stability, high electrical
vacancies, lithium ions can be inserted into the NNCF electro- conductivity, and oxygen dynamics.28 The ability to easily tune
des dominated by the Ni sites, thus exhibiting excellent lithium the structure of A+ and B+ cations brings tremendous improve-
ion storage behavior.60 Huang et al. successfully synthesized ments in the performance of perovskite oxides in various
the first ternary Ni/Co/Mn perovskite containing K+ vacancies applications. On the other hand, perovskite structural versati-
with excellent lithium ion storage performance (K0.89Ni0.02- lity depends on the ability to accommodate a large number
Co0.03Mn0.95F3.0, KNCMF-3#), exhibiting excellent overall per- of oxygen vacancies in the ABO3d stoichiometry of the oxide.
formance and conversion/insertion mechanism dominated by This is crucial for energy conversion materials because the
pseudocapacitive behavior, which lead to the excellent rate and emergence of oxygen vacancies enables oxygen to diffuse
cycling performance. By forming composites with rGO, the specific through the solid.80 In addition, the size and morphology of
capacity of the KNCMF-3# material was increased again, and the nanocrystals are two elements that affect the electrochemi-
KNCMF-3#@rGO exhibited excellent electrochemical performance cal performances of perovskites. The quality of the structured
(217 mA h g1@100 mA g1, 150%/1000 cycles@2 A g1).58 nanocrystals, the presence of defects in the lattice, the A- and/or

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Fig. 6 SEM micrograph (a) and cycling performance (b) of NaNbO3.81 Copyright r 2019 Royal Society of Chemistry. SEM micrographs (c and e), cycling
performance (d) and rate performance (f) of nanostructured flowerlike KTaO3.82 Copyright r 2019 Elsevier.

B-site doping of the perovskite lattice, the porosity of the nano- reversible specific capacity of 763 mA h g1 after 100 cycles at
crystals and the presence of synergistic effects in the bifunc- 0.5 A g1.83 Similarly, Liu et al. synthesized SmFeO3 and
tional morphology all play vital roles in the ultimate electro- Sm0.92Bi0.08FeO3 as electrode materials in lithium-ion batteries.
chemical behavior. The first discharge capacities of SmFeO3 and Sm0.92Bi0.08FeO3
It is an interesting work to explore perovskite oxides electrodes were 450 and 550 mA h g1, respectively, and their
with multiple morphological features. Yan et al. synthesized corresponding reversible capacities were 300 and 400 mA h g1,
NaNbO3 as the anode for lithium-ion batteries with bulk respectively. It is very interesting to note that SmFeO3 still
morphology (Fig. 6a), which can reach a reversible specific retained 98% of the discharge capacity of the previous cycle,
capacity of 130–55 mA h g1 at the current densities of while Sm0.92Bi0.08FeO3 seemed to lose capacity extremely
0.1–3.2 A g1.81 In particular, NaNbO3 can achieve a cycle quickly after the 20th cycle. Discharging resulted in partial loss
retention rate of 185% after 1000 cycles (Fig. 6b). Unlike the of crystallinity, whereas charging slightly restored the crystal-
bulk material, the flower-like nanostructured KTaO3 prepared linity of SmFeO3 but not that of the Bi-doped SmFeO3. The lack
by Sumedha et al. had a high interfacial area and a short charge of crystallinity restoration may be associated with the poorer
transport length, which were the main reasons for exhibiting rate properties observed in this doping solution.84
favorable electrochemical properties (Fig. 6c–f). It still had a The defect engineering in perovskite oxides (ABO3) has been
high specific capacity of 256 mA h g1 after 200 cycles at a extensively investigated as a key factor affecting ion and charge
current rate of 0.1 C and a high coulomb efficiency (B99%). transfer properties.85 The study of defect chemistry in these
The material exhibited an excellent specific capacity of oxides has allowed us to tailor novel materials with suitable
74 mA h g1 at high current rates (3 C).82 oxygen vacancy densities, mixed ionic/electrical conductivity,
The design of new perovskite materials with special combi- and other features. The oxygen defect concentration in perovs-
natorial arrangements by A- or B-site doping to boost their kites can be substantially adjusted through doping with low
optical and electronic properties is also a means to promote and/or high valence cations at the B/A-site vacancies. As a
the practical implementation of perovskite oxides in energy consequence, perovskites containing transition metals facilitate
storage. Ko et al. first explored the Mn-doped Nd0.9Mn0.1FeO3 the subsequent tuning of the structure to promote electrocatalytic
perovskite as the anode material with fascinating specific and electronic processes.86 Yang et al. synthesized cationic defec-
capacity in place of the common graphite anodes. The perovs- tive perovskite CeNb3O9 (CNO) with particle size in the order of
kite was prepared by a simple hydrothermal strategy and was microns, which can store adequate amounts of lithium at high
structurally confirmed for the occurrence of manganese in charge/discharge rates. At 60 C (15 A g1), the CNO anode
its distorted octahedral structure. The introduction of manga- provided more than 52.8% of the theoretical capacity. Additionally,
nese significantly accelerated the electron conduction of the the CNO anode material had excellent long-term cycling
material, thus shortening the ion/electron transport length and stability at an ultrahigh rate of 50 C (12.5 A g1). The superior
improving the electrochemical properties. The material had a cycling performance was ascribed to the formation of atomic

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Fig. 7 Li+ insertion point of CNO calculated by DFT (a). The iDPC image along the [101] direction after charging (b). The Li+ migration pathway (c) and the
energy profile (d).87 Copyright r 2022 Wiley VCH.

short-range ordering, which significantly prevented the local The construction of composites can also improve the con-
and long-range structural rearrangements and stabilized the ductivity and stability of perovskite oxides during lithium
bulk structure responsible for small volume variation. The storage. Ganapathy et al. reported the excellent specific capacity
insertion sites, migration paths and the corresponding energy and cycling behavior of perovskite BaSnO3 nanoparticles (NPs)
distribution of Li+ within the CNO structure were calculated by decorated on two-dimensional graphene flakes. The prepared
DFT (Fig. 7). The A-site cation vacancies in the Ce atomic layer BaSnO3/rGO20 (20 wt% rGO) composite provided a maximum
provided more pathways for Li+ migration, increasing the capacity of 1200 mA h g1 at 0.5 C (650 mA g1), which was far
dimensionality of long-distance diffusion to three dimensions. higher than that of the single BaSnO3 and graphene anodes.89
Therefore, the infinite three-dimensional Li+ migration paths Qin et al. used few-layer Nb2CTx MXene (f-Nb2CTx) as a pre-
within CNO promoted the diffusion of Li+ and produced cursor and synthesized S-P-NNO/f-Nb2CTx hybrids on the basis
excellent rate performance of the CNO.87 of single crystal perovskite NaNbO3 nanocubes (S-P-NNO NCs)
Gao et al. elucidated the characteristics of cation ordering in by a freeze-drying process. Profiting from the optimized com-
A-site defective perovskite single crystals of La(1x)/3LixNbO3 position and synergistic effect between S-P-NNO NCs and
(x = 0 and x = 0.04). Both materials were found to have a f-Nb2CTx, the optimal S-P-NNO/f-Nb2CTx nanohybrids exhib-
complex modulated crystal structure, which possessed two ited a large reversible capacity of 157 mA h g1 at 2.0 A g1.90
kinds of A-type cation orderings, i.e., long-range layer ordering The FeMnO3-CNTCN (carbon nanotube conductive network) was
in the alternating (001)p plane and short-range (in-domain) prepared using an electrostatic self-assembly strategy by Li et al.,
columnar ordering in the La-rich (001)p layer, respectively. which showed splendid cyclability and rate performance.91 FeMnO3
It was also observed that even a small amount of Li substitution microspheres with multi-step redox reactions can provide abun-
for La significantly affected the columnar arrangement, result- dant active sites, while the highly conductive and flexible CNT
ing in a suite of structural and even microstructural changes substrate ensures fast lithium-ion transport and electron transfer.
that may have detrimental effects on the lithium ion conduc- Table 1 summarizes the electrochemical properties of all-inorganic
tivity of the material.88 perovskite materials for lithium-based energy storage devices.

