Journal of Energy Chemistry 57 (2021) 516–542

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Journal of Energy Chemistry

journal homepage: www.elsevier.com/locate/jechem

Review

Oxide-based cathode materials for rechargeable zinc ion batteries:

Progresses and challenges
Yingze Zhou a, Fandi Chen a, Hamidreza Arandiyan b,c, Peiyuan Guan a, Yunjian Liu d,⇑, Yuan Wang e,⇑,
Chuan Zhao e, Danyang Wang a, Dewei Chu a
a
School of Materials Science and Engineering, The University of New South Wales, Sydney 2052, Australia
b
Laboratory of Advanced Catalysis for Sustainability, School of Chemistry, The University of Sydney, Sydney 2006, Australia
c
The University of Sydney Nano Institute (Sydney Nano), The University of Sydney, NSW 2006, Australia
d
School of Material Science and Technology, Jiangsu University, Zhenjiang 212013, Jiangsu, China
e
School of Chemistry, The University of New South Wales, Sydney, New South Wales 2052, Australia

a r t i c l e i n f o a b s t r a c t

Article history: With the increasing demands for electrical energy storage technologies, rechargeable zinc ion batteries
Received 29 May 2020 (ZIBs) have been rapidly developed in recent years owing to their high safety, low cost and high energy
Revised 13 August 2020 storage capability. The cathode is an essential part of ZIBs, which hosts zinc ions and determines the
Accepted 16 August 2020
capacity, rate and cycling performance of the battery. The mainstream cathodes for ZIBs are oxide-
Available online 28 August 2020
based materials with tunnel, layer or 3D crystal structures. In this review, we mainly focus on the latest
advanced oxide-based cathode materials in ZIBs, including manganese oxides, vanadium oxides, spinel
Keywords:
compounds, and other metal oxide based cathodes. In addition, the mechanisms of zinc storage and
Zinc ion batteries
Oxide-based cathode
recent development in cathode design have been discussed in detail. Finally, current challenges and per-
Manganese oxides cathode spectives for the future research directions of oxide-based cathodes in ZIBs are presented.
Vanadium oxides cathode Ó 2020 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by
ELSEVIER B.V. and Science Press. All rights reserved.

Yingze Zhou received her B.E. degree from Qilu Fandi Chen received his undergraduate degree in
University of Technology (Jinan, China) in 2012 and M. Metallurgical and Materials Engineering from Univer-
E. degree at the University of New South Wales sity of Alabama in May 2018. He is currently a Master
(UNSW), Sydney in 2017. She is currently pursuing her student of Materials Science and Engineering at UNSW
PhD degree under the supervision of A/Prof. Dewei Chu Sydney.
and A/Prof. Danyang Wang in the School of Materials
Science and Engineering at UNSW. Her research
interest is on advanced cathode materials for zinc ion
batteries.

⇑ Corresponding authors.
E-mail addresses: lyjian122331@163.com (Y. Liu), yuan.wang4@unsw.edu.au (Y. Wang).

https://doi.org/10.1016/j.jechem.2020.08.038
2095-4956/Ó 2020 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press. All rights reserved.
Y. Zhou, F. Chen, H. Arandiyan et al.
Hamidreza Arandiyan received his Ph.D. from Tsin-
ghua University in 2014. He was awarded Vice-
Chancellor’s Research Fellowship from the University
of New South Wales (UNSW) in 2015, under the
supervision of Scientia Prof. Rose Amal, and was
awarded the University of Sydney Fellowship in the
School of Chemistry under the direction of Prof. Tho-
mas Maschmeyer in 2018. His research interest lies in
heterogeneous catalysis for environmental remedia-
tion and energy applications.
Peiyuan Guan received the B.S. degree from Gansu
Agricultural University, Lanzhou, China in 2012 and M.
S. degree from University of New South Wales
(UNSW), Sydney in 2018. He is currently working
toward the PhD degree in the School of Materials Sci-
ence and Engineering at UNSW. His research interest is
focused on surface modification of cathode materials
for lithium-ion batteries.
Yunjian Liu obtained his PhD degree in 2009 from
Central South University. Then he entered Chery
Automobile Company Postdoctoral Research Station,
China as a post-doc researcher. At present, he is a
professor in the School of Materials Science and Engi-
neering, Jiangsu University. His research interest
focused on advanced energy materials and electro-
chemistry. He gained supports of the National Natural
Science Foundation of China. He possessed over 20
highly cited publications and 10 patents.
Yuan Wang (Helena) received her PhD degree under
the supervision of Scientia Prof. Rose Amal in the
School of Chemical Engineering at the University of
New South Wales (UNSW) in 2018. She has been as a
Research Assistant at the National Research Center for
Geoanalysis, Chinese Academy of Geological in 2013.
She is currently working as a Postdoctoral Research
Associate under the supervision of Prof. Chuan Zhao in
the School of Chemistry at UNSW. Her research inter-
est focuses on the development and characterization of
nanoporous materials for energy-related applications.
1. Introduction
With the development and popularisation of renewable energy
sources such as wind, tidal, and solar, there is a great demand for
the development of energy storage technologies that meet the
storage and utilization of intermittent renewable energy [1–3].
For the thirty years since the first commercialization in the
1990s, rechargeable lithium-ion batteries (LIBs) have been widely
used as the most popular energy storage technology in electronic
devices and vehicles [2,4,5]. However, technological weaknesses
of LIBs including high cost and safety issues have urged the devel-
opment of new energy storage technologies to obtain safe, low cost
and environmentally friendly battery technologies [6–11]. Inspired
by LIBs, researchers have a huge interest in developing other
517
Journal of Energy Chemistry 57 (2021) 516–542
Chuan Zhao received his Doctoral Degree from
Northwest University in 2002. He then completed
four-year postdoctoral research at the University of
Oldenburg. In 2006, he moved to Monash University as
a senior research fellow. In 2010, he started his inde-
pendent research career at the University of New
South Wales, Sydney. At present, he is a professor in
the School of Chemistry at UNSW. His research focuses
on developing electrochemical technologies, discover-
ing the novel nanomaterials and their implications for
clean energy and biomedicine applications. He is also
interested in ionic liquids chemistry and the applica-
tions for electrochemical energy conversion and storage and sustainable chem-
istry.
Danyang Wang is currently an associate professor and
Australian Research Council Future Fellow in the
School of Materials Science and Engineering at UNSW,
Sydney. He obtained his PhD degree in applied physics
from the Hong Kong Polytechnic University in
December 2006. He is a materials scientist specializing
in experimental design and optimization of a broad
range of novel functional oxide thin films and nanos-
tructures for nanoelectronic, photonic and energy-
related applications. He has been at the forefront of
understanding the processing techniques/conditions
that control the materials properties, improving the
performance of existing materials, and exploring new functionalities and their
related device applications.
Dewei Chu received his PhD degree Materials Science
from Shanghai Institute of Ceramics, Chinese Academy
of Science in July 2008. He worked in Advanced Insti-
tute of Science and Technology (AIST) Japan for 3 years.
He is currently working as an associate professor in the
School of Materials Science and Engineering at UNSW.
His research interest focuses on nanoionic materials
for energy-related applications.
mobile metal ion based rechargeable batteries, such as
aluminium-ion, magnesium-ion, zinc-ion, sodium-ion and
potassium-ion batteries [12–15]. However, the large radii of Na+
and K+ make it difficult to find suitable electrode materials to
accommodate the reversible intercalation and extraction of these
cations, and these two metals have high activity and potential
safety issues. Instead, multivalent cations Al3+ and Mg2+, Zn2+ with
lower activity and abundant natural sources are promising candi-
dates for rechargeable batteries. Among them, zinc ion batteries
(ZIBs) have received intense attention as a new type rechargeable
battery because of their advantages of high safety, low cost, easy
assembly, large capacity, environmental friendliness, and abun-
dant zinc resources [15–17]. As shown in Fig. 1, ZIBs usually consist
of zinc metal anode, zinc ion host material cathode, and zinc-
Y. Zhou, F. Chen, H. Arandiyan et al.
Fig. 1. Electrochemical principles of (a) alkaline zinc-based batteries, and (b) rechargeable aqueous ZIBs. Reproduced from Ref. [18] with permission from Wiley-VCH.
containing electrolyte, which is very similar to the structure of
LIBs. Zinc ions move between the anode and cathode electrodes
during charging and discharging.
Based on different electrolytes, ZIBs can be categorized into
aqueous type (zinc salt aqueous electrolyte) and nonaqueous type
(gel polymers electrolyte). Among them, the aqueous electrolyte of
ZIBs usually is a mildly acidic or neutral zinc-containing elec-
trolyte with pH values from 3.6 to 6 (such as ZnSO4, Zn(CF3SO3)2,
Zn(NO3)2, Zn(CH3COO)2, Zn(TFSI)2, ZnF2, ZnCl2, and Zn(ClO4)2),
which have been widely explored. Nevertheless, to avoid the
safety concern caused by leakage and dissolution of electrode
materials in aqueous electrolyte, the nonaqueous electrolyte gel
polymer electrolyte (GPE) with limited free water volume has been
rapidly developed in recent years. GPE can act as a separator, sim-
plifying the assembling process of ZIB [19], and replacing the bin-
ders [20] to alleviate the growth of zinc dendrites [21]. To date,
various gel polymer electrolytes were investigated, including poly
(vinyl alcohol) (PVA)-based gel, gelatin-based hydrogel gel [22]
and polyacrylamide (PAM)-based hydrogel gel [23]. In recent
years, some novel hydrogel electrolytes with self-healing, cooling
recovery, electrochromism, thermal response, and photo-
response capabilities were also investigated [24,25]. Unlike Li-ion
batteries that need to be assembled under air isolation, ZIBs can
be safely assembled in the open air. The liquid electrolyte ZIBs
are usually assembled into coin cells or soft-packed batteries: as
shown in Fig. 2(a), the coin cell is assembled by pressing various
components (including top and bottom caps, electrodes and sepa-
rator, spacer, and wave spring) together. The pouch-type battery
consists of several anode–separator–cathode stacks, as shown in
Fig. 2(b). In contrast, the solid-state electrolyte ZIBs are usually
assembled into sandwich structures or cable structures (Fig. 2c
and d). The basic configuration of the flexible ZIBs is also anode–
electrolyte–cathode: the active material and Zn can be separately
coated on flexible current collectors, or simply using the flexible
electrode materials. The sandwich structure solid-state electrolyte
ZIBs have almost the same structure as liquid electrolyte ZIBs,
except that a gel electrolyte is used instead of the separator. The
cable type ZIBs have different designs. The wind the yarn cathode
and Zn yarn anode on to an elastic fiber, and then coat a gel elec-
trolyte between two electrodes to form a double-helix yarn struc-
ture. The gel electrolyte and flexible cathode layers are wrapped
on the surface of the Zn wire sequence and assembled into a coax-
ial cable structure. Besides, it can also be printed as flexible ZIBs
with ultrathin polymer electrolyte [26]. In addition to traditional
energy storage devices, the most attractive application of ZIB is
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Journal of Energy Chemistry 57 (2021) 516–542
mechanical flexibility. The flexible ZIBs can be used in wearable
devices such as smartwatches, smart insoles, and wearable pulse
sensors [27].
In recent years, the research on ZIBs has made considerable pro-
gress, but the development of ZIBs still faces a series of scientific
and technical difficulties. First of all, the anode of ZIBs has the
problems of dendrite growth (especially under high current) and
poor reversibility. Moreover, aqueous system ZIBs are limited by
factors such as water decomposition whereas nonaqueous system
ZIBs with polymer electrolytes suffer from insufficient mechanical
strength, undesirable ionic conductivity, and fast degradation,
which makes them face the problem of narrow voltage window
[15,17]. Especially, as the critical component of ZIBs, cathode mate-
rials largely determine the working mechanism, capacity, rate and
cycle performance. Bottlenecks of cathode materials such as low
capacity and short life have become key factors hindering the
development of ZIBs. Up to now, many different types of cathode
materials of ZIB have been developed for ZIBs, most of which exhi-
bit ample tunnel space and 3D frameworks that can support
enough space to host zinc ions. Among them, oxide-based materi-
als including manganese-based oxide and vanadium-based oxide
are the most widely used cathode materials because of the variety
of crystal structures and multiple oxidation states, which make
them generally exhibit the superior electrochemical performance
than other kinds of cathode materials. Besides the selection of
cathode materials, materials morphology control and cathode
design in ZIBs studies have also become hotspots in past years.
In addition, the great variety of metal oxides cathode materials
such as MnO2, Mn2O3, Mn3O4, V2O5, V2O5∙nH2O, H2V3O8 and tran-
sition metal ion-stabilized vanadium oxides are also widely used in
other energy storage device (for example, zinc-ion hybrid capaci-
tors) [30]. The study of metal oxides cathode materials for ZIBs
are also helping to solve the challenges in supercapacitors develop-
ment such as manganese dissolution from the MnO2 cathode, the
low operating potentials of vanadium oxides.
However, there is a lack of review papers on the oxide-based
cathodes for ZIBs, which mainly cover the mechanism, cathode
design and recent progress. Therefore, it is necessary to review
the recent progress in the metal oxide cathode materials, including
their materials design and working mechanisms in ZIBs. In this
review, we have classified the metal oxide cathode into manganese
oxide-based, vanadium oxide-based, other metal oxides cathodes,
and some spinel compounds cathodes, and review their recent pro-
gress in working mechanisms study, morphology control, and cath-
ode design. The summary and perspective are provided for future
Y. Zhou, F. Chen, H. Arandiyan et al.
Fig. 2. Schematic diagrams of (a) coin cell, (b) pouch cell. Reproduced from Ref. [28] with permission from Nature Publishing Group. (c) Fabrication and encapsulation of the
yarn ZIB. Reproduced from Ref. [23] with permission from the American Chemical Society, and (d) schematic diagrams of flexible soft-packaged. Reproduced from Ref. [29]
with permission from Wiley-VCH.
research directions, hoping to provide help for ZIBs’ study. The
review is divided into five parts: (1) research background and
introduction of ZIBs, focus on oxide-based cathodes based on (2)
manganese oxide-based cathodes, (3) vanadium oxide-based cath-
odes, (4) other oxide-based cathodes and (5) summary of current
challenges and perspective for future research directions.
2. Manganese oxide-based cathodes
Manganese oxides have been widely used as battery materials
in ZIBs in the last decades due to the high operating voltage and
comparable specific capacity [31]. In order to better understand
the manganese oxides used in ZIBs and the effects of the crystal
structure of manganese-based materials on the mechanism of ZIBs,
we summarised the latest research of working mechanisms and
electrode design on manganese oxide cathodes.
2.1. Manganese dioxide (MnO2)
To date, the most commonly studied cathode material for ZIBs
is MnO2 due to its high valence state and abundant crystal struc-
ture. The performance of the ZIBs highly depends on the crystal
structure of MnO2. MnO2 have various crystal structures, including
tunnel structures, layer structure and spinel structure. This is
because the basic unit MnO6 octahedra can build different tunnel
structures by sharing corners or edges as chains, layers or tunnel
structures [32]. As shown in Fig. 3(a)–(c), (i) MnO6 octahedra are
assembled into single/double/triple chains by sharing edges to
form the different tunnel structures by sharing corners, including
pyrolusite-type (b-MnO2) with (1*1) tunnels, ramsdellite-type (R-
MnO2) with (1*1) + (1*2) tunnels, nsutite-type (c-MnO2) with
(1*1) + (1*2) tunnels, hollandite-type (a-MnO2) with (2*2) tunnels,
519
Journal of Energy Chemistry 57 (2021) 516–542
romanechite-type with (2*3) tunnels and todorokite-type MnO2
with (3*3) tunnels; (ii) Layered MnO2 (d-MnO2) is composed of
MnO6 octahedra sheets, assembled with MnO6 octahedra through
sharing edges; (iii) The 3D structure is a spinel-like structure (k-
MnO2), where Mn2+ and Mn3+ are located in tetrahedral and octa-
hedral sites, respectively.
As shown in Fig. 3(d), MnO2 exhibits different electrochemical
performances according to the pH value and potential. In fact, in
addition to the pH of the aqueous electrolyte, the cycling parame-
ters also influence the energy storage mechanism of the batteries,
which is not fully understood yet. In recent years, the reported
reaction mechanisms are generally divided into three mechanisms:
Zn2+ reversible intercalation mechanism, chemical conversion
reaction mechanism and H+ and Zn2+ co-insertion mechanism. A
typical Zn2+ reversible intercalation was initially reported in Zn/
a-MnO2 batteries (dZn2+ + 2de
+ MnO2 M ZndMnO2 [33], dZn2+ + 2-
e
+ 2MnO2 M ZndMn2O4 [34]), which refers to the migration of
Zn2+ between tunnels of a-MnO2 cathode and Zn anode. The chem-
ical conversion reaction occurs between a-MnO2 and MnOOH,
which is caused by the reaction between MnO2 with a proton from
water (H2O M H+ + OH
, MnO2 + H+ + e
M MOOH) [35]. The co-
insertion mechanism of H+ and Zn2+ is that the cathode materials
with open tunnels or layered structure may enable the co-
insertion of H+ and Zn2+. Most types of MnO2 cathodes have been
reported not only Zn2+ reversible intercalation mechanism, which
may be triggered by the different types of electrolyte and cycle
conditions. The formation of ZHS (Zn4(OH)6(SO4)5H2O) or its ana-
logues on the surface of many types of MnO2 cathodes during
charge/discharge cycles can help to improve the capacity and
kinetic performance of the battery. However, the working mecha-
nisms of ZIBs have not yet reached a consensus. In this part, these
three energy storage mechanisms of ZIBs will be discussed based
on the different crystal structures of MnO2.
Y. Zhou, F. Chen, H. Arandiyan et al.
Fig. 3. (a–c) Different Mn oxide structures, and (d) Pourbaix diagram of MnO2. Reproduced from Ref. [32] with permission from the Royal Society of Chemistry.
2.1.1. a-MnO2
The hollandite-type MnO2 with 2*2 tunnels is the most widely
studied manganese oxide. The basic unit MnO6 octahedra in
hollandite-type MnO2 is assembled by sharing corners into double
chains. In 2009, researchers proposed a partially crystallized a-
MnO2 intercalated by reversible Zn2+ (dZn2+ + 2de
+ MnO2 M Znd-
MnO2), whose capacity can reach 210 mAh g
1 [33]. Subsequently,
a new intercalation process (dZn2+ + 2e
+ 2MnO2 M ZndMn2O4)
was discovered, and the newly formed ZnMn2O4 phase was
revealed by electrochemical impedance spectroscopy (EIS) [34].
The reversible formation/deformation of ZnMn2O4 and the reversi-
ble phase transition of Mn4+/Mn3+ were observed by X-ray diffrac-
tion (XRD) and ex-situ synchrotron X-ray absorption spectroscopy
(XAS) during the discharge/charge process [36]. It was found that a
reversible phase transition occurred between layered Zn birnessite
and a-MnO2 accompanied by the insertion of Zn2+ [37]. As shown
in Fig. 4(a), the insertion of Zn2+ and the dissolution of manganese
during the discharge process cause the phase transformation of a-
MnO2 into layered Zn birnessite (Mn4+(s) + e
? Mn3+(s), 2Mn3+(-
s) ? Mn4+(s) + Mn2+(aq)). During the charging process, Mn2+ rein-
serts into the lattice and rebuilds the tunnel structure of a-MnO2
(Mn2+(aq) ? Mn4+(s) + 2e
). These studies speculated that Zn2+
could be reversibly inserted/extracted into a-MnO2, but the exact
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Journal of Energy Chemistry 57 (2021) 516–542
process is still controversial. Fig. 4(b) shows another phase transi-
tion process between layered Zn birnessite and a-MnO2. The lay-
ered Zn birnessite (7 Å interlayer spacings) is not a direct
product of Zn2+ insertion but is transformed from the unstable
Zn-buserite (10 Å interlayer spacings) by losing water molecules.
The reversible phase transition between Zn-buserite and a-MnO2
is triggered by a series of single- and two-phase electrochemical
reactions on the cathode [38]. In general, the reactions occurred
during Zn2+ insert/extract progress are still under debate, but the
influence of different electrolyte should be paid more attention
in future work.
In addition to the Zn2+ insertion/extraction mechanism, another
mechanism shown in Fig. 4(c) is the formation of Zn4(OH)6(SO4)
5H2O (ZHS) on the surface of a-MnO2 (i.e., 4Zn2+ + 6OH
+ SO2

4 + 5H2-
O M Zn4(OH)6(SO4)5H2O;) [35]. The dissolution of Mn2+ causes
increasing pH value of the electrolyte, which in turn results in
the formation of ZHS. Firstly, manganese dioxide on the cathode
provides active trivalent manganese by the reaction of Mn4+(-
s) + e
? Mn3+(unstable), then following the reaction Mn3+(-
unstable) ? Mn4+(s) + Mn2+(aq), manganese is dissolved into the
aqueous electrolyte. Therefore, the increase of pH is caused by
the reaction of MnO2 + 2H2O + 2e
? Mn2+ + 4OH
[35]. During
this process, Zn2+ will not be inserted into the a-MnO2 cathode,
Y. Zhou, F. Chen, H. Arandiyan et al.
Fig. 4. (a) a-MnO2 with a 2*2 tunnel structure incorporates zinc ions during discharge. Reproduced from Ref. [37] with permission from Nature Publishing Group, (b) the
structural development of a-MnO2 after the insertion of zinc ions (buserite) and drying in the oven (birnessite). Reproduced from Ref. [38] with permission from the Royal
Society of Chemistry, and (c) discharge process for a-MnO2/Zn cell employing aqueous ZnSO4 electrolyte. Reproduced from Ref. [35] with permission from Wiley-VC.
because after washing off the ZHS layer, there is no Zn2+ in the a-
MnO2 cathode [35]. The good cycling stability (100% capacity
retained after 1500 cycles at 500 mA g
1) was achieved by directly
applying ZHS as a cathode [39]. Furthermore, Pan et al. reported
the formation of ZHS by conversion reaction between a-MnO2
and H+ [40]. The cathode reaction equations are as follows:
H2 O $ Hþ þ OH

MnO2 þ Hþ þ e
$ MOOH
1 2þ 1 x 1 Fig. 5(d) showed the formation of the MOOH phase (triggered by
Zn þ OH
þ ZnSO4 þ H2 O $ Zn4 ðOHÞ6 ðSO4 Þ  xH2 O
2 6 6 6
The interaction between MnO2 and water proton triggered the
formation of MOOH (Eq. (2)). Then, the neutral charge (OH
from
Eq. (1)) reacts with ZnSO4 and H2O to form a large flake-like ZHS
(Eq. (3)). The above reactions, which provide a high energy density
of the battery (~170 Wh kg
1 at C/3) were confirmed by scanning
transmission electron microscopy-energy-dispersive X-ray spec-
troscopy (STEM-EDS) mapping. In addition to conventional a-
MnO2 cathodes, some new a-MnO2 cathodes have been reported
in recent years, such as onion-like carbon (OLC) integrated a-
MnO2 nanorods (a-MnO2/OLC) composite cathode with an
enlarged surface area [41]. Many studies have focused on a-
MnO2 because it shows high potential as a cathode candidate
material for ZIBs. However, the working mechanisms of a-MnO2
are under debate. Even though the initial reported Zn2+ reversible
intercalation mechanism is a conflict with the phenomenon that
the water molecules are the important participant of the reaction,
it is the cornerstone for further study. More effort is required to
clarify the reaction mechanism of the a-MnO2 cathode, for exam-
ple, the in-situ XRD may be a choice to analyse the phase transition
and reaction process during the charge/discharge process.
Journal of Energy Chemistry 57 (2021) 516–542
2.1.2. e-MnO2
Akhtenskite-MnO2 (e-MnO2) is a metastable phase, exhibiting
hexagonal symmetry, in which Mn4+ is randomly distributed in
one-half of the octahedron [42]. There are only a few reports on
e-MnO2 cathodes. For example, in 2017, a co-insertion mechanism
of H+ and Zn2+ in e-MnO2 was reported [43]. As shown in Fig. 5(a),
the binder-free cathode was synthesized by an electrodeposition
method. The surface of carbon fibre paper (CFP) was fully covered
ð1Þ with nanostructured MnO2, which was confirmed by the SEM
results (shown in Fig. 5b). The galvanostatic intermittent titration
technique (GITT) profiles of e-MnO2 electrodes described a signifi-
ð2Þ cant resistance difference between charge transfer and diffusion in
the region I and II, which was attributed to the H+ and Zn2+ inserted
continuously into MnO2 cathode (Fig. 5c). The XRD patterns in
ð3Þ the H+ insertion) and the ZnMn2O4 phase (triggered by the Zn+
insertion) and confirmed the co-insertion of Zn2+ and H+. After that,
a transformed e-MnO2 from Mn3O4 was reported as a cathode
material [44]. The prepared Mn3O4 cathode was converted into e-
MnO2 at a low current density (100 mA g
1) in the first 10 cycles,
and the reversible conversion reaction between MnO2 and MnOOH
occurred in the subsequent cycles. The transformed e-MnO2 can
achieve a high reversible capacity (221 mAh g
1 at 100 mA g
1)
and excellent capacity retention (>92% after 500 cycles at
500 mA g
1). La3+-doped e-MnO2 (denoted as LMO), Ca2+-doped
e-MnO2 (denoted as CMO), and La–Ca co-doped e-MnO2 (denoted
as LCMO) through a facile coprecipitation method were reported
in 2020 [45]. The enlarged lattice spacing contributes to the large
capacities, which increase the insertion of H+ and Zn2+. As shown
in Fig. 5(e), the capacity of LCMO is higher than the pristine MO
at all current densities. All modified MnO2 cathodes (including
CMO, LMO and LCMO) have a positive effect on the increase of
MO capacity, and the capacity intention for long cycles of modified
MnO2 is much higher than pristine MnO2 (Fig. 5f and g), which
indicates that the doping ions can significantly improve the
reversibility of the MnO2 cathode by enlarged lattice spacing. In
521
Y. Zhou, F. Chen, H. Arandiyan et al. Journal of Energy Chemistry 57 (2021) 516–542

Fig. 5. (a) Schematic illustration of the nanocrystalline MnO2 electrodeposited on CFP process, and the corresponding SEM images of CFP before and after electrodeposition,
(b) SEM image of MnO2@CFP, (c) discharge galvanostatic intermittent titration technique (GITT) profiles of the Zn/MnO2@CFP cell (50 mA g
1 for 120 s followed by 4 h rest),
and (d) ex-situ XRD patterns of the MnO2@CFP cathode at depth of discharge at 1.3 and 1.0 V (inset of Fig. 4d), respectively. Reproduced from Ref. [43] with permission from
the American Chemical Society. (e) Discharge capacities of the MO and LCMO electrodes at different current densities. (f) Capacities of the MO, LMO, CMO and LCMO
electrodes at 0.1 A g
1. (g) Cycling performance of the MO and LCMO electrodes. Reproduced from Ref. [45] with permission from the Royal Society of Chemistry.