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Table 1 The electrochemical properties of all-inorganic perovskite materials for lithium-based energy storage devices

Operating Specific capacity Cycling behavior

Material Electrolyte potential (V) (mA h g1/mA g1) (%/cycles/mA g1) Ref.
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CsPbBr3 0.5 M LiTFSI in BMIMTFSI 0–2 376–142/30–200 79/100/60 48

CsPbCl3 1 M LiBF4 in BMIMBF4 0.01–3.6 612.3–275.2/50–250 — 49
CsPbI3 1 M LiPF6 in EC : DMC = 1 : 1 0.1–3 — 156/100/40 50
CsPbBr3@CNTs 1 M LiPF6 inEC : DMC = 1 : 1 0.01–3 644.6/100 73/200/100 53
Cs2NaBiCl6 1 M LiPF6 in EC : EMC : DMC = 1 : 1 : 1 0.01–2.5 775/75 38/25/75 56
Cs2NaErCl6 1 M LiPF6 in EC : EMC : DMC = 1 : 1 : 1 0–2.5 522/300 71/500/300 57
K0.89Ni0.02Co0.03Mn0.95 1 M LiPF6 in EC : EMC : DMC = 1 : 1 : 1 0.01–3 217–97/100–3200 150/1000/2000 58
F3.0@rGO
Na0.85Ni0.45Co0.55F3.56 1 M LiPF6 in EC : EMC : DMC = 1 : 1 : 1 0.01–3 286–115/100–3200 187/600/1000 60
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KFeF3; NH4FeF3 1 M LiPF6 in EC : PC : DMC = 1 : 1 : 1 2–4.5; 2–4.5 60/40 C (1 C = 176); 63/100/C/10; 65

206/1/2 C 74/300/5 C
KZnF3 1 M LiPF6 in EC : EMC : DMC = 1:1:1 0.01–3 134–33/100–3200 136/1000/1000 66
KCuF3 1 M LiPF6 in EC : EMC : DMC = 1:1:1 0.01–3 66–48/100–3200 191/1000/1000 67
KNi0.1Co0.9F3 1 M LiPF6 in EC : EMC : DMC = 1:1:1 0.01–3 166–73/100–3200 197/1000/1000 68
K0.97Ni0.31Co0.34Mn0.35F2.98 1 M LiPF6 in EC : EMC : DMC = 1:1:1 0.01–3 343–63/100–3200 80/400/1000 69
K1.1Zn0.17Mn0.83F3.03 1 M LiPF6 in EC : EMC : DMC = 1:1:1 0.01–3 111–47/100–3200 334/1000/2000 70
KCo0.54Mn0.46F3/rGO 1 M LiPF6 in EC : EMC : DMC = 1:1:1 0.01–3 288–106/100–3200 169/1000/2000 71
K1.00Ni0.06Co0.14Mn0.80F2.92 1 M LiPF6 in EC : EMC : DMC = 1:1:1 0.01–3 240–110/100–3200 72/1000/2000 77
NaNbO3 1 M LiPF6 in EC : EMC : DMC = 1:1:1 0.01–3 130–55/100–3200 185/1000/2000 81
with 1% VC
KTaO3 1 M LiPF6 in EC : DEC : DMC = 2 : 1 : 2 0.01–3 401–102/0.1–2 C 59/200/0.1 C 82
Nd0.9Mn0.1FeO3 1 M LiPF6 in EC : DEC : DMC = 1 : 1 : 1 0.02–3 — 86/50/500 83
CeNb3O9(CNO) 1 M LiPF6 in EC : DEC : DMC = 1 : 1 : 1 0.8–3 195–103/0.2–60 C 96.6/200/1 C 87
(1 C = 250)
BaSnO3/rGO 1 M LiPF6 in EC : DEC = 1 : 1 0.01–3 1059/10 C 1200 mA h g1/ 89
100th/650
S-P-NaNbO3/f-Nb2CTx 1 M LiPF6 in EC : DEC = 1 : 1 0.01–3 398–157/0.05–2 170/1500/1000 90
FeMnO3-CNTCN 1 M LiPF6 in EC : EMC : DMC = 1 : 1 : 1 0.01–3.0 1074–383/100–5000 83/1000/1000 91

3. All-inorganic perovskite for other mechanisms for Na+ storage, exhibiting intriguing specific
energy storage batteries capacity (770 mA h g1).96 The use of perovskite based
insertion-type hosts is a promising method to conquer the
3.1 Sodium ion battery huge volume swelling due to alloying/de-alloying in the SIB
Considering the high price, safety issues, and poor lifespan anode. Bharathi et al. synthesized perovskite Na0.5Bi0.5TiO3
of LIBs, researchers have started to explore other alternative (NBTO) which exhibited high sodium storage capacity, fast
energy storage systems that can achieve sustainable energy sodium storage diffusion kinetics and splendid recyclability
storage.92,93 Because of the low cost and abundant natural through alloying/de-alloying reactions. It also provided specta-
reserves of sodium metal, SIBs are regarded as a potential cular capacity (470–230 mA h g1@100–230 mA g1).97 NaFeF3
substitution for lithium-ion battery technology. Sodium is had the potential to be used as a cathode material in sodium
chemically comparable to lithium, because it is the second ion batteries.98 Unfortunately, the electrochemical property of
lightest alkali metal after lithium. In addition to these, sodium NaFeF3 was restricted even after the synthesis of nanostruc-
is available in the earth crust in various mineral and ore tured chalcogenides by complex chemical or mechanochemical
forms, which makes sodium metal cost-competitive compared methods, because the Na-filled channels are still not enough to
to lithium metal. Since sodium–aluminum alloys cannot be provide fast (de)embedding.99 Equimolarly larger K can be used
formed in the operating voltage range of SIBs, aluminum foil instead of filled Na to expand the lattice channels without
can also be used as a collector for cathode and anode instead of causing degradation of the perovskite structure. Cao et al.
the more expensive and heavier copper foil, further reducing proposed a pre-expanded calixarene iron fluoride (KFeF3)
the cost of SIBs. In addition, owing to the larger ionic radius of skeleton by filling it with the large size K+ cation as a channel
Na+ (1.02 Å for Na+ and 0.76 Å for Li +), the desolvation energy of filler. The FeF6 octahedra were not deformed during the electro-
Na+ in various organic solvents is lower, which can facilitate chemical exchange between Na and K and Na insertion cycles,
diffusion kinetics.94 Nevertheless, the lack of more suitable and the K+ filling can maintain a more ‘‘regular’’ cubic phase,
electrode materials hinders the practical application of SIBs, where rapid diffusion occurred. The electrode achieved high rates
and it is necessary to explore new materials. of sodium storage with a reversible capacity of 110 mA h g1
Wang et al. synthesized polycrystalline ZnSnO3 as an anode at 0.1 C.100 Furthermore, K+ vacancies can be viewed as another
material for SIBs, followed by a simple etching reaction to host site to accommodate the insertion of alkali metal cations
obtain hollow structures, which achieved a reversible capacity (Na-ions), thus promoting the diffusion of Na-ions during electro-
of 315 mA h g1 at 30 mA g1.95 Ammu et al. synthesized chemical cycling. Tan et al. reported a new perovskite fluoride
BiFeO3 (BFO) electrode materials with conversion and alloying K0.82Co0.43Mn0.57F2.66@reduced graphene oxide (defined as

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Fig. 8 Co2p (a) and Mn2p (b) of KCMF(1-1)@rGO at different voltage points (ex situ XPS). TEM (c) and ICP-OES (d) of KCMF(1-1)@rGO samples. The
capacity and coulombic efficiency of KCMF@rGO with different Co/Mn ratios were obtained in the fifth cycle (e). Cycling stability (f).101 Copyright r 2021
Elsevier.

KCMF(1-1)@rGO) nanoparticle with vacancy defects as an or higher.105 Manganese-based perovskite fluoride KMnF3 has
anode material, which showed a pseudocapacitance-dominated attracted extensive research interest from scholars as a cathode
transition–insertion hybrid mechanism (Fig. 8a and b). The material for PIBs.
presence of defects in the structure can be seen by TEM and ICP- Poor electrical conductivity of manganese-based fluorides
OES (Fig. 8c and d). The KCMF(1-1)@rGO anode showcased caused by high band gap is a common issue when employed
excellent specific capacity, rate performance and cycling stability in electrode materials.106,107 Improving the conductivity of
(176–84 mA h g1 at 0.05–1 A g1, 67% retention@500 cycles and fluoride by a range of approaches, such as doping and nano-
0.3 A g1) due to the synergistic effects of Co and Mn active sizing, is an essential realm of research to enhance the electro-
species, fast pseudocapacitive kinetics, enhanced ion storage chemical property of electrode materials. Oxide has a narrow
capacity of K ion vacancies and unique nano-heterogeneous forbidden band gap in comparison to fluoride, so doping a
structure (Fig. 8e and f).101 small amount of oxygen in fluoride can boost its conductivity to
a larger degree.108,109 Meanwhile, the Bowling radius of O2
3.2 Potassium–ion battery similar to that of F (1.40 Å vs. 1.36 Å) makes O doping easier.
The scarcity, high price and the uneven geographical distribu- Wang et al. synthesized O-doped KMnF3 as a cathode for PIBs
tion of lithium resources seriously confine the sustainability of by a carbon coating cladding and etching method (Fig. 9a). The
lithium-based batteries for large-scale energy storage purposes. doping of O atoms increased the conductivity and slightly
Therefore, there is an urgent need to develop EES that can reduced the migration barrier of K (Fig. 9b–e). The carbon
replace Li-ion batteries based on low budget and sufficient coating served to prevent the direct contact of Mn-ions with the
natural resources (e.g., Na and K).102 In recent years, potassium electrolyte, thus possibly hindering the dissolution of Mn-ions
ion batteries (PIBs) have drawn much attention owing to the in the electrolyte. The carbon-coated KMnO0.125F2.875 electrode
higher abundance, lower cost as well as lower standard redox retained a specific charge capacity of 113.8 mA h g1 and a
potential of K+ than Li among the available energy storage specific discharge capacity of 103.6 mA h g1 after 40 cycles
technologies. The key to developing PIBs with excellent perfor- (Fig. 9f and g).110
mance is to design cathode materials with reasonable micro- Wang et al. prepared Co-doped KMnF3 as a cathode material
structures to achieve ideal K+ embedding/detachment. Manganese- for potassium ion batteries by a co-precipitation method under
based materials can be employed as anode and cathode materials mild conditions. By controlling the amount of cobalt doping,
for various types of batteries because of their abundant reserves the dissolution of manganese could be effectively mitigated and
and environmental friendliness.103,104 As the cathode of PIBs, the cycling behavior of the material could be boosted, so that
manganese-based fluoride electrode materials can overcome the material could still reach 118.2 and 103.4 mA h g1 of
the drawback that manganese-based oxide materials (K0.3MnO2 charging and discharging capacities after 60 cycles at 40 mA g1.111
and K0.5MnO2) cannot reach charging voltages greater than 4 V Wang et al. fabricated d-MnO2/KMnF3-30 (KMnF3 mass%: 30%)

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Fig. 9 Schematic diagram of the synthesis process. (a) Charge/discharge curves (b) and cycling performance (c) of KMnO0.125F2.875. Spin polarization of
DOS (d) and energy profile (e). Schematic diagram of K migration (f and g).110 Copyright r 2020 Elsevier.

with the multivalence manganese via a homogeneous precipi- and delocalization (Fig. 10f), and showed a specific capacity of
tation method and used it as the cathode for PIBs wherein 110 mA h g1 even after 10 000 cycles (Fig. 10g and h).113
d-MnO2 nanowires with different lengths can fully take advan-
tage of short-range filling of short nanowires and cross-linking 3.3 Zinc-ion battery
of long nanowires to produce more stable network connectivity. As a novel energy storage device with cost-effectiveness and
Moreover, the homogeneous insertion of KMnF3 nanograins environmental friendliness, aqueous zinc-ion batteries (ZIBs)
in d-MnO2 nanowires can effectively mitigate the volume swing have received broad interest from researchers.114,115 The
pertaining to ion embedding during the repeated cycling. The cathode is an important component of ZIBs, and significantly
composite combines the advantages of Mn-based fluoride and affects the electrochemical performance of the batteries.
oxide, and was used as an anode material, which displayed high Currently, the cathode materials used for ZIBs mainly include
capacity, good cycling and rate performances. Interestingly, the vanadium/manganese-based oxides, transition metal sulfides
capacity can still be as high as 90 mA h g1 after 200 cycles at and Prussian blue analogs. Vanadium-based oxides are good in
100 mA g1.112 their capacity and cycling performance, but have a low voltage
The low capacity and poor stability of PIBs, especially the window and high toxicity. Transition metal sulfides are used as
much huge volume change in comparison to traditional Li-ion electrode materials in ZIBs owing to their layered structure and
batteries, greatly hinder their rapid development. Liu et al. large layer spacing. However, the strong electrostatic interactions
demonstrated a new etching method to construct a new zero- between Zn2+ ions and the primary structure lead to still unsatis-
strain manganese-containing perovskite fluoride (KMnF-LE) factory capacity and rate performance.116 Prussian blue materials
with a hollow nanocube structure to improve the performance are of interest because of their non-toxicity and low price.
of the nanocube KMnF-L with respect to capacity, rate perfor- However, their capacity is low and rate capability is poor.117
mance, and cycling behavior (Fig. 10a–e). The prepared KMNF- Manganese-based oxides have high discharge voltage and
LE, rich in K/F vacancies, exhibited high capacity and ultrahigh specific capacity, but their conductivity is poor and active sites
stability, maintained its structure well during K+ embedding are insufficient.118 As such, exploring innovative cathode

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Fig. 10 Synthesis and characterization of hollow KMnF-LE (a–e). In situ XRD patterns of KMnF-LE (f). Cyclic stability (g) and rate performance (h) of
KMnF-L and KMnF-LE.113 Copyright r 2018 Royal Society of Chemistry.

materials for ZIBs is an effective way to further enhance their Table 2 summarizes the electrochemical properties of the
application prospects. above-mentioned all-inorganic perovskite materials for K/Na/
Zhang et al. synthesized a cathode material with perovskite Zn-ion batteries.
structure of bimetallic oxides (NiMnO3) for ZIBs, which exhibited a
high capacity of 300 mA g1 at a current density of 280 mA h g1 3.4 Zinc–air battery
and an excellent cycling capability of 120 mA h g1 even after Rechargeable lithium-ion batteries are the most abundantly
10 000 cycles at high current density.119 used rechargeable batteries on the market today, but their
Manganese-based cathodes are usually affected by man- energy density (200–250 W h kg1) is not high enough, thereby
ganese leaching and structural deformation, resulting in a hindering their practical application in more fields. In recent
continuous capacity decay during cycling. The by-products years, the metal–air battery has emerged into the limelight with
generated during the long cycling period will be deposited on a theoretical energy density several times higher than that of
the surface of the cathode materials, such as ZnO, Mn3O4, LIBs, while the low cost, environmental friendliness and safety
Zn(OH)2, and Mn(OH)2, which seriously affect the cycling life. features further promote the metal–air battery to be one of the
Zhu et al. synthesized porous filamentous Ni-doped LaMnO3 as most promising devices among a variety of future energy
a new cathode material for weakly acidic aqueous ZIBs (Fig. 11a storage devices.121 The high energy of the metal–air battery
and b), which has a morphology similar to that of porous originates from the redox reaction between the metal anode
loofah-like particles of several micrometers in diameter. The and the oxygen in the cathode air. In general, the cathode has
synergistic effect of nickel doping and La3+ cation vacancies an open pore structure that facilitates the continuous supply/
can significantly improve the electrochemical properties. The giving-off of oxygen.
vacancy of La (rLa3+ = 1.15 Å) promoted the insertion/exaction of As an important type of metal–air battery, zinc–air batteries
Zn2+ with a small ionic radius (rZn2+ = 0.74 Å), while the (ZABs) have received a high degree of attention. The zinc anode
structure does not undergo deformation (Fig. 11c and d). The features not only low cost and abundant natural reserves, but
small amount of the Zn4SO4(OH)6xH2O phase is associated also spectacular energy density by virtue of the participation of
with the side reaction of the electrolyte. The doping of Ni two electrons in the redox process.122 The energy storage
improves the electrical conductivity and hinders the dissolu- process of ZABs is a reversible reaction: during the discharge
tion of the active material. The LaNixMn1xO3 perovskite process, the zinc anode undergoes an oxidation reaction to
exhibited better electrochemical properties than LaMnO3 with form Zn(OH)2, while the oxygen of the air participates in the
quick diffusion kinetics of Zn2+ (Fig. 11e and f). The prepared reduction reaction to form OH. During charging, zinc hydro-
LaNixMn1xO3 (x = 0.2) still showed a specific discharge xide is reduced to metallic zinc, while OH is oxidized to form
capacity of 243 mA h g1 after the 100th cycle at 0.1 A g1.120 oxygen. As a result, the oxygen evolution reaction (OER) and the

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Fig. 11 SEM of LaNixMn1xO3 (x = 0.2) (a) and LaMnO3 (b). Charge/discharge curves (c), XRD at different voltages (d), GITT curves (e) and diffusion
coefficients (f) of LaNixMn1xO3 (x = 0.2).120 Copyright r 2022 Elsevier.