fact, doping is a hot point for cathode modifications, many
metal ions such as Ni, Ce and Al were also used in ZIBs’ cathode
doping.
2.1.3. k-MnO2 (Spinel MnO2)
The Zn2+ and H2O intercalation mechanism in 3D structured
spinel MnO2 (k-MnO2) has been reported. After studying the cath-
ode in lithium batteries, researchers found that ZnMn2O4 (ZMO)
can also be a cathode material for ZIBs because Zn2+ (0.06 nm)
and Li+ (0.059 nm) have very similar ion radii. [46] However, the
performance of ZnMn2O4-ZIB is low due to limited space for Zn2+
in the 3D structure. Therefore, the researchers believed that the
cation defective ZMO spinel could be a better cathode material to
host Zn2+. In 2016, N. Zhang et al. reported a cation-defective
ZnMn1.86Y0.14O4 (Y denotes vacancy) as cathode of ZIBs (Fig. 6a),
which followed the reaction mechanism: ZnMn1.86Y0.14O4 M Zn1
x-
Mn1.86Y0.14O4 + 2xe
+ xZn2+ (0 < x < 1) [46]. In order to increase the
lattice space of the spinel structure ZMO, ZnMn2O4 nanoparticles
co-substituted by nickel and cobalt spinel were synthesized by
hydrothermal method, and the nanoparticles were homogeneously
loaded on the N-doped reduced graphene oxide (ZnNixCoyMn2-x-y-
O4@N-rGO) [47]. Compared with ZMO@N-rGO (a = b = 5.7131 Å
and c = 9.203 Å), ZNCMO@N-rGO with Ni and Co inserted in the
octahedron has a larger lattice parameter (a = b = 5.7421 Å and
c = 9.2565 Å), which was beneficial to the diffusion of zinc ions dur-
ing charging and discharging. The larger lattice parameter in the
active material reduced the hindrance of zinc ions during the pro-
cess of insertion/de-insertion and improved the structural frag-
mentation caused by the volume expansion of ions during the
insertion/de-insertion process, and significantly improved the
cycling performance of the material (as shown in Fig. 6b).
In addition, another spinel, Mn3O4, is regarded as one of the
potential cathode materials for ZIBs, due to its high discharge
capacity, low cost, and nontoxicity. Besides the phase transition
of Mn3O4 cathode described earlier (in e-MnO2 part), another
structure change was also found in the Mn3O4 cathode (the conver-
sion of Mn3O4 to brinessite-type MnO2), which was caused by the
Mn2+ dissolution and H2O insertion (2Mn3O4 ? Mn5O8 + Mn2+ + 2e
,
Mn5O8 + xH2O ? 4MnO2xH2O + Mn2+ + 2e
, shown in Fig. 6c) [48].
However, since the discovery of MOOH and ZHS proved the H+
insertion mechanism, the mechanism of this study is more
complex.
Besides the pure Mn3O4 cathode material, some Mn3O4-based
nanocomposite cathodes have been investigated in recent years.
A cube-like Mn3O4@C cathode was synthesized by hydrothermal
method followed by calcination, exhibiting interconnected pores
and carbon layers [49]. The porous structure of cathode material
and 3D thin carbon coating layer network can prevent structure

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Y. Zhou, F. Chen, H. Arandiyan et al. Journal of Energy Chemistry 57 (2021) 516–542

Fig. 6. (a) Schematic illustration of Zn2+ insertion/extraction in an extended 3D ZMO spinel framework. Reproduced from Ref. [46] with permission from the American
Chemical Society, (b) comparison of cycling performance for ZNCMO@N-rGO and ZMO@N-rGO at 500 mA g
1 and 1000 mA g
1. Reproduced from Ref. [47] with permission
from Elsevier, and (c) schematic reaction pathway of spinel Mn3O4 in the first cycle. Reproduced from Ref. [48] with permission from Elsevier.

Fig. 7. Joint non-diffusion controlled Zn2+ intercalation and H+ conversion reaction mechanism in d-MnO2. Reproduced from Ref. [53] with permission from Wiley-VC.

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Y. Zhou, F. Chen, H. Arandiyan et al. Journal of Energy Chemistry 57 (2021) 516–542

Fig. 8. Schematic of Zn2+ insertion processes in c-MnO2. Reproduced from Ref. [58] with permission from the American Chemical Society.

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Y. Zhou, F. Chen, H. Arandiyan et al. Journal of Energy Chemistry 57 (2021) 516–542

damage, increase active surface area and ion diffusion channels,
and improve electrochemical activity. Another novel NixMn3-xO4@-
C (x = 1) cathode was formed by mixing highly porous NixMn3
xO4
(low-band-gap and rich in Mn4+) and carbo, where the reversible
intercalation mechanism of Zn2+ is responsible for the reaction
(NixMn3
xO4 + yZn2+ + 2ye
M 4ZnyNixMn3
xO4) [50]. The substitu-
tion of cation-site Ni with high doping concentration can greatly
improve electronic conductivity and decrease the bandgap of
active materials. In this study, excellent rate capability (139.7
and 98.5 mAh g
1 at 50 and 1200 mA g
1, respectively) and out-
standing cycling stability (128.8 mAh g
1 remaining at 400 mA g
1
after 850 cycles) were reported for the developed cathode [50]. As
a conclusion, spinel manganese cathode materials with limited 3D
space could increase the lattice space by doping and prevent the
structure damage by coating and morphology control. These new
methods of spinel manganese cathode modification provide an
opportunity to design other types of cathodes.
2.1.4. d-MnO2
The Zn2+ reversible insertion/extraction mechanism and the H+
intercalation mechanism were both reported on birnessite-type
MnO2 (d-MnO2). d-MnO2 has various phases including chalcophan-
ite, birnessite, buserite and vernadite. The intercalation of Zn2+ was
found to trigger the structure change [16]. In 2015, d-MnO2 nano-
flake with a layered structure was used in aqueous ZIBs, and
spinel-type ZnMn2O4 was observed after the discharge process
[51]. Then in 2017, hydrate d-MnO2 (K0.11MnO20.7H2O) was used
in a nonaqueous electrolyte ZIBs to reversibly convert between
MnO2 and ZnxMnO2 through Zn2+ intercalation [52]. Although the
capacity of aqueous d-MnO2 ZIBs (250 mAh g
1) is much higher
than that of nonaqueous electrolyte (120 mAh g
1), it is still lower
than the theoretical capacity (308 mAh g
1). In 2019, a new reac-
tion mechanism with non-diffusion intercalation of Zn2+ in original
d-MnO2 during the initial discharge process, then followed by H+
reversible insertion was reported in a d-MnO2 cathode (Fig. 7)
[53]. The detailed reaction process of d-MnO2 needs to be further
studied, and the dissolution of Mn2+ and the decomposition of
the electrolyte should be further considered [17]. In particular,
recent research has found that through annealing after hydrother-
mal synthesis, the ordered stacking, surface area and conductivity
of d-MnO2 cathode can be significantly improved leads efficient
charge transfer and excellent cyclability [54].
2.1.5. c-MnO2
The Nsutite-type MnO2 (c-MnO2) with 1*1 and 1*2 tunnels
used as a cathode in ZIBs was firstly reported in 1986 [55]. After
that, Kumar et al. used Zn(CF3SO3)2 salt as gel electrolyte for the
ZIB and proposed the Zn2+ reversible insertion/extraction mecha-
nism in c-MnO2 [56]. However, different H+ intercalation mecha-
nisms were reported in c-MnO2 ZIBs with aqueous ZnSO4 and Zn
(NO3)2 electrolytes in 2012 [57]. Later in 2015, a structural trans-
formation study of mesoporous c-MnO2 cathode was conducted
[58]. As shown in Fig. 8, with the insertion of Zn2+, the c-MnO2
cathode underwent a gradual phase transformation, and finally, a
mixture of manganese spinels was obtained. Besides, most of the
discharge process can be restored to the original c-MnO2 state
after the recharging process, which reveals a Zn2+ reversible inser-
tion/extraction mechanism.
2.1.6. b-MnO2
Similar to d-MnO2, pyrolusite-type MnO2 (b-MnO2) was
reported to only obey the Zn2+ reversible insertion/extraction
mechanism at the beginning of the study [59,60]. For example, in
2017, Islam et al. reported a Zn2+ insertion mechanism in b-
MnO2 cathode, and the b-MnO2 transformed into a spinel structure
after a long cycle [60]. Even if the b-MnO2 had only 1*1 tunnels, the

Table 1
Summary of electrochemical performance of selected manganese oxide cathode materials in ZIBs.

Cathode Electrolyte Specific capacity Cycle performance (Capacity retention) Ref.

Phase Synthesis method
a-MnO2 Self-reacting Zn(NO3)2 210 mAh g
1 at 0.2 A g
1 No capacity fading after 50 cycles at 1 A g
1 [33]
microemulsion
a-MnO2 Hydrothermal method ZnSO4 233 mAh g
1 at 83 mA g
1 63% retained after 50 cycles at 83 mA g
1 [36]
a-MnO2 Hydrothermal method ZnSO4 285 mAh g
1 at C/3 92% retained after 5000 cycles at 5 C [40]
a-MnO2 Hydrothermal method ZnSO4 + MnSO4 382.2 mAh g
1 at 0.3 A g
1 94% retained after 3000 cycles at 3 A g
1 [74]
e-MnO2 on CFP Electrodeposition ZnSO4 + MnSO4 290 mAh g
1 at 90 mA g
1 0.007% capacity decay rate per cycle for 10 000 [43]
cycles at 6.5 C
LiMn2O4 Impregnation method ZnSO4 + LiSO4+ MnSO4 300 mAh g
1 at 0.1 A g
1 90% retained after 2000 cycles at 2 A g
1 [75]
c-MnO2 Electrolytic manganese Zn(CF3SO3)2 in 105 mAh g
1 at 10 mA g
1 65% retained after 65 cycles at 200 mA g
1 [56]
dioxide PC + EC + PVDF
c-MnO2 Redox reaction process ZnSO4 285 mAh g
1 at 0.05 mA cm
2 63% retained after 40 cycles at 0.5 mA cm
2 [58]
c-MnO2-graphene Hydrothermal method ZnSO4 + MnSO4 301 mAh g
1 at 0.5 A g
1 64.1% retained after 300 cycles at 20 mA cm
2 [76]
b-MnO2 Microwave-assisted ZnSO4 270 mAh g
1 at 100 mA g
1 75% retained after 200 cycles at 200 mA g
1 [60]
hydrothermal method
b-MnO2 Hydrothermal method Zn(CF3SO3)2 + Mn 258 mAh g
1 at 0.65 C 94% retained after 2000 cycles at 6.5 C [28]
(CF3SO3)2
d-MnO2 Thermal decomposition ZnSO4 250 mAh g
1 at 83 mA g
1 46% retained after 100 cycles at 83 mA g
1 [51]
ZnMn1.86Y0.14O4 Oxidation precipitation Zn(CF3SO3)2 150 mAh g
1 at 500 mA g
1 94% retained after 500 cycles at 500 mA g
1 [46]
N-CC@MnO2 Electrodeposition Aqueous 353 mAh g
1 at 0.5 A g
1 93.6% retained after 1000 cycles at 0.5 A g
1 [63]
K1.33Mn8O16 Two step sonochemical ZnSO4 + MnSO4 312 mAh g
1 at C/10 80% retained after 650 cycles at 5 C [77]
synthesis
a-Mn2O3 Metal-Organic Framework- ZnSO4 + MnSO4 225 mAh g
1 at 0.05 A g
1 53.3% retained after 1700 cycles at 2 A g
1 [78]
derived method
Mn3O4 Chemical reaction ZnSO4 239.2 mAh g
1 at 100 mA g
1 73% retained after 300 cycles at 500 mA g
1 [48]
Zn4(OH)6SO4∙5H2O Precipitation route ZnSO4 + MnSO4 100% retained after 1500 cycles [39]
MnO2/rGO Hydrothermal method Guar 308.2 mAh g
1 at 0.3 A g
1 100% retained after 1900 cycles, 85% retained [68]
gum + ZnSO4 + MnSO4 after 2000 cycles at 6 A g
1
Ca0.28MnO20.5H2O Hydrothermal method ZnSO4 + MnSO4 227 mAh g
1 at 0.35 A g
1 92% retained after 5000 cycles at 3.5 A g
1 [79]

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Y. Zhou, F. Chen, H. Arandiyan et al. Journal of Energy Chemistry 57 (2021) 516–542

resulting Zn intercalation phases allowed Zn2+ insertion and Cathode:

achieved good electrochemical performance (Table 1). Another
H2 O $ Hþ þ OH
ð4Þ
study in 2017 confirmed another phase change of b-MnO2 during
the (dis)charge cycles [28]. As shown in Fig. 9(a) and (b), at the first
MnO2 þ Hþ þ e
$ MOOH ð5Þ
discharge, b-MnO2 was transformed into layered Zn-buserite, and
then Zn2+ was reversibly inserted/extracted into the latter struc-
1 2þ 1 x
ture. The XANES (X-ray near edge absorption structure) profiles Zn þ OH
þ ZnSO4 þ H2 O
2 6 6
of the Mn K-edge of the b-MnO2 electrode confirmed the decrease
1  
in the average Mn oxidation state during discharge (Fig. 9c). The $ ZnSO4 ZnðOHÞ2 3  xH2 O ð6Þ
edge position moved back slightly to higher energy but remained 6
almost unchanged in the second cycle. During the first full dis- Anode:
charge, the decrease of Mn-Mnconrner peak was greater than that
1 1
of Mn-O and Mn-Mnedge signals (Fig. 9d), which confirmed the Zn $ Zn2þ þ e
ð7Þ
2 2
breakage of the MnO6 octahedra shared by corners. The results
showed that the phase changed into layered Zn-buserite during Overall:
the first discharge cycle. Recently, a mechanism of H+ insertion 1 x 1
rather than Zn2+ insertion was reported in a b-MnO2 with rich oxy- MnO2 þ Zn þ H2 O þ ZnSO4
2 6 6
gen defects [61], which was the same as previously reported mech- 1  
anism in a-MnO2: $ MOOH þ ZnSO4 ZnðOHÞ2 3  xH2 O ð8Þ
6

Fig. 9. (a) Schematic illustration of the Zn-MnO2 cell using CF3SO3 based electrolyte, (b) schematic depiction of the unit cell of b-MnO2, (c) Mn-K edge XANES curves at
selected discharge/charge states, with reference to standard MnO, Mn2O3, and Mn3O4, and (d) EXAFS spectra. Reproduced from Ref. [28] with permission from Nature
Publishing Group.