Table 2 The electrochemical properties of the above-mentioned all-inorganic perovskite materials for K/Na/Zn-ion batteries

Operating Cycling behavior

Material Electrolyte potential (V) Specific capacity (%/cycles/mA g1) Ref.
1 1
ZnSnO3 1 M NaClO4 in EC : PC = 1 : 1 0.01–3.00 315 mA h g at 30 mA g 92/100/250 95
Na0.5Bi0.5TiO3 1 M NaClO4 in PC with 2% FEC 0.001–3 470–230 mA h g1 at 45.7/50/100 97
100–250 A g1
NaFeF3 1 M NaClO4 in PC — 130 mA h g1 at 0.2 mA cm2 — 98
KFeF3 1 M NaClO4 in EC : PC = 1 : 1 1.5–4.5 110–40 mA h g1 at 0.1–10 C — 100
K0.82Co0.43Mn0.57 1 M NaPF6 in EC : 0.01–3 176–84 mA h g1 at 0.5–1 A g1 67/500/300 101
F2.66@rGO EMC : DMC = 1 : 1 : 1
Carbon-coated 0.8 M KPF6 in EC : DEC = 1 : 1 1.2–4.2 113.8 mA h g1 at 35 mA g1 61 mA h g1/200th/100 110
KMnO0.125F2.875
K(Mn,Co)F3 0.85 M KPF6 in EC : DEC = 1 : 1 1.2–4.2 170.5 mA h g1 at 40 mA g1 60.6/60/40 111
(Mn : Co = 10 : 1)
1
d-MnO2/KMnF3-30 0.85 M KPF6 in EC : EMC = 1 : 1 1.0–4.3 — 90 mA h g /200th/100 112
K0.6Mn1F2.7-NC frame 0.8 M KPF6 in EC : DEC = 1 : 1 0.01–2.6 182–78 mA h g1 at 20–1000 mA g1 110 mA h g1/10 000th/400 113
NiMnO3 2 M ZnSO4 + 0.1 M MnSO4 0.8–1.8 291–152 mA h g1 at 0.1–1 A g1 236 mA h g1/1000th/300 119
LaNi0.2Mn0.8O3 2 M ZnSO4 + 0.2 M MnSO4 1.0–1.8 208–93 mA h g1 at 0.1–3.2 A g1 46.5/1000/500 120

oxygen reduction reaction (OER) play critical roles in the energy among the non-precious metal catalysts, have a large specific
storage process of ZABs, determining their overall performance surface area and strong electrical conductivity/mass transfer
and cost. However, the sluggish kinetic process has a detri- capabilities, yet they are gradually oxidized and corroded
mental effect on the power density and energy utilization during OER. Other metal compounds enjoy bifunctional cata-
efficiency of ZABs, thus making them fall short of their theore- lytic activity, but suffer from the shortcomings of low active
tical capacity. Therefore, the design and construction of high- sites as well as inferior electron and mass transport features.124
efficiency electrocatalysts with excellent stability for OER and An ideal electrocatalyst should possess the advantages of a high
ORR is one of the most significant strategies in current research density of active sites, a robust structure, good catalytic activity
on ZABs.123 and high electrical conductivity.
Although noble metals have high catalytic activity compared In ZABs, perovskite materials like LaCoO3 display excellent
to other researched catalysts, their high cost and inability to catalytic activity. A number of studies have been carried out in
simultaneously satisfy ORR and OER requirements make them the latest years to boost the overall performance of perovskite
a less desirable option. Carbon-based nanomaterials, which are catalysts. The larger the specific surface area of the material,

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the greater the number of active sites that can participate in the pristine PBC catalyst, the 20 wt% GDC decorated PBC catalyst
catalysis, which facilitates the enhancement of catalytic perfor- delivered a higher signal intensity, denoting more surface oxygen
mance. Shim et al. prepared nanofibrous LaCoO3, which had a vacancies after GDC decoration (Fig. 12b). The concentration of
bigger surface area and more active sites than bulk LaCoO3, O22/O representing surface active oxygen vacancies increased
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showing better catalytic activity.125 Ishihara et al. created from 24.86% on the pristine PBC catalyst to 35.96% for the 20 wt%
La0.6Ca0.4CoO3 with a substantial percentage of mesopores as GDC decorated PBC catalyst, fairly agreeing with the EPR result
well as a high specific surface area. The addition of mesopores (Fig. 12c). From the calculation results, it can be seen that the
enhanced the catalytic stability of La0.6Ca0.4CoO3, and simi- presence of oxygen vacancies increased the adsorption energy of
larly, the potential of OER and ORR of La0.6Ca0.4CoO3 remained O2 and H2O on the surface of GDC, which was beneficial to the
stable after 90 cycles at a current density of 20 mA cm2.126 OER and ORR reactions (Fig. 12d–g). The ZABs assembled with
Open Access Article. Published on 22 October 2022. Downloaded on 5/20/2024 1:55:12 AM.

The electrical conductivity and electronic configuration of this composite exhibited a maximum peak power density of
perovskite materials have an impact on the ability of electron 207 mW cm2 and a significant durability of 200 h.128
conduction to the active site; hence the electrical conductivity The preparation of composites to overcome some of the
of the material cannot be overlooked. Furthermore, defects in drawbacks of a single material is one of the typical methods to
the structure of catalysts not only allow the fabrication of more improve the catalytic activity of perovskite catalysts. Especially
edge structures to increase the active sites but also reduce the in ZABs, catalysts are required to meet both ORR and OER high
potential barriers of the rate-determining step to strengthen performance requirements. Generally, the design of suitable
the catalytic activity. Ran et al. synthesized sulfur-doped LaCoO3 composites is a simple and efficient method. Considering that
(S-LCO) catalysts for ZABs, where sulfur doping and the introduc- CoO can provide more suitable active sites for oxygen adsorp-
tion of oxygen defects promoted the electrical conductivity and tion and boost the electrical conductivity, Zheng et al. prepared
simultaneously optimized the filling state of the eg, thus enhan- the composite electrocatalyst by introducing CoO onto
cing the electrocatalytic performance of LaCoO3. When used as the LaMnO3. In particular, CoO solved the problem of poor OER
cathode of ZABs, S-LCO had a power density of 92 mW cm2, a performance of LaMnO3. The assembled ZABs based on the
high specific capacity of 747 mA h g1 at 5 mA cm2, and a long composite possessed a power density of 101.48 mW cm2
cycling life (100 h).127 Gui et al. demonstrated the oxygen vacancy- and intriguing cycling stability.129 Wang et al. synthesized
rich Ce0.9Gd0.1O2d (GDC) modified Pr0.5Ba0.5CoO3d (PBC) as a bifunctional composites (Pt-SCFP) with excellent electro-
bifunctional catalyst for ZABs (Fig. 12a). The surface modification chemical activity and durability based on Pt and perovskite
of GDC not only introduced abundant electrochemically active Sr(Co0.8Fe0.2)0.95P0.05O3d (SCFP). Pt–O–Co bonds existed in the
oxygen vacancies for ORR and OER (Fig. 12b and c), but also Pt-SCFP/C-12 samples from the ball milling method, and a
enhanced the structural stability of the perovskite. In contrast to large number of electrons were transferred from Pt to SCFP

Fig. 12 Schematic diagram of the GDC-modified PBC bi-functional catalyst (a). Comparison of the EPR spectra (b) and O 1s spectra (c) of PBC before
and after GDC modification. Schematic diagram of adsorption of O2 and H2O molecules on PBC (d and f) and GDC (e and g).128 Copyright r 2021
Wiley VCH.

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Table 3 Electrochemical properties of the above-mentioned all-inorganic perovskite materials for zinc–air batteries

E1/2 (vs. RHE) DE Maximum power

Catalysts Electrolyte (V) EOER (vs. RHE) (V, EOER  EORR) density (mW cm2) Ref.
1.594 V/10 mA cm2
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S-LaCoO3 6 M KOH and 0.2 M Zn(Ac)2 0.704 0.89 92 127

20 wt% GDC-Pr0.5Ba0.5CoO3-d 6 M KOH and 0.2 M Zn(Ac)2 0.71 1.65 V/10 mA cm2 0.94 207 128
LaMnO3–CoO 6 M KOH and 0.2 M Zn(Ac)2 0.56 1.78 V/10 mA cm2 1.22 101.48 129
Pt-Sr(Co0.8Fe0.2)0.95P0.05O3d/C-12 6 M KOH and 0.2 M ZnCl2 0.87 1.6 V/10 mA cm2 0.73 122 130
Sr2TiMnO6 6 M KOH and 0.2 M Zn(Ac)2 0.67 1.91 V/5 mA cm2 1.24 97 131
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through these Pt–O–Co bonds, thus changing the electronic diffusion of oxygen molecules and lithium ions. In parallel, the
structure of Pt and SCFP and forming a strong electronic mesopores facilitated the impregnation of the electrolyte and
interaction between Pt and SCFP in the Pt-SCFP/C-12 compo- the deposition of products. LaSrMnO3 reduced the reaction
sites. Meanwhile, the spillover effect also favored the enhancement overpotential, and graphene accelerated the electron transport
of catalytic activity. The best sample, Pt-SCFP/C-12, exhibited capability. When used as the cathode of Li–O2 batteries, it
impressive bifunctional activity for the oxygen reduction and exhibited high specific capacity, excellent rate performance and
oxygen evolution reactions with a potential difference of 0.73 V. good cycling stability.134 Moreover, there is no doubt that the
Remarkably, the initial discharge and charging potentials loaded metal nanoparticles favor the improvement of catalyst
of the ZABs based on this catalyst were 1.25 and 2.02 V at activity. Cong et al. proposed a new solution to obtain a
5 mA cm2, accompanied by excellent cycling stability.130 perovskite co-decorated with CoFe alloy and Co metal on the
Furthermore, A2B 0 B00 O6 compounds can contain elements basis of La0.8Fe0.9Co0.1O3d by varying the annealing tempera-
that are not possible in individual perovskites because they can ture. Benefiting from the change of cation exchange behavior at
allow the expansion of their composition space. Bhardwaj et al. different temperatures, the Co cations in the perovskite gradu-
investigated a new-type perovskite material Sr2TiMnO6 (STMO) ally exsolved onto the surface of nanoparticles, and the Fe
for rechargeable ZABs. The constructed ZABs exhibited a atoms in the CoFe alloy gradually migrated back to the per-
maximum peak power density of 97 mW cm2 and a cycling ovskite. The obtained composites demonstrated an excellent
stability of 6.6 h cycles.131 Table 3 summarizes the electro- specific discharge capacity of 6549.7 mA h g1 and a cycle
chemical properties of the above-mentioned all-inorganic per- stability of 215 cycles when used in Li–O2 batteries.135
ovskite materials for ZABs. In the structure of perovskite oxides, doping at the A-site
may form O defects, which indirectly affects the ORR/OER
3.5 Lithium–air battery activity of perovskite oxides. The doping of different ions in
As another type of metal–air battery, the lithium–air (Li–O2) the B-site directly can influence the B–O–B angle, thereby
battery has also attracted research interest. Among the various increasing the intrinsic activity. Sung et al. synthesized Sr-
types of Li–O2 batteries, the nonaqueous type is the most and V-doped perovskite La0.8Sr0.2VO3 with a nanofibrous shape
promising one. Its energy density is ultra-high, but all other and investigated the kinetic behavior of the composed Li–O2
electrochemical performance aspects are unsatisfactory, such battery (Fig. 13). Doping Sr at the A-site may be accompanied by
as coulombic efficiency, rate performance, and cycling life.132 an increase in the number of oxygen vacancies. The variable
During the discharge process, O2 is reduced and reacts with Li+ valence states of vanadium ions (V3+, V 4+ and V5+) contributed
(ORR-LO) and forms soluble Li2O2, which later decomposes to provide donor–acceptor chemisorption sites to facilitate
into Li+ and O2 (OER-LO) during charging. Considering the ORR-LO/OER-LO. The doped electrode can maintain 253
difference from the Zn–air batteries, the oxygen reduction reversible cycles at a current of 2000 mA g1.136 The Li0.34La0.55-
reaction and oxygen evolution reaction in the Li–air batteries MnO3-d perovskites designed by Sang et al. exhibited high
in this review are denoted as ORR-LO and OER-LO, respectively. electronic (2.04  103 S cm1) and lithium ion (8.53 
Slow charge transfer and insufficient catalyst activity lead to 105 S cm1) conductivity in experiments, and when applied
sluggish kinetics of ORR-LO and OER-LO, which in turn affect in the carbon-free cathode of lithium–air batteries, they show-
the electrochemical performance of Li–O2 batteries.133 Air cased excellent reversibility at 0.21 mA h cm2 over 100 cycles
cathodes with high surface area, excellent electrical conductiv- while avoiding the degradation related to carbon-containing
ity, good electrochemical stability, and efficient bifunctional materials.137 Li et al. introduced surface permeable nanolayers
catalytic activity for ORR-LO and OER-LO are extremely impor- and oxygen vacancies on mesoporous hollow LaCoxMn1xO3s
tant for high-performance Li–O2 batteries. perovskite catalysts by in situ cation replacement using surface
ABO3-type perovskite oxide is a cost-effective and stable structure and defect engineering strategies. The O2-electrode
bifunctional cathode catalyst for Li–O2 batteries with tunable using the LaCo0.75Mn0.25O3s catalyst manifested an extremely
catalytic activity, good electrochemical stability, etc. Yang et al. impressive discharge capacity of 10 301 mA h g1 in the initial
designed a new graphene/LaSrMnO3 composite with a layered cycle at 200 mA g1. The excellent electrochemical performance
porous structure to address the porosity and conductivity of of LaCo0.75Mn0.25O3s may be owing to the synergistic effect of
ABO3. The macropores between the nanosheets promoted the the graded hollow structure and the large amount of oxygen

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Fig. 13 TEM (a) and SEM (b) of La0.8Sr0.2VO3 (LSV3 p-NFs). Schematic illustration of LSV3 p-NFs used in rechargeable Li–O2 batteries (c).136 Copyright r
2020 Elsevier.

Table 4 Electrochemical properties of the above-mentioned all-inorganic perovskite materials for Li–O2 batteries

Charge A restricted capacity Current density Cycling

Material Electrolyte potential (VLi) (mA h g1) (mA g1) life Ref.
G/meso-LaSrMnO3 1 M LiTFSI in TEGDME 4.21 500 500 50 134
CoFe@La0.8Fe0.9Co0.1O3d 1 M LiTFSI in TEGDME 4.4 500 200 215 135
La0.8Sr0.2VO3 1 M LiNO3 in DMAc 4.8 1000 2000 200 136
LixLayMO3 1 M LiTFSI in PC 4.2 0.21 mA h cm2 100 100 137
LaCoxMn1xO3s 1 M LiTFSI in TEGDME 4.5 500 200 60 138
LaF3/La0.8Fe0.9Co0.1O3d 1 M LiTFSI in TEGDME 4.4 500 200 157 139

vacancies covered over the catalyst surface. The introduced power density and long cycling life but poor energy density.140
oxygen vacancy can act as an effective substrate for the combi- The functions and properties of SCs originate from the inter-
nation of intermediate products and decomposition of Li2O2 action of their electrodes and electrolyte materials. According
during discharge and charge protocols.138 Hou et al. demon- to the energy storage mechanism, materials used for SCs are
strated a surface reconstruction strategy on perovskite generally classified into two categories, including capacitive
La0.8Fe0.9Co0.1O3-d (LFCO) to prepare a LaF3/LFCO composite, materials and pseudocapacitive materials.141,142 Electrode
which induces a modified surface and also manipulates the materials for double-layer capacitors rely on purely physical
electronic structure.139 The optimized surface and electronic electron accumulation occurring on the surface of the material,
structure adjusted the discharge reaction pathway and formed such as activated carbon, carbon fiber cloth, graphene, carbon
thin petal-like F-doped Li2O2, which displays better conduc- nanotubes and so on.143 Materials with pseudocapacitive pro-
tivity and benefits Li–O2 battery performance. Table 4 sum- perties have completely different electrochemical properties,
marizes the electrochemical properties of the above-mentioned where the current response is neither purely capacitive nor bulk
all-inorganic perovskite materials for Li–O2 batteries. Faraday (battery-like).144 The redox reaction occurs during
the energy storage process which endows pseudocapacitive
materials with higher capacity. The energy storage mechanisms
4. All-inorganic perovskite for of pseudocapacitive materials can generally be divided into
supercapacitors three categories. The first is through the adsorption/desorption
of ions from/into the electrolyte, which usually occurs as a
Both rechargeable batteries and supercapacitors (SCs) as energy monolayer on the electrode surface. The second is the redox
storage devices are expected to meet the characteristics of fast reaction that occurs on the surface of the material. The third
storage mechanism, high energy density, high power density, mechanism is that ions in solution intercalate/deintercalate
longer life cycle and environmental protection. The power into/out of pores or layers of the material, then react with the
density of batteries is inferior to that of SCs. SCs have high surrounding atoms and transport electrons through redox