526
Y. Zhou, F. Chen, H. Arandiyan et al.
The water solvent decomposed into OH
and H+, and then
reacted with ZnSO4 and b-MnO2 to form ZHS and MOOH respec-
tively during the discharge process, which is confirmed by XRD
and FTIR. In this report, the oxygen defects facilitated the insertion
of H+ into b-MnO2 by reducing the binding energy, which highly
improves the capacity of the battery. Efficient oxygen defect engi-
neering is an excellent strategy to improve the electrochemical
performance of b-MnO2 in rechargeable batteries.
2.1.7. Todorokite-type MnO2
Todorokite-type MnO2 with large 3*3 tunnels is considered to
have excellent performance because its larger tunnel can accom-
modate Zn2+. Nevertheless, many cations and water molecules
exist in the large tunnel, which affects the intercalation of Zn2+
[17]. There are a few studies on todorokite-Type MnO2, and the
results are not satisfactory [62]. More attention needs to be paid
to the synthesis method of todorokite-type MnO2 and analysis of
the discharge process. Because of the most popular synthetic
method of MnO2 is hydrothermal, it is hard to avoid the water
molecules insert into the large 3*3 tunnels. Other synthetic meth-
Fig. 10. (a) Crystallographic structure of b-MnO2 and Ce doped MnO2, (b) CV curves at a scan rate of 0.1 mV s
1, (c) charge-discharge voltage profiles at 0.5 C, (d) cycling
performances, and (e) rate capabilities. Reproduced from Ref. [65] with permission from the American Chemical Society.
527
Journal of Energy Chemistry 57 (2021) 516–542
ods such as thermal decomposition could be considered to solve
this problem.
2.1.8. Design and discussion of MnO2 cathode
The most widely used synthetic method of MnO2 is hydrother-
mal method, which has a unique advantage of high crystallinity
and controllable morphology. Thermal decomposition [51] and
electrodeposition of manganate salt (for example, KMnO4) method
[63] were also used to synthesize MnO2 as a cathode material.
Besides, in recent years, new strategies for doping other elements
into MnO2 have been proposed. For example, nitrogen-doped
MnO2 has been reported as a cathode material with improved elec-
trochemical performance, which can prevent electrode dissolution
and reduce the accumulation of by-products [64]. In 2019, Ce-
doped b-MnO2 (1*1 tunnel) cathode was synthesized by a one-
step hydrothermal method. As shown in Fig. 10(a), after doping
Ce, the structure of MnO2 was transformed from 1*1 tunnels to
(1*1)+(2*2) tunnels. The larger tunnel structure facilitated faster
and reversible Zn2+ migration [65]. As shown in Fig. 10(b), the
cathodic peaks shifted to higher potentials while the anodic peak
Y. Zhou, F. Chen, H. Arandiyan et al. Journal of Energy Chemistry 57 (2021) 516–542

became narrower and shifted to lower potentials. The voltage dif-
ferences (D) of Ce-doped-MnO2 between the anode and cathode
peak centre were much smaller than those of b-MnO2 (as shown
in Fig. 10c). These results indicated that the diffusion of Zn2+ in
MnO2 became better after Ce doping. In addition, Ce-doped-MnO2
exhibited better cycling stability and rate capability (Fig. 10d and
e). Compared with the undoped b-MnO2, the doped MnO2 cathode
showed better electrochemical stability and reversibility with
lower charge-transfer resistance and higher ion diffusivity. Doping
has become a hot strategy for cathode modifications, many metal
ions such as Ni, Ce, Al, La, Ca, Co were used in ZIBs.
In recent years, some novel MnO2 cathodes have been devel-
oped to improve ion conductivity, decrease the dissolution of Mn
and increase the surface area. For example, a novel N-MnO2–
x@TiC/C cathode for ZIB was reported in 2019 (285 mAh g
1 at
0.2 A g
1, 85.7% retained after 1000 cycles at 1 A g
1). As shown
in Fig. 11(a) [66], N-MnO2–x coated on TiC/C nanorod array
achieved excellent conductivity, good chemical and mechanical
stability compared to TiC/C. It increased the activity of MnO2 by
annealing in an NH3 atmosphere. Another MnO2/rGO/PANI cathode
was synthesized by a hydrothermal method and an in situ poly-
merization process. The obtained cathode also achieved an excel-
lent performance (241.1 mAh g
1 at 0.1 A g
1) and stability
(82.7% retained after 600 cycles) [67]. The graphene nanosheets
framework significantly improved the conductivity and diffusion
rate of the active material, and the coated cathode decreased the
Mn dissolution, thereby enhancing the cycling stability and rate
performance of the battery. In addition, carbon cloth also played
an important role in the design of flexible cathode. As shown in
Fig. 11(b) and (c), MnO2 nanorod arrays were deposited on the sur-

Fig. 11. (a) Fabrication process of N-MnO2–x@TiC/C core-shell arrays, SEM image of N-MnO2–x@TiC/C arrays. Reproduced from Ref. [66] with permission from Wiley-VC, (b)
formation of orthorhombic d-MnO2 via hydrothermal method, SEM image of d-MnO2 (inset showing the high-magnified SEM). Reproduced from Ref. [54] with permission
from Nature Publishing Group, and (c) flexible N-CC@MnO2/N-CC@Zn battery, SEM images of the N-CC@MnO2; the inset is the corresponding magnified SEM image (inset
showing the high-magnified SEM). Reproduced from Ref. [63] with permission from the Royal Society of Chemistry.

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Y. Zhou, F. Chen, H. Arandiyan et al. Journal of Energy Chemistry 57 (2021) 516–542

face of a 3D N-doped porous carbon cloth through electrodeposi-
tion method. They were directly grown on the current carbon col-
lector by the hydrothermal method without using a binder or
vacuum filtration during deposition [54,63,68]. In addition to pre-
viously reported MnO2 cathodes, another oxygen-defect
K0.8Mn8O16 (with similar crystallographic structure of a-MnO2)
revealed that the K+ ions could effectively alleviate the dissolution
of Mn during the cycle, and it was found that the oxygen defects in
cathode material are beneficial for the fast reaction kinetics [69].
The oxygen defects in K0.8Mn8O16 could increase the donor density
and reduce the energy of the electron transport and charge transfer
during the redox reaction. Furthermore, it could open the MnO6
polyhedron walls in K0.8Mn8O16, thereby facilitating H+ diffusion
(H+ is the main charge transport carrier in this work: K0.8Mn8O16 +-
xH+ + xe– M HxK0.8Mn8O16), which greatly improves the electro-
chemical reactivity and reaction kinetics. Whether surface
coating or engineering oxygen defects, they are the excellent
strategies for cathode modification to decrease the Mn dissolution
and improve reaction kinetics of cathodes.
Different energy storage mechanisms of MnO2 have been
reported in different structures. It was found that the tunnel struc-
ture phase a-type, b-type, c-type can undergo a phase change in
aqueous electrolyte during charge/discharge process. For example,
in a-type (2*2) and b-type (1*1) MnO2, the initial MnO2 cathode
can transfer into layered structure along with the dissolution of
manganese, and the c-type MnO2 cathode underwent a compli-
cated gradual phase transformation as shown in Table 2. Moreover,
with manganese dissolution and H2O insertion, the spinel structure

Table 2
Summary of selected types of MnO2, mechanisms, and electrolyte.

Phase Mechanisms Electrolyte Schematic Ref.

a-type (2*2) Reversible phase 1 M aqueous ZnSO4 [37]
transition between
layered Zn birnessite
and a-MnO2

Formation of ZHS 1 M aqueous ZnSO4 [35]

phase or its analogues

b-type (1*1) Phase change of 3 M Zn(CF3SO3)2 + 0.1 M Mn [28]

b-MnO2 (CF3SO3)2

c-type Gradual phase 1 M aqueous ZnSO4 [58]

(1*1 + 1*2) transformation

k-type (Spinel) Spinel Mn3O4 to 2 M ZnSO4 solution [48]

brinessite-type MnO2

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Y. Zhou, F. Chen, H. Arandiyan et al.
Fig. 12. (a) Schematic of a-Mn2O3 as cathode material for zinc ion battery, (b) CV curve at 0.5 mV s
1, (c) cycling performance at 100 mA g
1, (d) rate capability of ZIB with a-
Mn2O3 cathode in 2 M ZnSO4 electrolyte, and (e) SEM image of a-Mn2O3 second fully discharged cathode. Reproduced from Ref. [71] with permission from Elsevier.
of Mn3O4 changed into brinessite-type MnO2 as well. In addition,
attention should be paid to the relationship between cathode and
electrolyte. In aqueous electrolyte, the formation of ZHS phase or
its analogues on the surface of the cathode were reported in many
types of manganese-based cathode. For example, in order to com-
pare the kinetics of an electrode reaction in different electrolytes,
the LiMn2O4 cathode was studied in aqueous electrolyte (elec-
trolyte with sufficient water content), ‘‘water-in-salt” electrolyte
and organic electrolyte in 2020 [70]. It was found that the ionic
conductivity of aqueous electrolyte is much higher than that of
‘‘water-in-salt” electrolyte and organic electrolyte. The rich active
water in aqueous electrolyte can accelerate the desolvation of
Zn2+. As shown in Table 2, the OH
group on the cathode surface
will first capture the Zn2+ from [Zn(OH2)6]2+ to form [Zn(OH)n]2
n,
which greatly accelerates the desolvation of Zn2+, then the [Zn
(OH)n]2
n groups sequentially combine with the SO2
4 groups to
form Zn4SO4(OH)64H2O phase on the surface of the electrode. In
general, the rules of transition between different phases and the
internship between cathodes and different types of electrolytes
should be analyzed in detail in future.
2.2. Other manganese oxide cathodes
2.2.1. Mn2O3
One of the earliest reports on manganese oxides with Mn(III)
state as cathode for ZIB was in 2017 [71]. As shown in Fig. 12(a),
an a-Mn2O3 cathode with a bixbyite structure (Mn3+ ions in octa-
hedral coordination and four Mn ions surround each O ion) was
reported by B.Z. Jiang et al. During reversible insertion and extrac-
tion of zinc ions, a-Mn2O3 underwent a reversible phase transition
530
Journal of Energy Chemistry 57 (2021) 516–542
from bixbyite structure to layered-type zinc birnessite (xZn2+ + 2-
xe
+ Mn2O3 M ZnxMn2O3). SEM results in Fig. 12(e) confirmed
reversible morphology change between tiny nano-flake-like/
flower-like structure and larger nano-flake-like structure. As
shown in Fig. 12(b)–(d), the battery delivered good rate perfor-
mance, but it should be noted that the a-Mn2O3 cathode needed
to be activated in the first cycle and the cell delivered a higher dis-
charge capacity from the second cycle.
2.2.2. MnO
Currently, most research work is focused on MnO2 cathodes,
and manganese monoxide (MnO) was not studied as a ZIB cathode
material until 2019. During the first charging process, the MnO
cathode was electrochemically oxidized into layered-type MnO2
on the surface, which became an active material for subsequent
energy storage. In the following charge/discharge process, the reac-
tion mechanism is the same as the Zn2+ and H+ reversible co-
insertion mechanism described previously [72]. However, a differ-
ent Zn2+ insertion/extraction mechanism was reported in 2019
[73]. As shown in Fig. 13(a), during the first charging process,
Mn2+ was extracted from MnO framework and induced the forma-
tion of Mn defects: MnO ? Mn0.61h0.39O + 0.39Mn2+ + 0.78e
(h
refers to Mn defect). Then Zn2+ reversible insert/extract occurred
in the following cycles: Mn0.61h0.39O + yZn2+ + 2ye
M ZnyMn0.61-
h0.39O (h refers to Mn defect). As shown in Fig. 13(b), the enriched
Mn defects in MnO promoted the Zn2+ diffusion, leading to a uni-
form charge distribution in the MnO. At the same time, the elec-
trons accumulated around Mn defects to form a strong
electrostatic field in Mn0.61h0.39O. The electrons accumulation
strongly attracted Zn2+ on the Mn defects, resulting in a high
Y. Zhou, F. Chen, H. Arandiyan et al.
Fig. 13. (a) Schematic illustration of Zn2+ insertion/extraction in a MnO framework, (b) charge distribution of MnO and Mn0.61h0.39O, and the structures after Zn2+ insert, and
(c) comparison of the Ragone plot of the Mn0.61h0.39O with other previous cathode materials for aqueous ZIBs. Reproduced from Ref. [73] with permission from Elsevier.
energy density (383.88 Wh kg
1 at 135.6 W kg
1) and long-term
cycling performance, with a reversible capacity of 116 mAh g
1 at
1 A g
1 after 1500 cycles. In Fig. 13(c), compared with other
reported ZIBs, the battery achieved a high-level energy density.
Activation of Mn-based cathode by inducing Mn vacancy through
a charge process is a smart cathode design through defect
engineering.
In general, various crystal structures of MnO2 (a-, e-, k-, c-, b-,
d- and todorokite-MnO2) and some other Mn oxide-based cathode
materials have been studied in ZIBs. Manganese oxides-based
materials have advantages such as low price, nontoxic and rich
source, which can deliver high operating voltage, excellent capac-
ity, and stable cycle ability. Until now, MnO2 with diverse crystal
structures, Mn2O4, Mn3O4, Mn2O3, and MnO were developed as
one of the most favourable cathode materials for ZIBs. The chal-
lenges of Mn oxide cathodes include Mn dissolution, low ion con-
ductivity and different mechanisms. Although each of them
exhibits unique performance and mechanisms, more efforts should
be made to further improve their performance as cathode for ZIBs.
The following Table 1 listed the selected manganese-based cathode
reported in recent years.
3. Vanadium oxide-based cathodes
Vanadium oxide-based materials are also promising electrodes
because of their excellent stability and flexible structure. Vana-
dium oxides are composed of various V-O coordination polyhedral,
531
Journal of Energy Chemistry 57 (2021) 516–542
including tetrahedron, trigonal bipyramid, square pyramid, dis-
torted octahedron and regular octahedron [80]. The oxidation
states of vanadium are usually +5, +4, or +3 (even +2). The meta-
morphosis of vanadium coordination polyhedral is shown in
Fig. 14: (i) The V5+ in the tetrahedra is a typical polyhedron, and
the V-oxides with pure tetrahedra structures are usually chains
like. (ii) By adding a fifth O atom on the opposite side of any face
and moving the V atom to the centre of this face at the same time,
the tetrahedra can change to trigonal bipyramid. The trigonal
bipyramid typically has one short V@O bond or two short bonds
in its base. If the V atoms are coplanar with four bottom O atoms,
the structure will become a square pyramid. The oxidation state of
vanadium in square pyramid and trigonal bipyramid is +4 or +5.
(iii) Adding the sixth O atom in a row, the square pyramid will
become a distorted octahedron (V4+ or V5+), and then a regular
octahedron (V3+ or lower oxidation state). These five different
types of polyhedral can share corners or edges to build a large fam-
ily of vanadium oxides with different frames (chains, layers, 3D
frameworks). In this section, recently reported vanadium oxide
cathodes would be discussed based on the working mechanisms
and electrochemical performance.
3.1. V2O5 and MxV2O5
V2O5 and MxV2O5 compounds (M = alkali, alkaline earth, metals)
consist of square pyramidal (VO5) or octahedral (VO6) building
units [16]. In 1992, it was reported that using an ion-exchange
Y. Zhou, F. Chen, H. Arandiyan et al. Journal of Energy Chemistry 57 (2021) 516–542

Fig. 14. Metamorphosis of the vanadium coordination polyhedral. Reproduced from Ref. [17] with permission from Wiley-VCH.