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reactions. From the kinetic analysis, most of the first two by the oxygen vacancies created by doping with Sr. The specific
mechanisms are dominated by surface control, while for the capacitance of LSCM can be as high as 752 F g1 at 1 mV s1.
third one, diffusion control accounts for a large part. The Tomar et al. demonstrated cation and anion (de)embedded
energy density and comprehensive performance of SCs are hybrid electrodes that were nanocomposites (MLMO) containing
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significantly affected by many factors, such as the electro- MXene (Ti3C2Tx) and perovskite oxide (LaMnO3d, LMO) (Fig. 14a).
chemical properties of the electrode material, the choice of Multilayer MXene and anoxic LMO showed embedded pseudo-
the electrolyte, and the potential window of the electrode. capacitance based on cations (K+) and anions (OH), respectively,
Therefore, a lot of research efforts have been focused on contributing to total charge storage. Thus, MLMO exhibits high
developing advanced materials for SC electrodes with appro- capacitance retention (70.82%) even at a high current density of
priate structural design to facilitate efficient electron transport 30 A g1 (313.6 F g1) (Fig. 14b and c).152 However, the increase in
Open Access Article. Published on 22 October 2022. Downloaded on 5/20/2024 1:55:12 AM.

and ion diffusion.145–147 Recently, perovskite materials have oxygen vacancies cannot solve the problems of high internal
shown excellent potential for supercapacitor applications. resistance and slow charge transfer rate of the material. Sun
et al. combined Ca0.5Ca0.5MnO3 (LCM) with Ag by a two-step
4.1 ABO3 type perovskite fluoride process based on sol–gel and silver mirror reaction. The pre-
Recently, perovskite oxide (ABO3) materials have attracted con- pared LCM@Ag composite had an excellent specific capaci-
siderable attention due to their valence change at the ‘‘B’’ tance of 287 C g1 (179 F g1) at 1.5 A g1, whereas pure LCM
transition metal, oxygen ion mobility and electron conduction, provided only 187 C g1 (117 F g1). The key to the improved
and three-dimensional BO6 octahedral network. Transition performance can be attributed to the introduction of silver
metal-containing perovskite oxides, with their stable structure nanoparticles that enhanced the electron transport and ion
and wide potential window, are suitable for the construction diffusion capabilities of the composites.153 Tian et al. con-
of supercapacitor electrodes.148 Mefford et al. revealed the structed LaMnO3@NiCo2O4 materials with layered nanosheet
mechanism of oxygen vacancy-mediated redox pseudocapaci- morphology on nickel foam for SCs. The encapsulation of
tance of nanostructured lanthanide-based perovskite LaMnO3. LaMnO3 nanoparticles in NiCo2O4 nanosheets effectively sup-
This was the first example of anion-based intercalation pseudo- pressed the leaching of Mn species during reversible intercala-
capacitance and the first use of oxygen intercalation for tion and significantly improved the electrical conductivity.
fast energy storage. The oxygen embedding mechanism also Materials with flower-like nanosheets with open surfaces facili-
occurred in other lanthanide-based perovskites such as LaNiO3 tate mass transfer and can provide abundant electroactive sites
with similar charge storage behavior.31 But the main problems for surface redox reactions.154
are its lower conductivity and shorter cycling life. The multiple The double perovskite structure has a more ordered struc-
possibilities of altering the electronic and physical properties of tural arrangement than element-doped perovskites, which
perovskites and perovskite-derived structures may lead to can prevent lattice distortion and improve cyclic stability.
materials with high energy density. Agglomeration easily occurs Tomar et al. revealed that the B-site cation ordering in the
during the synthesis of perovskite materials, resulting in a large double perovskite Sr2CoMoO6d (DP-SCM) tends to favor the
number of active sites being encapsulated inside the particles. rock salt structure (0D arrangement). The synergistic effect of
Morphology changes could improve the overall utility of the Co/Mo with excellent redox ability further promotes high oxy-
active site. gen mobility. The high content of oxygen vacancies helps to
Zhang et al. prepared a honeycomb LaMnO3 material using increase the oxygen anion diffusion rate. Additionally, the fast
a carbon sphere material as a template to control the mor- kinetics of charge storage prevents any phase transition, reflect-
phology.149 It has an excellent specific capacitance (535 F g1), ing excellent cycling life (125% retention up to 5000 cycles).
higher than that of the LaMnO3 perovskite (247 F g1) without DP-SCM achieved a specific capacitance of 747 F g1 at 1 A g1,
the addition of carbon spheres as a template. The crystallinity, and the rate can still be maintained at 56% at currents up to
microstructure, morphology, elemental composition and 10 A g1.155 Li et al. fabricated 2D perovskite LaNiO3 nanosheet
chemical bonding state of LaMO3 perovskites were studied in assemblies with abundant pores by a facile sol–gel method and
detail by Hu et al. to elucidate the electrochemical properties of subsequent thermal treatment. The crystal structure, morpho-
LaMO3 perovskite nanofibers as supercapacitor electrodes. The logy, and electrochemical performance of LaNiO3 can be simply
specific capacitances of LaFeO3, LaCoO3 and LaNiO3 nano- tuned by adjusting the heating temperature and time. The
fibers at a current density of 1 A g1 were 183.6, 95.8 and optimized sample achieved a high specific capacitance and
116.3 F g1, respectively.150 By replacing the metal cations at cycling stability.156
the A- or B-site with other cations, non-chemo-metric perovs-
kites can be developed to increase the oxygen vacancies. 4.2 ABF3 type perovskite fluoride
A common approach to increase the conductivity of the LaBO3 In recent years, perovskite fluorides containing transition
perovskite is to partially replace the trivalent lanthanides at the metals have shown good potential for application in the field
A-site with divalent alkaline earth metals (Ca2+, Sr2+, etc.), which of SCs. They have a similar structure to ABO3-type perovskites,
can introduce more oxygen vacancies. La0.75Sr0.25Cr0.5Mn0.5O3 but the strong electronegativity of F makes it possible to lower
(LSCM) electrode materials were synthesized by Rehman the Fermi energy level and increase the operating voltage
et al.151 The charge storage capacity of LSCM was enhanced window as anode materials.157 The perovskite fluoride ABF3

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Fig. 14 Schematic illustration of reversible cation and anion (de)intercalation in MLMO (a). Comparison of CV curves (b) and specific capacitances (c) of
LMO, MXene and MLMO.152 Copyright r 2022 Elsevier.

features a robust open framework, intersecting tetragonal cavity and Mn species exhibit enhanced electrical conductivity and
chains and three-dimensional diffusion channels that favor ion electrochemical stability.163 Li et al. synthesized perovskite
mobility, and thus shows excellent rate performance in SCs. In SCs KNi0.8Co0.2F3 nanocrystals by a one-pot solvothermal strategy
with alkaline electrolytes, unlike the oxygen embedding mecha- for use as an electrode material for SCs. Due to the synergistic
nism of ABO3, ABF3 usually undergoes mainly conversion reactions effect of Ni and Co, it exhibited excellent specific capacity and
for charge storage. In addition, monometallic perovskite fluoride rate performance (673–619 C g1, 1–32 A g1), and its compre-
was found to have low conductivity and poor stability when hensive performance was superior to that of monometallic
applied in SCs.158–160 Therefore, it is necessary to design perovskite perovskites KNiF3 and KCoF3.164 Shi et al. prepared a Co- and
fluorides with improved properties in terms of crystal properties, Mn-doped (K–Co–Mn–F, Co/Mn = 6 : 1) KMF3 electrode material
morphology, and electrical conductivity for better electrochemical doped at the B-site, and the anode showed a specific capacity of
performance. 113 C g1 at a current density of 1 A g1 due to the synergistic
Modulation by adjusting the morphology and surface area of effect of Co and Mn redox substances. Its large particle size and
the material is a technique that has been extensively studied to many active sites could not be fully utilized resulting in a low
improve the specific capacity and cycling stability in energy capacity, but after activating the material during cycling,
storage processes.161 Micro/nanostructures with hollow spheres the capacity reached 118% of the initial capacity at the
have the unique structural advantage of adsorbing more ions, 5000th cycle.165 Doping of zinc in electrode materials or elec-
significantly shortening the diffusion path of ions and elec- trocatalysts usually contributes to special features such as
trons, and significantly reducing the volume expansion during increased reactivity, electrical conductivity and surface rough-
cycling. Hussain et al. synthesized a fluorinated perovskite ness, which can improve electrochemical performance.166,167
(NaNiF3) with hollow spheres and explained the mechanism Jia et al. synthesized a novel Zn-doped ABF3 electrode material
of hollow sphere formation in depth, and the method helped to K0.95Ni0.30Co0.38Zn0.32F3.05 (KNCZF) and applied it to SCs. The
construct other ABF3 materials with hollow structures. As a monometallic perovskite fluoride KZnF3 has no capacity in
cathode material for SCs, it had a high specific capacitance alkaline electrolytes, but the introduction of Zn in KNCZF
(1342 F g1), excellent rate performance and long cycle stability enhanced the activity of Ni and Co species. It was confirmed
(90%/8000 cycles).162 by multiple characterization means that KNCZF has more
Materials with redox properties containing transition metal electroactive sites, larger charge transfer ability, and stronger
components are commonly used in SCs and have a higher hydroxyl adsorption capacity compared to K1.03Ni0.39Co0.61F3.35
specific capacity than carbon materials. Compared to their (KNCF) (Fig. 15). The KNCZF electrode demonstrates excellent
corresponding monometallic counterparts, the binary/polyme- specific capacity (368 C g1/1 A g1) and cycle retention (75%/
tallic candidates typically have higher activity and conductivity 10 000 cycles/15 A g1).168
and exhibit excellent integrated electrochemical behavior, The construction of composites is also one of the effective
which is mainly caused by the synergistic effect between multi- means to enhance the performance of fluorinated perovskites
ple transition metal redox species. Previous studies have found in SCs. Jing et al. prepared composites (NaCo0.2Ni0.8F3/rGO)
Ni species to show enhanced electrochemical activity, while Co consisting of perovskite and rGO, considering the superiority of

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Fig. 15 Top view of the structures of KNCZF and KNCF (a and b). Eads (OH) (c). The distance between OH and the metal atom (dM–O) (d). Top view
(e, h, k and n) and side view (f, i, l and o) of different sites after OH adsorption. Differential charge densities of selected Ni/Co sites with OH and Bader
charge analysis (g, j, m and p). Peak positions of Ni2p3/2 (q) and Co2p3/2 (r) and the percentage of corresponding species for KNCF and KNCZF at the first
complete charge (C), complete discharge (D) and pristine state (P).168 Copyright r 2021 Wiley VCH.

Table 5 The electrochemical properties of all-inorganic perovskite materials for supercapacitors

Operating
Material Electrolyte potential (V) Specific capacity Cycle (%/cycles/A g1) Ref.
1 1
NaNiF3 3 M KOH and 0.5 M LiOH 0–0.5 1342–1080 F g at 5–50 A g 490%/8000/20 162
KNi0.8Co0.2F3 3 M KOH and 0.5 M LiOH 0.1–0.55 1530–1407 F g1 at 1–16 A g1 — 164
K–Co–Mn–F3(Co/Mn = 6 : 1) 3 M KOH and 0.5 M LiOH 0–0.55 113–100 C g1 at 1–16 A g1 118%/5000/8 165
K0.95Ni0.30Co0.38Zn0.32F3.05 3 M KOH and 0.5 M LiOH 0–0.55 368–294 C g1 at 1–32 A g1 75%/10000/15 168
NaCo0.2Ni0.8F3/rGO 3 M KOH and 0.5 M LiOH 0–0.5 805.7–661.4 C g1 at 0.5–16 A g1 92%/5000/8 169
KNi0.4Co0.2Mn0.4F3/Ag(37%) 3 M KOH and 0.5 M LiOH 0–0.6 489–278 C g1 at 1–128 Ag1 73%/10000/30 170
MnO2@NH4MnF3 1 M Na2SO4 0–1.0 240–38.9 F g1 at 1–30 A g1 98%/1000/1 171

rGO materials. More redox reactions can be promoted by the (MnO2@NH4MnF3) has less Mn2+ and more Mn4+, and more O
adjustment of the Co/Ni ratio of the variable metal ions, which defects, exhibiting better electrical conductivity and moderate
helps to increase the specific capacity of the material. capacitive contribution. What’s more, the graded porous
In addition, the addition of rGO improves the electrical con- morphology facilitates the diffusion of ions in the electrolyte,
ductivity of the material and reduces the degree of agglomera- which can add more interfaces. The specific capacitance of the
tion of the perovskite nanoparticles, resulting in improved nanorods reached 240 F g1 at a current density of 1 A g1 and
cycling stability and rate performance. As an anode the material maintained 98.0% of the initial value after 1000 cycles.171
shows a specific capacity of 805.7 C g1 at a current density of Table 5 summarizes the electrochemical properties of all-
50 mA g1, and can maintain 92% of the initial capacity after inorganic perovskite materials for SCs.
5000 cycles.169 Ying et al. prepared a polymetallic Ni–Co–Mn
perovskite (K1.0Ni0.4Co0.2Mn0.4F3.2/Ag) composite electrode
promoted by nanosilver, showing the synergistic effect of Ni, 5. Summary and outlook
Co and Mn redox substances and a substantial increase in the
comparative capacity of Ag active substances. It exhibited a As one of the most prominent material classes, all-inorganic
multi-electron phase transition mechanism and a kinetic beha- perovskite-type compounds have recently received significant
vior of pseudocapacitance and diffusion mixing. The best attention as the functional materials in the field of energy
composite electrode has a specific capacity of 489 C g1 at a storage, such as lithium-ion batteries, potassium–ion batteries,
current density of 1 A g1.170 This new nanoscale composite zinc-ion batteries, sodium-ion batteries, zinc–air batteries,

98 | Mater. Adv., 2023, 4, 79–104 © 2023 The Author(s). Published by the Royal Society of Chemistry
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Table 6 The charge storage mechanism of various all-inorganic perovskite materials in different types of devices

Types of
Material devices Electrolyte Reaction mechanism Ref.
CsPbBr3 + xLi + xe 2 CsPbBr3Lix
+ 
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CsPbBr3 Li-ion battery 0.5 M LiTFSI in BMIMTFSI 48