Fig. 15. (a) Schematic illustration of the reaction mechanism of the Zn/V2O5 battery, (b) CV profile of Zn/V2O5 battery at 1.2 mV s
1. The blue region shows the capacitive
contribution to the total current, (c) long-cycling performance of Zn/V2O5 battery at 5.0 A g
1, inset shows the capacity evolution in the initial 19 cycles. Reproduced from Ref.
[85] with permission from the American Chemical Society, (d) schematic illustration of the reaction mechanism of vanadium oxide electrode, and (e) GITT profiles at the 5th
cycle and the calculated Zn2+ diffusion coefficient of the cathode. Reproduced from Ref. [86] with permission from Elsevier.

method Zn2+ was intercalated into vanadium oxides to form ZnxV2-
O5yH2O [81]. Later, the intercalation of Zn2+ into V2O5 aerogel was
reported in 1998, which indicated that the high-energy intercala-
tion batteries based on Zn2+ might be attainable [82]. XAS (X-ray
absorption spectroscopy) study further confirmed the details of
the large intercalation capacity in 1999 [83]. The reported Zn/
V2O5 hybrid-ion ZIBs [84] was the first hybrid-ion battery using
concentrated electrolytes in ZIBs, achieving a high capacity of
238 mAh g
1. Since then, a higher capacity of 470 mAh g
1 has
been obtained in layered V2O5 in 2018 [85]. As shown in Fig. 15

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Y. Zhou, F. Chen, H. Arandiyan et al. Journal of Energy Chemistry 57 (2021) 516–542

Fig. 16. (a–d) SEM and TEM images of hollow V2O5 nanospheres, (e) CV curves of hollow V2O5 nanospheres at 0.5 mV s
1, (f) GCD profiles of hollow V2O5 nanospheres at 0.1 A
g
1, (g) cycle stability at 3.0 A g
1, (h) rate performance of hollow V2O5 nanospheres and commercial V2O5, and (i) GCD profiles of hollow V2O5 nanospheres at varied current
densities. Reproduced from Ref. [87] with permission from Elsevier, and (j) schematic illustration of the formation process of binder-free V2O5 nanofibers (BCS-VONF) on
carbon cloth. Reproduced from Ref. [89] with permission from MDPI.

(a), the reaction mechanism can be described as reversible interca-
lation of hydrated Zn2+ within layered V2O5, while the co-
intercalated H2O shielded the electrostatic reactions between
Zn2+ and the host anions.
It was also found that the morphology changed gradually from
bulk V2O5 into porous nanosheets during the cycling process, lead-
ing to a rapid increase of specific surface area of the cathode. In
addition, the capacitive contribution cannot be ignored here. As
shown in Fig. 15(c), the capacity current (blue region) accounted
for 48.5% of total current at 1.2 mV s
1. Considering all these fac-
tors, the reported Zn/V2O5 battery exhibited an excellent reversible
capacity (470 mAh g
1 at 0.2 A g
1) and long-term cycling stability

Table 3
Summary of electrochemical performance of selected vanadium oxide cathode materials in ZIBs.

Cathode Electrolyte Specific capacity Cycle performance (Capacity retention) Ref.

Phase Synthesis method
Na0.56V2O5 Hydrothermal ZnSO4 + Na2SO4 317 mAh g
1 at 0.1 A g
1 87% retained after 1000 cycles at 1 A g
1 [98]
Zn0.25V2O5nH2O Microwave approach ZnSO4 300 mAh g
1 at 1 C 80% retained after 1000 cycles at [91]
2400 mA g
1
Ca0.25V2O5nH2O Hydrothermal method ZnSO4 340 mAh g
1 at 0.2 C 64% retained after 5000 cycles at 80 C [92]
K0.23V2O5 Hydrothermal Zn(CF3SO3)2 284 mAh g
1 at 0.1 A g
1 92.8% retained after 500 cycles at 2 A g
1 [95]
Mn0.15V2O5nH2O Microwave-assisted strategy Zn(ClO4)2 367 mAh g
1 at 0.1 A g
1 ~ 100% retained after 8000 cycles at 10 A g
1 [120]
d-Ni0.25V2O5nH2O Hydrothermal method ZnSO4 420 mAh g
1 at 0.2 A g
1 98% retained after 1200 cycles at 5 A g
1 [121]
PANI-intercalated In situ hydrothermal reaction Zn(CF3SO3)2 197.1 mAh g
1 at 20 A g
1 97.6% retained after 2000 cycles at 20 A g
1 [122]
V2O5
MnVO Hydrothermal Zn(CF3SO3)2 260 mAh g
1 at 4 A g
1 96% retained after 2000 cycles at 4 A g
1 [123]
KV12O30-ynH2O Hydrothermal method Zn(CF3SO3)2 436 mAh g
1 at 0.05 A g
1 92% retained after 3000 cycles at 5 A g
1 [124]
Cu3V2O7(OH)22H2O Hydrothermal Zn(CF3SO3)2 216 mAh g
1 at 0.1 A g
1 89.3% retained after 500 cycles at 0.5 A g
1 [109]
LiV3O8 Soild-state ZnSO4 172 mAh g
1 at 133 mA g
1 75% retained after 65 cycles at 133 mA g
1 [100]
H2V3O8 Hydrothermal method Zn(CF3SO3)2 423.8 mAh g
1 at 0.1 A g
1 94.3% retained after 1000 cycles at 5 A g
1 [102]
NH4V3O80.5H2O Hydrothermal method Zn(CF3SO3)2 420 mAh g
1 at 0.1 A g
1 50.1% retained after 1000 cycles at 1 A g
1 [105]
(NH4)2V6O16 Hydrothermal reaction Zn(CF3SO3)2 322 mAh g
1 at 0.1 A g
1 78.3% retained after 2000 cycles at 5 A g
1 [125]
V3O7H2O/rGO Hydrothermal method ZnSO4 245 mAh g
1 at 79% retained after 1000 cycles [126]
1500 mA g
1 at 1500 mA g
1
RGO/VO2 film Freeze-drying + high temperature Zn(CF3SO3)2 276 mAh g
1 at 0.1 A g
1 99% retained after 1000 cycles [127]
reduction + mechanical
compression
VO2 Hydrothermal method ZnSO4 272 mAh g
1 at 3 A g
1 75.5% retained after 945 cycles at 3 A g
1 [111]
VO2 (B) nanofibers Hydrothermal method Zn(CF3SO3)2 357 mAh g
1 at 0.1 A g
1 92.6% retained after 300 cycles at 5 C [128]
VO2.0.2H2O&VOG Microwave-assisted strategy ZnSO4 423 mAh g
1 at 0.25 A g
1 87% retained after 1000 cycles at 8 A g
1 [129]
CuV2O6 Hydrothermal Zn(CH3F3SO3)2 338 mAh g
1 at 100 mA g
1 ~100% retained after 1200 cycles at 5 A g
1 [114]
Na3V2(PO4)2F3 Sol-gel method Zn(CF3SO3)2 75 mAh g
1 at 80 A g
1 95% retained after 4000 cycles at 1 A g
1 [117]
Ag2V4O11 Hydrothermal Zn(CF3SO3)2 213 mAh g
1 at 0.2 A g
1 93% retained after 6000 cycles at 5 A g
1 [130]
Na3V2(PO4)3 Hydrothermal + calcination Zn(CH3COO)2 97 mAh g
1 at 0.5 C 74% retained after 100 cycles at 0.5 C [116]
Na2V6O161.63H2O Hydrothermal Zn(CF3SO3)2 352 mAh g
1 at 50 mA g
1 90% retained after 6000 cycles at [101]
5000 mA g
1
VS2 Hydrothermal reaction ZnSO4 190.3 mAh g
1 at 0.05 A g
1 98% retained after 200 cycles at 0.5 A g
1 [118]
Zn3V2O7(OH)22H2O Microwave process ZnSO4 213 mAh g
1 at 50 mA g
1 68% retained after 300 cycles at 200 mA g
1 [107]
(NH4)2V10O258H2O Hydrothermal Zn(CF3SO3)2 417 mAh g
1 at 0.1 A g
1 59% retained after 500 cycles at 0.5 A g
1 [131]
VNxOy Nitriding method ZnSO4 200 mAh g
1 at 30 A g
1 75% retained after 2000 cycles at 20 A g
1 [119]

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Y. Zhou, F. Chen, H. Arandiyan et al. Journal of Energy Chemistry 57 (2021) 516–542

(91.1% capacity retention after 4000 cycles at 5 A g
1, as shown in
Fig. 15b). Recently, a different reversible Zn2+ intercalation mecha-
nism has been reported in porous V2O5 nanofibers cathode [86]. As
shown in Fig. 15(d), the phase was transformed from orthorhombic
V2O5 to an open-structured zinc pyrovanadate (Zn3+x(OH)2V2O7∙2-
H2O, ZVO) at the initial discharge, and the Zn2+ reversible interca-
lated in the open-structured ZVO during the subsequent cycling.
Both XRD and Raman results verified the phase transition and
the reversible Zn2+ intercalation in ZVO. ZVO provided excellent
electrochemical performance because the transformed ZVO pro-
vided a high Zn2+ diffusion coefficient (DZn, 10
9–10
11 cm2 s
1),
which was confirmed by the galvanostatic intermittent titration
technique (GITT) measurement (Fig. 15e).
In addition, significant progress in V2O5 cathodes has been
reported in both aqueous and nonaqueous ZIBs. Most reported
cathodes aim to improve surface capacitive behaviour, and electro-
chemical kinetics by enlarging Zn2+ ion diffusion coefficient. In
2019, Chen et al. reported a hollow V2O5 nanospheres cathode
material (with a diameter of about 450 nm and shell thickness of
50 nm), designed to reduce structural stress upon cycling, shorten
ion and electron transport paths, and enhance surface capacitive
behaviour [87]. As shown in Fig. 16(a)–(d), SEM images illustrated
a uniform spherical shape and an apparent contrast between the
interior core and outside shell, which verified the hollow structure
of synthesized V2O5. The slight changes between different cycles
(Fig. 16e and f) demonstrated good reversibility and excellent elec-
trochemical stability of the electrode. The novel hollow V2O5 cath-
ode delivered a high reversible capacity (327 mAh g
1 at 0.1 A g
1),
excellent rate performance (146 mAh g
1 at 20 A g
1) and superior
cyclic performance (147 mAh g
1 after 6000 cycles at 10 A g
1; 122
mAhg
1 after 10,000 cycles at 15 A g
1). As shown in Fig. 16(g) and
(h), hollow V2O5 demonstrated a better cyclic performance and
rate capability than the commercial V2O5. In addition, even at the
high current density of 20 A g
1, the GCD curves (galvanostatic
charge-discharge curves) of hollow V2O5 nanospheres still could
be noticed (Fig. 16i). Another rod-like anhydrous V2O5 (RA-V2O5)

Fig. 17. (a) Schematic of the aqueous rechargeable Zn–LVO cell, (b) rietveld refinement of the XRD pattern of the LVO, (c) comparison of normalized V K-edge XANES spectra
of initial state (LVO) and the standard vanadium oxides with those obtained at different depth-of-discharge (DOD) conditions during discharge cycling, and (d) schematic of
the Zn-intercalation mechanism in the present LiV3O8 cathode. Reproduced from Ref. [100] with permission from the American Chemical Society.