CsPbI3 Li-ion battery 1 M LiPF6 in EC : DMC = 1 : 1 Discharge: CsPbI3 + Li+ + e - LixCsPbI3 50
CsPbBr3@CNTs Li-ion battery 1 M LiPF6 in EC : DMC = 1 : 1 Discharge: CsPbBr3 + Li+ + e - Li-CsPbBr3 53
Li-CsPbBr3 + Li+ + e - CsBr + LiBr + Pb
Pb + Li+ + e - LixPb (1r x r 4.5)
K0.89Ni0.02Co0.03 Li-ion battery 1 M LiPF6 in EC : EMC : xK0.89M(II)0.89 M(III)0.11F3 + 2.11xLi+ + 58
Mn0.95F3.0@rGO DMC = 1 : 1 : 1 with 1% VC 2.11xe - xM + 0.89xKF +2.11xLiF
yM +2yLiF 2 yMF2 + 2yLi+ + 2ye
K0.89M(II)0.89 M(III)0.11F3 + zLi+ + ze 2
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LizK0.89M(II)0.89+z M(III)0.11zF3
(M = Ni, Co, Mn; 0 o x o 1; 0 o z o 0.11, 0 o y o x)
KCuF3 Li-ion battery 1 M LiPF6 in EC : EMC : xKCuF3 + 2xLi+ + 2xe - xCu + xKF + 2xLiF 67
DMC = 1 : 1 : 1 with 1% VC yCu + 2yLiF 2 yCuF2 + 2yLi+ + 2ye
(0 o x o 1; 0 o y o x)
KNi0.1Co0.9F3 Li-ion battery 1 M LiPF6 in EC : EMC : yKMF3 + 2yLi+ + 2ye - yKF + 2yLiF + yM 68
DMC = 1 : 1 : 1 with 1% VC yM + 2yLiF 2 yMF2 + 2yLi+
(M = Ni, Co; 0 o y o 1)
K0.97Ni0.31Co0.34 Li-ion battery 1 M LiPF6 in EC : EMC : xABF3 + 2xLi+ + 2xe - xB + xAF + 2xLiF 69
Mn0.35F2.98 DMC = 1 : 1 : 1 with 1% VC yB + 2yLiF 2 yBF2 + 2yLi+ + 2ye
(A = K; B = Ni, Co, Mn; 0 o x o 1; 0 o y o x)
K1.1Zn0.17 Li-ion battery 1 M LiPF6 in EC : EMC : xKMF3 + 2xLi+ + 2xe - xKF + 2xLiF + xM 70
Mn0.83F3.03 DMC = 1 : 1 : 1 with 1% VC yM + 2yLiF 2 yMF2 + 2yLi+ + 2ye
aZn + aLi+ + ae 2 aLiZn
(M = Zn, Mn; 0 o x o 1; 0 o y o x; 0 o a o 0.17x)
NaNbO3 Li-ion battery 1 M LiPF6 in EC : EMC : xNaNb5+O3 + xLi+ + xe 2 xLiNaNb4+O3, 0 o x o 1 81
DMC = 1 : 1 : 1 with 1% VC yLiNaNb4+O3 + yLi+ + ye 2 yLi2NaNb3+O3, 0 o y o x
KTaO3 Li-ion battery 1 M LiPF6 in EC : DEC : 2KTaO3 + 10Li + + 10e - 2Ta + K2O + 5Li2O 82
DMC = 2 : 1 : 2 Ta + 3Li2 2 LiTaO3 + 5Li+ + 5e
BaSnO3/rGO Li-ion battery 1 M LiPF6 in EC : DEC = 1 : 1 BaSnO3 + 4Li+ + 4e - BaO + 2Li2O + Sn 89
BaO + 2Li + + 2e 2 Li2O + Ba
Sn + 4.4Li + + 4.4e 2 Li4.4Sn
Ba + 4Li + + e 2 Li4Ba
ZnSnO3 Na-ion battery 1 M NaClO4 in EC : PC = 1 : 1 ZnSnO3 + 6Na+ + 6e - 3Na2O + Zn + Sn 95
4Sn + 15Na+ + 15e 2 Na15Sn4
13Zn + Na+ + e 2 NaZn13
Na0.5Bi0.5TiO3 Na-ion battery 1 M NaClO4 in PC Na0.5Bi0.5TiO3 + 12Na+ + 12e - TiO2 + Na2O + Bi 97
with 2%FEC Bi + 4Na+ + 4e - NaxBi
Bi + Na+ + e 2 BiO + Na
K0.82Co0.43Mn0.57 Na-ion battery 0.85 M NaPF6 in EC : xK0.82MF2.66 + 1.84xNa+ + 1.84xe - 101
F2.66@rGO EMC : DMC = 1 : 1 : 1 xM + 0.82xKF + 1.84xNaF
with 1% FEC yM + 2yNaF 2 yMF2 + 2yNa+ + 2ye
K0.82MF2.66 + zNa+ + ze 2 NazK0.82MF2.66
(M = Co; Mn. 0 o x o 1; 0 o z o 1; 0 o y ox)
LaNi0.2Mn0.8O3 Zn-ion battery 2 M ZnSO4 + 0.2 M MnSO4 LaNixMn1xO3 + yZn2+ + 2ye 2 LaZnyNixMn1xO3 120
NaNiF3 SCs 3 M KOH and 0.5 M LiOH Ni2+ + 3OH - NiOOH + H2O + e 162
KNi0.8Co0.2F3 SCs 3 M KOH and 0.5 M LiOH Ni2+ + 3OH 2 NiOOH + H2O + e 164
Co2+ + 3OH 2 CoOOH + H2O + e
K–Co–Mn–F3 SCs 3 M KOH and 0.5 M LiOH M2+ + 3OH 2 MOOH + H2O + e 165
(Co/Mn =6 : 1) MOOH + OH 2 MO2 + H2O + e (M = Mn, Co)
K0.95Ni0.30Co0.38 SCs 3 M KOH and 0.5 M LiOH K0.95[M2+0.58M3+0.10]Zn0.32F3.05 + 2.68OH - 168
Zn0.32F3.05 0.95K+ + 3.05F + 0.68MOOH+ 0.32ZnO + H2O +0.58e
CoOOH + OH 2 CoO2 + H2O + e
NiOOH + H2O + e 2 Ni(OH)2 + OH
CoOOH + H2O + e 2 Co(OH)2 + OH
NiOOH + e 2 NiO + OH
3CoOOH + e 2 Co3O4 + H2O + OH
Co3O4 + 4H2O + 2e 2 3Co(OH)2 + 2OH (M = Ni, Co)
NaCo0.2Ni0.8F3/rGO SCs 3 M KOH and 0.5 M Ni2+ + 3OH 2 NiOOH + H2O + e 169
LiOHH2O Co2+ + 3OH 2 CoOOH + H2O + e
K1.0Ni0.4Co0.2 SCs 3 M KOH and K1.0[M2+0.8M3+0.2]F3.2 + 3OH - K+ + 3.2F + MOOH + H2O + 0.8 e 170
Mn0.4F3.2/Ag(37%) 0.5 M LiOH CoOOH + OH 2 CoO2 + H2O + e
MnOOH + OH 2 MnO2 + H2O + e
NiOOH + H2O + e 2 Ni(OH)2 + OH
NiOOH + e 2 NiO + OH
CoOOH + H2O + e 2 Co(OH)2 + OH
3CoOOH + e 2 Co3O4 + H2O + OH
3MnOOH + e 2 Mn3O4 + H2O + OH
2Ag + 2OH 2 AgO2 + H2O + 2e
Ag2O + 2OH 2 2AgO + H2O + 2e (M = Ni/Co/Mn)

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Li–O2 batteries and supercapacitors. Table 6 summarizes the adaptability to load variations and toughness under adverse
charge storage mechanism of various all-inorganic perovskites conditions. (6) When perovskites are used as electrode materials
in different types of devices. However, there are no practical for energy storage devices, the entire electrode material is usually
commercial energy storage devices based on perovskite materi- composed of active materials, conductive agents, and binders.
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als. Although perovskite materials have shown diverse merits in Therefore, the design of self-supporting electrodes is an attractive
different energy-related applications, some key performance research area, which can enhance active material utilization,
factors must be optimized before they can be widely used charge transfer efficiency, and structural stability. (7) Perovskites
in real devices. The modulation of materials in terms of still need to be further enhanced in terms of catalytic activity,
microstructure, morphology and surface area can enhance stability and conductivity when applied as catalysts in metal–air
the capacity, cycling stability, etc., such as designing nanoscale batteries. Doping, defect, facet, and morphology engineering all
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electrode materials with hollow, porous, flower-like, and core– could strengthen OER/ORR catalytic performance, but composites
shell shapes. In addition, the strategy of A-site, B-site or a with internal synergies are far more promising catalysts for future
combination of A-site and B-site doping can tune the crystal metal–air batteries.
structure, reactivity, catalytic activity, etc., and significantly In conclusion, all-inorganic perovskites have made great
increase the overall electrochemical performance of the mate- progress in the field of electrochemical energy storage in the
rial. The double-perovskite structure possesses a more ordered past few decades, and we believe that a deep understanding of
structural arrangement than the element-doped perovskite, the fundamental principles, optimization methods, and appli-
which prevents lattice distortion and improves cycle stability. cation requirements will further advance the development of
The defect engineering of perovskite oxides and fluorides has energy storage devices.
been extensively studied, which is a key factor affecting the
quality and charge transfer performance. The ion size and the
valence change of B-site ions, as well as oxygen vacancies in Conflicts of interest
perovskite ABO3, determine the occupancy site, the electrical
conductivity and the ionic conductivity, respectively, while the There are no conflicts to declare.
ionic conductivity in ABF3 is related to the vacancies of A-site
and F. Loading certain amounts of metals or making compo-
sites with good electron conductors such as Ag, carbon nano- Acknowledgements
tubes, graphene or MXene can effectively improve the electron Financial support from the National Key R & D Program of
conductivity and cyclic stability. All the above means of mate- China (2021YFB2400400), the Key Project of National Natural
rial modification can promote the application of all-inorganic Science Foundation of China (52131306), Project on Carbon
perovskite-type materials in energy storage. Emission Peak and Neutrality of Jiangsu Province (BE2022031-4)
It should also be emphasized that there are still some and the Research Foundation of State Key Lab (ZK201805,
challenges when perovskite materials are used in the field of ZK201717) is greatly appreciated.
energy storage. (1) The exploration of new all-inorganic
perovskite-type materials is still necessary, and the material
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