534
Y. Zhou, F. Chen, H. Arandiyan et al.
exhibited high performance with a large reversible capacity for
449.8 mAh g
1 at 0.1 A g
1, good rate capability for 314.3 mAh
g
1 at 2 A g
1, and 86.8% capacity retention after 2000 cycles at
2 A g
1. The excellent performance was attributed to the large
specific surface area (218 m2 g
1), which made electrolyte perme-
ation and Zn2+ insertion more favourable in RA-V2O5 [88].
To avoid the toxicity of binder and minimize the disruption to
the mobility of Zn2+ during the charge/discharge process, binder-
free composite paper/cloth cathodes were investigated. By a sim-
ple one-step hydrothermal method, a binder-free V2O5 nanofiber
with single-crystalline was grown on carbon cloth (Fig. 16j) [89].
This novel cathode exhibited good adhesion between active mate-
rial and current collector, which also prevented active material
from dissolving in aqueous electrolyte. It was also found that for
the V2O5 cathode, a 3.0 M Zn(OTf)2 electrolyte is superior to the
3.0 M ZnSO4 electrolyte, which was caused by the dissolution of
V2O5 in the traditional electrolyte ZnSO4. Another flexible free-
standing V2O5/carbon nanotube (V2O5/CNT) composite paper cath-
ode also achieved excellent battery performance (specific capacity
of 312 mAh g
1 at 1 A g
1, 81% capacity retention after 2000 cycles
at 1 A g
1) [90]. These binder-free flexible cathodes with non-toxic
and lightweight cast light on the design of wearable zinc ion
batteries.
Similar to V2O5, MxV2O5 compounds (M = alkali, alkaline earth,
metals) can be characterized by single- or double-layer lattices,
which consist of square pyramidal (VO5) or octahedral (VO6) build-
ing units. For MxV2O5 compounds, Zn0.25V2O5 [91], Ca0.25V2O5 [92],
Na0.33V2O5 [93], K2V8O21 [94], K0.23V2O5 [95], and Ag0.4V2O5 [96]
were investigated as cathode materials in ZIBs. In 2016, Kundu
et al. reported a reversible Zn2+ insertion/extraction process of
Zn0.25V2O5 cathode under fast rates: the interlayer distance of cath-
ode material increased from 10.8 Å to 12.9 Å after immersion in the
electrolyte and then reduced to 11.0 Å during the discharge process
[91]. This phenomenon can be explained as follows: the water
molecules were inserted into the interlayer of Zn0.25V2O5 (increas-
ing the interlayer distance), and then removed when Zn2+ was
intercalated during the discharge process (reducing the interlayer
distance).
In the meantime, a freestanding hierarchical porous composite
of bilayered NaxV2O5nH2O (NVO) nanobelts, carbon nanotubes
(CNTs), and reduced graphene oxide (rGO) with a 3D cross-linked
structure were reported in 2020 [97]. This hybrid material exhib-
ited superior electrochemical properties as cathodes in both K-
ion batteries and zinc-ion batteries. Na0.33V2O5 was composed of
the quadruple octahedra chains, which was linked by double
chains of square pyramids through the shared corners [80]. With
the insertion of Zn2+ during the discharge process, a new ZnxNa0.33-
V2O5 phase appeared, and a high capacity decay was observed in
the first two cycles, while Zn2+ intercalated in ‘‘dead sites”. In
2020, a Na0.56V2O5 nanobelt cathode material was synthesized
via a hydrothermal method [98]. The prepared NVO samples deliv-
ered a larger interlayer space (for example, an enlarged interplanar
distance of pristine V2O5 from 0.2 nm to 0.35 nm for (202) plane)
by chemically intercalating Na+ into the V2O5, thereby
achieving an excellent capacity and good cyclic stability (as listed
in Table 3).
3.2. MxV3O8
MxV3O8 (M = alkali ion or H) compounds are composed of VO6
octahedra and VO5 square pyramids and the crystalline structure
based on the shared corner of these two polyhedra [17]. According
to the connectivity, there are two different types of structures: (1)
the edge shared octahedral (VO6), and square pyramids (VO5)
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Journal of Energy Chemistry 57 (2021) 516–542
chains through the shared corners, along with the alkali ions in
interstitial sites link V3O8 layers together with z-axis to construct
V3O8 layers, such as LiV3O8 and NaV3O8 [99]. Both LiV3O8 and
NaV3O8 have a layered structure that can accommodate Zn2+
[99,100]. For LiV3O8 cathode, a specific capacity of 172 mAh g
1
can be achieved in a simply designed coin cell (Fig. 17a and b).
When increasing the depth-of-discharge (DOD), the main absorp-
tion edge shifted to the lower binding energies, which confirmed
that the oxidation state of V was reduced due to the Zn2+ interca-
lation (Fig. 17c). The Zn2+ was reversibly inserted/extracted to
cathode material, and almost no structure change was found in
LiV3O8. As shown in Fig. 17(d), a reversible phase transition
occurred during discharge/charge process, where ZnLiV3O8 was
formed by the Zn ion intercalation, and a solid-solution ZnyLiV3O8
phase appeared. For NaV3O8 nanowires, after 4000 cycles at
5000 mA g
1, only 17% of the initial capacity was retained [101].
On the other hand, the Na2V6O161.63H2O (2(NaV3O8)nH2O) nano-
wires showed excellent performance with a high specific capacity
of 352 mAh g
1 at 50 mA g
1 and 90% retention after more than
6000 cycles at 5000 mA g
1 [101]. The difference was caused
by the critical role of crystalline water in vanadium oxides. (2)
The VO6 octahedra and VO5 square pyramids were connected
to each other to form the V3O8 layers through different conjunc-
tion methods, in which H atoms were bonded to the O atoms of
VO6 octahedra, such as H2V3O8(V3O7∙H2O) [16]. In H2V3O8(V3O7∙-
H2O), high capacity and excellent cycling stability were observed
[102]. After encapsulating H2V3O8 with graphene sheets, the
electrochemical performance was further improved [103]. The
electrochemical reaction mechanism was described as the co-
intercalation of reversible Zn ion and molecular water [103]. In
addition, in another study, a new phase of Zn2V3O7∙H2O was
reported during the discharge process [104]. Water molecules
play an important role in MxV3O8 compounds cathodes. Another
NH4V3O8∙0.5H2O nanobelts cathode (H2O intercalated NH4V3O8)
was synthesized by a low-temperature hydrothermal method
recently [105]. Ex situ studies (including Ex situ XRD, Ex situ
XPS, Ex situ TEM) were used in this study and reveals that a
new Zn3(OH)2V2O7∙2H2O phase is formed during charge/dis-
charge process, and it co-exists with NH4V3O8∙0.5H2O. The H2O
play key roles in the super Zn2+ storage because of the presence
of water molecules during the discharge/charge process can offer
electrostatic shielding for Zn2+, resulting in excellent ion kinetics,
ion mobility and rate performance.
3.3. MxV2O7
In MxV2O7, V is tetrahedral coordination in [V2O7] groups, and
they are aligned along z-axis to build the frameworks [106]. It
was reported that zinc pyrovanadate (Zn3V2O7(OH)22H2O, ZVO)
nanowires with a porous crystal framework were used in ZIBs
[107]. Excellent cycling performance and high capacity (213
mAh g
1 at 50 mA g
1, 76 mAh g
1 at 3000 mA g
1) was
obtained. In addition, another layered a-Zn2V2O7 has been stud-
ied [108]. A high specific energy of 166 Wh kg
1 and high capac-
ity retention of 85% after 1000 cycles at 4000 mA g
1 was
obtained by the reported a-Zn2V2O7. In both studies, the HZS
(Zn4SO4(OH)64H2O [107], Zn4(OH)6SO4∙0.5H2O [108]) was found
in discharge process products, which might trigger the insertion
of H+ in cathode during discharge process. In 2020, a novel copper
pyrovanadate Cu3V2O7(OH)22H2O (CuVO) cathode was synthe-
sized by a simple hydrothermal method [109]. A hybrid mecha-
nism involving phase transitions and classical insertion/
extraction reaction were discovered. Firstly, Zn2+ was embedded
in CuVO and replaced Cu2+ to form a Zn3(OH)2V2O72H2O (ZnVO)
Y. Zhou, F. Chen, H. Arandiyan et al. Journal of Energy Chemistry 57 (2021) 516–542

Fig. 18. (a) Schematic of the electrochemical process in a Zn/VO2 battery during discharge with a ZnSO4 aqueous electrolyte. Reproduced from Ref. [111] with permission
from Wiley-VC, (b) rate capability of VO2 and VO2/RGO electrodes at various current densities from 0.1 to 10 A g
1, (c, d) cycling performances of VO2 and VO2/RGO at the
current densities of 0.2 and 5 A g
1, respectively. Reproduced from Ref. [112] with permission from Elsevier.

phase. Secondly, Zn2+ was repeatedly inserted into the ZnVO lat-
tice, and a highly conductive Cu0 matrix was generated during the
cycling. The Cu0 matrix can significantly improve electronic trans-
port, and this Zn/CuVO battery system exhibited excellent elec-
trochemical performance (as listed in Table 3).
3.4. MxVO2
MxVO2 consists of square pyramids with 2*2 tunnels [17]. In
2017, a hollandite-type Al-doped VO1.52(OH)0.77 was used in aque-
ous ZIBs for Zn2+ intercalation material [110]. After replacing V3+ in

536
Y. Zhou, F. Chen, H. Arandiyan et al.
V1-xAlxO1.52(OH)0.77 with Al, the electrochemical performance was
improved. The strong Al-O bonds can improve operating voltage
and stability of V1-xAlxO1.52(OH)0.77. In 2019, Li et al. reported a
new mechanism that the VO2 cathode toward proton insertion
accompanied by Zn2+ insertion through the reversible deposition
of Zn4(OH)6SO45H2O on the cathode surface [111]. The working
mechanism was believed to depend on the anion and Zn2+ cation
species in aqueous electrolytes. As shown in Fig. 18(a), Zn2+ is typ-
ically coordinated with H2O molecules to form [Zn(H2O)6]2+, with
the reversible inter/extract of H+ in VO2 lattice, concurrent with
the reversible formation/decomposition of Zn4(OH)6SO45H2O on
the surface of the cathode (12 Zn + 16ZnSO4 + 11 6
H2O + VO2 M 16
[Zn4(OH)6SO45H2O] + HinsertVO2).
Recently, a new cathode material VO2(B)/reduce graphene oxide
(RGO) composite by a simple hydrothermal reaction was reported.
The RGO improved the electronic conductivity of the system and
prevented the structure collapse, thereby profoundly improving
the electrochemical performance of the battery. As shown in
Fig. 18(b)–(d), compared with VO2 cathode, the VO2/RGO cathode
significantly improved the rate capability and cycling performance
of ZIB. This result suggested that the dissolution ratio of V is minor,
and the stability of VO2/RGO is excellent [112].
3.5. MxV2O6
CuV2O6, which is composed of CuO6 octahedron and VO6 octa-
hedron, has been investigated for lithium-ion batteries for many
years. In recent years, CuV2O6 has been used as a cathode material
in ZIBs. For example, CuV2O6 nanobelts cathode with excellent
specific capacity (427 mAh g
1 at the current density of 0.1 A
g
1), long-term cycling stability (0.7% capacity loss after 3000
cycles at 5 A g
1) and high energy density (317 Wh kg
1 at
210 W kg
1) were reported in 2019 [113]. The reversible phase
transition between CuV2O6 and ZnV2O6 occurred during charge/
discharge process, which was trigged by zinc ion insertion/extrac-
Fig. 19. CV images of (a) MoO3, (c) Fe3O4 and (e) TiO2, at a rate of 0.5 mV s
1; galvanostatic cycling of (b) MoO3, (d) Fe3O4 and (f) TiO2 at a current density of 50 mA g
1.
Reproduced from Ref. [132] with permission from the Royal Society of Chemistry, (g) schematic illustration of the evolution and formation process of porous MoO2/Mo2N
heterostructured nanobelts on long-term cycling, (h) zinc-intercalation induced activation and stabilization process and cycling performance, (i, j) SEM images of porous
MoO2/Mo2N heterostructured nanobelts, (k) cycling performance at 100 mA g
1 for 100 cycles. Reproduced from Ref. [133] with permission from Elsevier.
537
Journal of Energy Chemistry 57 (2021) 516–542
tion (CuV2O6 + x Zn2+ + xe
M ZnxV2O6∙nH2O + Cu0)). The exchange
between Zn and Cu is completely displacement, resulting in that
the vanadium oxide polyhedral chains are always linked by diva-
lent cations, while the exchange of Li and Cu are not fully displace-
ment (CuV2O6 + x Li+ + xe
? LixCuV2O6). The replacement
between Cu2+ and Zn2+ is less destructive to the structure than
those between Cu2+ and Li+, making CuV2O6 more suitable as a
ZIB cathode material. In this work, by wrapping graphene oxide
on CuV2O6 nanocomposites, the specific capacity of the battery
can be significantly enhanced (at least 30% improvement). Another
study also confirmed that the reduction and oxidation of Cu2+/Cu0
were reversible during the electrochemical process, which pro-
vides a new strategy to design more cathode materials based on
the displacement reaction mechanism for ZIBs and other multiva-
lent metal-ion batteries [114].
3.6. MxVO4
A typical example of MxVO4 is an ultrathin layered Zn2(OH)VO4
cathode with 3D framework, which was reported in 2018 [115].
Excellent performance (101 mAh g
1 at 50 C/10 A g
1, 99% capacity
retained after 2000 cycles) has been obtained in this study based
on the unique morphology and structure of Zn2(OH)VO4. In addi-
tion to previously listed vanadium based cathode materials, vana-
dium phosphates (Na3V2(PO4)3 [116], Na3V2(PO4)3F3 [117]),
vanadium sulfides (VS2 [118]) and surface-oxidized vanadium
nitride (VNxOy [119]) have also been studied for ZIBs. During dis-
charge process, the V state in ASICON structured Na3V2(PO4)3
wrapped with graphene-like carbon changed from V4+ to V3+, and
Zn2+ was inserted into the cathode material. The electrochemical
performance of Na3V2(PO4)3F3 has been improved, all of which
are presented in Table 3. For the layered VS2 cathode material,
the interlayer space is 5.76 Å, which allowed the Zn2+ to intercalate
and form Zn0.09VS2, and then Zn0.23VS2 during the discharge pro-
cess [118]. The electrochemical performance is also listed in
Y. Zhou, F. Chen, H. Arandiyan et al. Journal of Energy Chemistry 57 (2021) 516–542

Table 3. Inspired by VS2, more layered transition-metal dichalco-
genides can be suitably applied in ZIBs. Furthermore, considering
the high electrical and ionic conductivity of vanadium nitride, a
surface-oxidized vanadium nitride (noted as VNxOy, the oxygen
atoms insert into the VN lattice without changing its structure)
has been developed [119]. The surface oxidation in VN could
improve its electrochemical activity, further improving the reac-
tion kinetics. By comparing VNxOy, VN/V2O3, and V2O5 electrodes,
VNxOy delivers the best average operating voltage and long cycles
stability. The working mechanism of VNxOy is not only Zn2+&H+
de-/intercalation accompanied by reversible cationic redox reac-
tion (V3+ M V2+), but also combining with the release/uptake of
OH
on the surface of VNxOy with reversible anionic (N3
M N2
)
redox: VN + mZn2+ + nH+ + (2 m + n) e
M ZnmHnVN (insertion
reaction), VNxOy + nOH
M VNxOy-(OH)n + ne
(surface redox
reaction).
In conclusion, vanadium-based materials exhibit high capacity
and excellent rate capability, attributed to their open layered
structure and multiple oxidations. Compared to manganese-
based cathode materials, vanadium-based materials deliver higher
capacity and better cycling stability, but the operation voltage is
lower than manganese-based cathodes. For example, recent
reported V-based cathodes VO2.0.2H2O&VOG and NH4V3O80.5H2O
achieved more than 400 mAh g
1, and many reported V-based
cathodes have 80% capacity retained after 1000 cycles (as shown
in Table 3). The operation voltage of V-based cathodes is much
lower than Mn-based cathodes, which has been summarized in
‘‘Summary and Perspective”. Further research should be included
in the vanadium-based cathode study, such as the selection of
stable structure and large lattice space V-based cathode materials
from the large family of vanadium oxides, surface engineering for

Fig. 20. (a) Schematic of the Zn-ion battery, the enlarged part is the structure change during the electrode reaction. Reproduced from Ref. [134] with permission from the
American Chemical Society, (b) schematic charge and discharge processes for a ZnNi1/2Mn1/2CoO4 electrode. Zn/Ni: silver; O: red; Mn/Ni/Co: green. Reproduced from Ref.
[135] with permission from Wiley.

Fig. 21. Specific capacities and average discharge potentials of representative cathode materials in ZIBs.

538
Y. Zhou, F. Chen, H. Arandiyan et al. Journal of Energy Chemistry 57 (2021) 516–542

cathode modifications and detailed reaction process shown in Fig. 21. Manganese oxides-based and vanadium oxides-
characterization. based cathodes exhibit superior capacity than other types of cath-
odes. Moreover, compared to Mn-O-based cathodes, the V-O-based
cathodes have low operation voltage, but other properties such as
4. Other oxide-based cathodes
cycling stability are superior to Mn-O-based cathode. Most other
types of cathodes show inadequate capacities, even if they have
In addition to manganese and vanadium oxides, there are some
high discharge potential [136–140]. So far, much work has been
other metal oxides (e.g. MoOx, TiO2, Fe3O4) [132,133] and spinels
focused on energy storage mechanisms analysis and performance
(e.g. ZnAlxCo2-xO4 [134], ZnNixMnxCo2-2xO4 (x = 1/2) [135]) used
improvement.
as cathode materials in ZIBs in recent years. MoO3 with a layered
In the past few years, various MnO2 (including a-, e-, k-, c-, b-,
structure, Fe3O4 with a 3D structure and TiO2 with an anatase
d- and todorokite-MnO2) have been studied as cathode materials,
structure are potential candidates for accommodating zinc ions.
which has different tunnelled, layered, or 3D structures. The
However, they still have poor battery performance [132]. As shown
energy storage mechanisms of MnO2 cathode are still under
in Fig. 19(a)-(f), a fast capacity fading and poor reversibility were
debate, including three reported mechanisms: Zn2+ reversible
found in MoO3, while the poor cycle performance in Fe3O4 indi-
intercalation, chemical conversion reaction and H+ and Zn2+ co-
cated that both materials could store zinc ions, but further studies
insertion. In addition to the MnO2 cathode, there are many other
should be conducted to improve the performance. For TiO2, the
manganese oxide cathode materials including MnO, Mn2O3,
weakly redox peaks and insufficient capacity were found in TiO2,
Mn3O4, ZnMn2O4, etc., even the by-product of Zn2+ insertion (Zn4(-
which indicates that anatase structure TiO2 is not suitable for cath-
OH)6(SO4)5H2O (ZHS)) was used as a cathode in ZIBs in recent
ode materials in ZIBs. In order to improve the battery performance
years. Besides Mn-O-based cathodes, V-O-based materials have
and clarify the reaction mechanism of MoO3, MoO2/Mo2N
been well developed in recent years, including V2O5/MxV2O5, Mx-
heterostructured nanobelts were prepared in 2018 [133]. As shown
V3O8, MxV2O7, MxVO2, MxV2O6, MxVO4 (M = alkali ion or H). Other
in Fig. 19(g), during the activation process (30–500 cycles), the
V-based materials have also been studied, such as vanadium phos-
MoO2 grains were formed in-situ in Mo2N nanobelts, which not
phates and vanadium sulfide. The energy storage mechanism of V-
only improved the zinc ions hosting ability but also increased ion
based materials is seemingly uncomplicated since the reversible
conductivity of the cathode material. Indeed, the capacity contin-
intercalation of Zn2+ is a consensus. However, the intrinsic electro-
ued to increase during activation process (Fig. 19h). The SEM
chemical process and the phase transition of active material during
images of porous MoO2/Mo2N heterostructured nanobelts are
Zn2+ insert/extract are still under debate.
shown in Fig. 19(i, j). The Mo2N matrix can help the MoO2 grains
To date, excellent electrochemical performance has been
avoid structure degradation during cycling and dissolution under
achieved in ZIBs. The morphology control of active materials and
weakly acidic electrolyte condition. In fact, the prepared material
cathode design are the two main directions for improving battery
exhibited an excellent capacity of 113 mAh g
1 for 1000 cycles at
performance. Researchers began to pay more attention to the mor-
0.1 A g
1, as well as high rate capacity and long-term cycle stability
phological aspects (specific surface area, porosity, nano-size, and
(Fig. 19k). Even though some metal oxides cathodes cannot achieve
shape) and novel design (surface coating, electrodeposition, com-
a satisfactory result in ZIBs, more and more suitable cathodes have
posite, etc.) of cathode materials. By improving the ion conductiv-
been found during the exploration. The other kinds of metal oxides
ity, reducing the active material dissolution, and increasing the
with large tunnel space or high ionic conductivity should be more
surface area to facilitate the Zn2+ ion diffusion coefficient, enhance
attempts to apply on ZIBs in future work.
the surface capacitive behaviour, and improve electrochemical
The spinel compounds exhibit high energy density, and through
kinetics.
Zn ions, intercalation/deintercalation, various reversible reactions
ZIBs are being developed as an ideal candidate for energy stor-
between Co4+/Co3+, Ni4+/Ni3+/Ni2+ and Mn4+/Mn3+ were observed.
age because of their simple structure, high safety, low toxicity,
Inspired by partial substitution of Co by Al to improve the CoO2
attractive mechanical flexibility and excellent electrochemical per-
stability in LiCoO2 battery, Al-doped ZnCoO4 cathode was prepared
formance. Despite tremendous achievements, ZIBs still have a long
by a sol–gel method and used in nonaqueous ZIB [134] (Fig. 20a).
way to go as lithium battery in commercial applications. Inspired
Due to reversible intercalation of zinc ions in ZnAlxCo2-xO4, a rever-
by the previous study, more efforts should be made in the research
sible conversion between Co3+ and Co4+ was responsible for the
of ZIBs, but there are still some problems that need to be revealed.
battery cycling. In addition, when x = 0.67, ZnAlxCo2-xO4 showed
Firstly, the mechanism of ZIBs cathodes should reach a consen-
best capacity in the nonaqueous ZIB system. Another spinel cath-
sus in the future. At the current stage, the controversies about the
ode using Mn and Ni substitute Co in ZnCo2O4 was investigated
oxidation state of manganese, Zn2+ and/or H+ (de)intercalation
in 2018 [135]. As shown in Fig. 20(b), multiple reversible transi-
mechanisms and the phase transition of manganese-based oxide
tions between Co4+/Co3+, Ni4+/Ni3+/Ni2+ and Mn4+/Mn3+ were
still exist. The in-situ characterization during charge and recharge
observed in the lattice during charging/discharging process. Both
process is a good choice for mechanism analysis.
reported spinels were consistent with reversible intercalation
Secondly, optimizing the synthesis method of cathode material
dynamics and achieved good cycling performance.
and exploring new types of cathodes are desirable in the future.
The morphology, surface area, and lattice space of active material
5. Summary and perspective have a substantial impact on the electrochemical performance of
the battery. These coefficients can be controlled by improving the
In summary, this review summarised various metal oxides as synthesis method. Low cost and safety are the principles for select-
cathode materials in ZIBs, including manganese oxide-based, vana- ing cathode candidate materials.
dium oxide-based and other metal oxide-based materials. These Thirdly, it is of considerable significance to deeply study the
metal oxide cathode materials have their unique crystal structures, interface between electrolytes and electrodes. The electrochemical
morphologies and cathode design, resulting in different working mechanism, electrode structure, electrode corrosion should be
mechanisms and distinct electrochemical performance. A sum- considered comprehensively. The compatibility of electrolytes
mary of the electrochemical properties of the selected ZIBs is with the electrode, preventing the zinc anode dendrite grow, and

539
Y. Zhou, F. Chen, H. Arandiyan et al.
preventing the corrosion of electrode are three main essential
requirements to the electrolyte. The most commonly used aqueous
electrolyte ZnSO4 and Zn(CF3SO3)2 have excellent performance, but
the price of Zn(CF3SO3)2 is much higher. The formation of ZHS is a
common phenomenon of ZnSO4 used in Mn-/V- based cathode. The
detailed process of ZHS formation needs further study. In addition,
the role of pH value of ZnSO4 (1 M 4.0) and Zn(CF3SO3)2 (3 M 3.6)
has not attracted attention in the past [17], and the lifetime and
reliability of ZIBs may be affected by this issue. Also, according to
common ion effect, Yan Jin et al. added MnSO4 to the ZnSO4 elec-
trolyte to prevent the Mn-cathode from dissolving. By adding
Mn-salt into electrolytes (MnSO4 into ZnSO4, Mn(TFSI)2 into Zn
(TFSI)2), the ion conductivity of the electrolyte can be improved,
and the pH value of electrolyte also become much closer to neutral
solution [53]. Besides, even though the aqueous electrolyte with
rich aqueous water content brings better electrochemical propri-
eties, the dendrite growth of Zn anode in aqueous electrolytes
should be noticed. Both ionic liquid electrolytes and organic elec-
trolytes are conducive to improving the stability and reversibility
of zinc anode [141,142]. It is a challenge to find a suitable elec-
trolyte that can both improve the stability and reversibility of
anode and guarantee the good electrochemical performance of
the cathode.
Fourthly, with the development of nonaqueous electrolytes,
there is an urgent need to explore soft polymer cathode material
that meets the requirements of flexible ZIBs. Besides, the current
collector, zinc anode and flexible electrolyte should also be consid-
ered. For example, the morphologic changes, optimization of
nanostructure mixture additives, and shape memory effect of zinc
metal are problems that hinder the development of flexible ZIB.
Synthesizing flexible zinc anode by electrodepositing zinc on a
flexible current collector or coating zinc metal on a flexible current
collector are two directions to avoid the shape memory effect. The
thickness of the current collector, which can affect the conductiv-
ity, should be considered. Metal mesh and metal foam are promis-
ing to reduce the risk of electrode dendrite growth.
Finally, more studies should carry out for the practical applica-
tions of ZIBs. Until now, the development of practical applications
of ZIBs cannot be compared with Li-ion batteries. As the most
promising application of ZIBs, flexible ZIBs with stretchability
and mechanical properties, self-healing, cooling recovery, elec-
trochromism, thermal response, and photo-response capabilities
are still in experimental stage. The parameters (such as large load-
ing mass, life span requirement, minimal electrolyte usage) should
be considered further when it comes to the industrial application.
Furthermore, flexibility, price, weight and safety are the most
important issues in designing wearable ZIBs.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
This work is funded by the Australian Research Council Project
(grant no. LP190100113). C.Z. is grateful for the award of a Future
Fellow from Australian Research Council (FT170100224).
References
[1] M. Armand, J.M. Tarascon, Nature 451 (2008) 652–657.
[2] B. Dunn, H. Kamath, J.-M. Tarascon, Science 334 (2011) 928–935.
[3] S. Chu, A. Majumdar, Nature 488 (2012) 294–303.
540
Journal of Energy Chemistry 57 (2021) 516–542
[4] X. Wang, J. Mujtaba, F. Fang, M. Ahmad, H. Arandiyan, H. Yang, G. Sun, H. Sun,
RSC Adv. 5 (2015) 91574–91580.
[5] C.J. Rydh, M. Karlström, Resour. Conserv. Recycl. 34 (2002) 289–309.
[6] Y. Yu, J. Li, J. Wang, X. Wu, C. Yu, T. Xu, B. Chang, H. Sun, H. Arandiyan,
Catalysts 9 (2019) 152.
[7] Y. Liu, H. Wan, H. Zhang, J. Chen, F. Fang, N. Jiang, W. Zhang, F. Zhou, H.
Arandiyan, Y. Wang, G. Liu, Z. Wang, S. Luo, X. Chen, H. Sun, ACS Appl. Nano
Mater. 3 (2020) 3892–3903.
[8] J. Mujtaba, H. Sun, G. Huang, Y. Zhao, H. Arandiyan, G. Sun, S. Xu, J. Zhu, RSC
Adv. 6 (2016) 31775–31781.
[9] X. Wang, Y. Liu, H. Arandiyan, H. Yang, L. Bai, J. Mujtaba, Q. Wang, S. Liu, H.
Sun, Appl. Surf. Sci. 389 (2016) 240–246.
[10] H. Wan, Y. Liu, H. Zhang, W. Zhang, N. Jiang, Z. Wang, S. Luo, H. Arandiyan, H.
Liu, H. Sun, Electrochim. Acta 281 (2018) 31–38.
[11] H. Arandiyan, Y. Wang, H. Sun, M. Rezaei, H. Dai, ChemComm 54 (2018)
6484–6502.
[12] S.-B. Son, T. Gao, S.P. Harvey, K.X. Steirer, A. Stokes, A. Norman, C. Wang, A.
Cresce, K. Xu, C. Ban, Nat. Chem. 10 (2018) 532–539.
[13] D. Wang, X. Gao, Y. Chen, L. Jin, C. Kuss, P.G. Bruce, Nat. Mater. 17 (2017) 16–
20.
[14] J.C. Pramudita, D. Sehrawat, D. Goonetilleke, N. Sharma, Adv. Energy Mater. 7
(2017) 1602911.
[15] W. Xu, Y. Wang, Nanomicro Lett. 11 (2019) 90.
[16] J. Ming, J. Guo, C. Xia, W. Wang, H.N. Alshareef, Mater. Sci. Eng. R Rep. 135
(2019) 58–84.
[17] M. Song, H. Tan, D. Chao, H.J. Fan, Adv. Funct. Mater. 28 (2018) 1802564.
[18] S. Huang, J. Zhu, J. Tian, Z. Niu, Chem. Eur. J. 25 (2019) 14480–14494.
[19] S. Zhang, N. Yu, S. Zeng, S. Zhou, M. Chen, J. Di, Q. Li, J. Mater. Chem. A 6 (2018)
12237–12243.
[20] X. Cheng, J. Pan, Y. Zhao, M. Liao, H. Peng, Adv. Energy Mater. 8 (2018)
1702184.
[21] W. Lu, C. Xie, H. Zhang, X. Li, ChemSusChem 11 (2018) 3996–4006.
[22] Z. Wang, Z. Ruan, W.S. Ng, H. Li, Z. Tang, Z. Liu, Y. Wang, H. Hu, C. Zhi, Small
Methods 2 (2018) 1800150.
[23] H. Li, Z. Liu, G. Liang, Y. Huang, Y. Huang, M. Zhu, Z. Pei, Q. Xue, Z. Tang, Y.
Wang, B. Li, C. Zhi, ACS Nano 12 (2018) 3140–3148.
[24] S. Huang, F. Wan, S. Bi, J. Zhu, Z. Niu, J. Chen, Angew. Chem. Int. Ed. 58 (2019)
4313–4317.
[25] F. Mo, H. Li, Z. Pei, G. Liang, L. Ma, Q. Yang, D. Wang, Y. Huang, C. Zhi, Sci. Bull.
63 (2018) 1077–1086.
[26] Y. Li, J. Fu, C. Zhong, T. Wu, Z. Chen, W. Hu, K. Amine, J. Lu, Adv. Energy Mater.
9 (2019) 1802605.
[27] H. Li, C. Han, Y. Huang, Y. Huang, M. Zhu, Z. Pei, Q. Xue, Z. Wang, Z. Liu, Z.
Tang, Y. Wang, F. Kang, B. Li, C. Zhi, Energy Environ. Sci. 11 (2018) 941–951.
[28] N. Zhang, F. Cheng, J. Liu, L. Wang, X. Long, X. Liu, F. Li, J. Chen, Nat. Commun.
8 (2017) 405.
[29] F. Wan, L. Zhang, X. Wang, S. Bi, Z. Niu, J. Chen, Adv. Funct. Mater. 28 (2018)
1804975.
[30] L. Dong, W. Yang, W. Yang, Y. Li, W. Wu, G. Wang, J. Mater. Chem. A 7 (2019)
13810–13832.
[31] Y. Zhao, Y. Zhu, X. Zhang, InfoMat 2 (2020) 237–260.
[32] R. Demir-Cakan, M.R. Palacin, L. Croguennec, J. Mater. Chem. A 7 (2019)
20519–20539.
[33] L. Liu, X. Guan, Z. Li, X. Zi, H. Dai, H. He, Appl. Catal. B 90 (2009) 1–9.
[34] C. Xu, S.W. Chiang, J. Ma, F. Kang, J. Electrochem. Soc. 160 (2013)
A93–A97.
[35] B. Lee, H.R. Seo, H.R. Lee, C.S. Yoon, J.H. Kim, K.Y. Chung, B.W. Cho, S.H. Oh,
ChemSusChem 9 (2016) 2948–2956.
[36] M.H. Alfaruqi, J. Gim, S. Kim, J. Song, J. Jo, S. Kim, V. Mathew, J. Kim, J. Power
Sources 288 (2015) 320–327.
[37] B. Lee, C.S. Yoon, H.R. Lee, K.Y. Chung, B.W. Cho, S.H. Oh, Sci. Rep. 4 (2014),
6066–6066.
[38] B. Lee, H.R. Lee, H. Kim, K.Y. Chung, B.W. Cho, S.H. Oh, ChemComm 51 (2015)
9265–9268.
[39] S. Zhao, B. Han, D. Zhang, Q. Huang, L. Xiao, L. Chen, D.G. Ivey, Y. Deng, W.
Wei, J. Mater. Chem. A 6 (2018) 5733–5739.
[40] H. Pan, Y. Shao, P. Yan, Y. Cheng, K.S. Han, Z. Nie, C. Wang, J. Yang, X. Li, P.
Bhattacharya, K.T. Mueller, J. Liu, Nat. Energy 1 (2016) 16039.
[41] N. Palaniyandy, M.A. Kebede, K. Raju, K.I. Ozoemena, L. le Roux, M.K. Mathe, R.
Jayaprakasam, Mater. Chem. Phys. 230 (2019) 258–266.
[42] D.E. Simon, R.W. Morton, J.J. Gislason, Adv. X-ray Anal. 47 (2004) 267–
280.
[43] W. Sun, F. Wang, S. Hou, C. Yang, X. Fan, Z. Ma, T. Gao, F. Han, R. Hu, M. Zhu, C.
Wang, J. Am. Chem. Soc. 139 (2017) 9775–9778.
[44] L. Wang, X. Cao, L. Xu, J. Chen, J. Zheng, ACS Sustain. Chem. Eng. 6 (2018)
16055–16063.
[45] M. Zhang, W. Wu, J. Luo, H. Zhang, J. Liu, X. Liu, Y. Yang, X. Lu, J. Mater. Chem.
A 8 (2020) 11642–11648.
[46] N. Zhang, F. Cheng, Y. Liu, Q. Zhao, K. Lei, C. Chen, X. Liu, J. Chen, J. Am. Chem.
Soc. 138 (2016) 12894–12901.
[47] Y. Tao, Z. Li, L. Tang, X. Pu, T. Cao, D. Cheng, Q. Xu, H. Liu, Y. Wang, Y. Xia,
Electrochim. Acta 331 (2020) 135296.
[48] J. Hao, J. Mou, J. Zhang, L. Dong, W. Liu, C. Xu, F. Kang, Electrochim. Acta 259
(2018) 170–178.
Y. Zhou, F. Chen, H. Arandiyan et al.
[49] H. Chen, W. Zhou, D. Zhu, Z. Liu, Z. Feng, J. Li, Y. Chen, J. Alloys Compd. 813
(2020) 151812.
[50] J. Long, J. Gu, Z. Yang, J. Mao, J. Hao, Z. Chen, Z. Guo, J. Mater. Chem. A 7 (2019)
17854–17866.
[51] M.H. Alfaruqi, J. Gim, S. Kim, J. Song, D.T. Pham, J. Jo, Z. Xiu, V. Mathew, J. Kim,
Electrochem. Commun. 60 (2015) 121–125.
[52] S.-D. Han, S. Kim, D. Li, V. Petkov, H.D. Yoo, P.J. Phillips, H. Wang, J.J. Kim, K.L.
More, B. Key, R.F. Klie, J. Cabana, V.R. Stamenkovic, T.T. Fister, N.M.
Markovic, A.K. Burrell, S. Tepavcevic, J.T. Vaughey, Chem. Mater. 29 (2017)
4874–4884.
[53] Y. Jin, L. Zou, L. Liu, M.H. Engelhard, R.L. Patel, Z. Nie, K.S. Han, Y. Shao, C.
Wang, J. Zhu, H. Pan, J. Liu, Adv. Mater. 31 (2019) 1900567.
[54] R.D. Corpuz, L.M.Z. De Juan, S. Praserthdam, R. Pornprasertsuk, T. Yonezawa,
M.T. Nguyen, S. Kheawhom, Sci. Rep. 9 (2019) 15107.
[55] T. Yamamoto, T. Shoji, Rechargeable ZnjZnSO4jMnO2-type cells, Inorgan.
Chim. Acta 117 (1986) L27–L28.
[56] G.G. Kumar, S. Sampath, Solid State Ion 160 (2003) 289–300.
[57] C. Xu, B. Li, H. Du, F. Kang, Angew. Chem. Int. Ed. 51 (2012) 933–935.
[58] M.H. Alfaruqi, V. Mathew, J. Gim, S. Kim, J. Song, J.P. Baboo, S.H. Choi, J. Kim,
Chem. Mater. 27 (2015) 3609–3620.
[59] C. Wei, C. Xu, B. Li, H. Du, F. Kang, J. Phys. Chem. Solids 73 (2012) 1487–1491.
[60] S. Islam, M.H. Alfaruqi, V. Mathew, J. Song, S. Kim, S. Kim, J. Jo, J.P. Baboo, D.T.
Pham, D.Y. Putro, Y.-K. Sun, J. Kim, J. Mater. Chem. A 5 (2017) 23299–23309.
[61] M. Han, J. Huang, S. Liang, L. Shan, X. Xie, Z. Yi, Y. Wang, S. Guo, J. Zhou,
iScience 23 (2020) 100797.
[62] J. Lee, J.B. Ju, W.I. Cho, B.W. Cho, S.H. Oh, Electrochim. Acta 112 (2013) 138–
143.
[63] W. Qiu, Y. Li, A. You, Z. Zhang, G. Li, X. Lu, Y. Tong, J. Mater. Chem. A 5 (2017)
14838–14846.
[64] Y. Huang, W. He, P. Zhang, X. Lu, Funct. Mater. Lett. 11 (2018) 1840006.
[65] J. Wang, X. Sun, H. Zhao, L. Xu, J. Xia, M. Luo, Y. Yang, Y. Du, J. Phys. Chem. C
123 (2019) 22735–22741.
[66] Y. Zhang, S. Deng, M. Luo, G. Pan, Y. Zeng, X. Lu, C. Ai, Q. Liu, Q. Xiong, X. Wang,
X. Xia, J. Tu, Small 15 (2019) 1905452.
[67] J. Mao, F.-F. Wu, W.-H. Shi, W.-X. Liu, X.-L. Xu, G.-F. Cai, Y.-W. Li, X.-H. Cao,
Chin. J. Polym. Sci. 38 (2020) 514–521.
[68] Y. Huang, J. Zhang, J. Liu, Z. Li, S. Jin, Z. Li, S. Zhang, H. Zhou, Mater. Today,
Energy 14 (2019) 100349.
[69] G. Fang, C. Zhu, M. Chen, J. Zhou, B. Tang, X. Cao, X. Zheng, A. Pan, S. Liang,
Adv. Funct. Mater. 29 (2019) 1808375.
[70] T. Zhang, Y. Tang, G. Fang, C. Zhang, H. Zhang, X. Guo, X. Cao, J. Zhou, A. Pan, S.
Liang, Adv. Funct. Mater. 30 (2020) 2002711.
[71] B. Jiang, C. Xu, C. Wu, L. Dong, J. Li, F. Kang, Electrochim. Acta 229 (2017) 422–
428.
[72] J. Wang, J.-G. Wang, H. Liu, Z. You, C. Wei, F. Kang, J. Power Sources 438 (2019)
226951.
[73] C. Zhu, G. Fang, S. Liang, Z. Chen, Z. Wang, J. Ma, H. Wang, B. Tang, X. Zheng, J.
Zhou, Energy Stor. Mater. 24 (2020) 394–401.
[74] B. Wu, G. Zhang, M. Yan, T. Xiong, P. He, L. He, X. Xu, L. Mai, Small 14 (2018)
1703850.
[75] L. Zhang, Y. Zhang, H. Dai, J. Deng, L. Wei, H. He, Catal. Today 153 (2010) 143–
149.
[76] C. Wang, Y. Zeng, X. Xiao, S. Wu, G. Zhong, K. Xu, Z. Wei, W. Su, X. Lu, J. Energy
Chem. 43 (2020) 182–187.
[77] K. Sada, B. Senthilkumar, P. Barpanda, J. Mater. Chem. A 7 (2019) 23981–
23988.
[78] M. Mao, X. Wu, Y. Hu, Q. Yuan, Y.-B. He, F. Kang, J. Energy Chem. 52 (2021)
277–283.
[79] T. Sun, Q. Nian, S. Zheng, J. Shi, Z. Tao, Small 16 (2020) 2000597.
[80] P.Y. Zavalij, M.S. Whittingham, Acta. Crystallogr. B 55 (1999) 627–663.
[81] J.-C. Badot, N. Baffier, J. Mater. Chem. 2 (1992) 1167–1174.
[82] D.B. Le, S. Passerini, F. Coustier, J. Guo, T. Soderstrom, B.B. Owens, W.H. Smyrl,
Chem. Mater. 10 (1998) 682–684.
[83] M. Giorgetti, S. Passerini, M. Berrettoni, W.H. Smyrl, J. Synchrotron Radiat. 6
(1999) 743–745.
[84] P. Hu, M. Yan, T. Zhu, X. Wang, X. Wei, J. Li, L. Zhou, Z. Li, L. Chen, L. Mai, ACS
Appl. Mater. Interfaces 9 (2017) 42717–42722.
[85] N. Zhang, Y. Dong, M. Jia, X. Bian, Y. Wang, M. Qiu, J. Xu, Y. Liu, L. Jiao, F. Cheng,
ACS Energy Lett. 3 (2018) 1366–1372.
[86] X. Chen, L. Wang, H. Li, F. Cheng, J. Chen, J. Energy Chem. 38 (2019) 20–25.
[87] L. Chen, Z. Yang, F. Cui, J. Meng, H. Chen, X. Zeng, Appl. Surf. Sci. 507 (2020)
145137.
[88] W. Zhou, J. Chen, M. Chen, X. Xu, Q. Tian, J. Xu, C.-P. Wong, RSC Adv. 9 (2019)
30556–30564.
[89] L.M. De Juan-Corpuz, R.D. Corpuz, A. Somwangthanaroj, M.T. Nguyen, T.
Yonezawa, J. Ma, S. Kheawhom, Energies 13 (2019) 31.
[90] B. Yin, S. Zhang, K. Ke, T. Xiong, Y. Wang, B.K.D. Lim, W.S.V. Lee, Z. Wang, J.
Xue, Nanoscale 11 (2019) 19723–19728.
[91] D. Kundu, B.D. Adams, V. Duffort, S.H. Vajargah, L.F. Nazar, Nat. Energy 1
(2016) 16119.
[92] C. Xia, J. Guo, P. Li, X. Zhang, H.N. Alshareef, Angew. Chem. Int. Ed. 57 (2018)
3943–3948.
541
Journal of Energy Chemistry 57 (2021) 516–542
[93] P. He, G. Zhang, X. Liao, M. Yan, X. Xu, Q. An, J. Liu, L. Mai, Adv. Energy Mater. 8
(2018) 1702463.
[94] B. Tang, G. Fang, J. Zhou, L. Wang, Y. Lei, C. Wang, T. Lin, Y. Tang, S. Liang, Nano
Energy 51 (2018) 579–587.
[95] W. Zhang, C. Tang, B. Lan, L. Chen, W. Tang, C. Zuo, S. Dong, Q. An, P. Luo, J.
Alloys Compd. 819 (2020) 152971.
[96] L. Shan, Y. Yang, W. Zhang, H. Chen, G. Fang, J. Zhou, S. Liang, Energy Stor.
Mater. 18 (2019) 10–14.
[97] G. Xu, X. Liu, S. Huang, L. Li, X. Wei, J. Cao, L. Yang, P.K. Chu, ACS Appl. Mater.
Interfaces 12 (2020) 706–716.
[98] P. Gao, Q. Ru, H. Yan, S. Cheng, Y. Liu, X. Hou, L. Wei, F. Chi-Chung Ling,
ChemElectroChem 7 (2020) 283–288.
[99] Durupthy, N. Steunou, T. Coradin, J. Maquet, C. Bonhomme, J. Livage, J. Mater.
Chem. 15 (2005) 1090–1098.
[100] M.H. Alfaruqi, V. Mathew, J. Song, S. Kim, S. Islam, D.T. Pham, J. Jo, S. Kim, J.P.
Baboo, Z. Xiu, K.-S. Lee, Y.-K. Sun, J. Kim, Chem. Mater. 29 (2017) 1684–1694.
[101] P. Hu, T. Zhu, X. Wang, X. Wei, M. Yan, J. Li, W. Luo, W. Yang, W. Zhang, L.
Zhou, Z. Zhou, L. Mai, Nano Lett. 18 (2018) 1758–1763.
[102] P. He, Y. Quan, X. Xu, M. Yan, W. Yang, Q. An, L. He, L. Mai, Small 13 (2017)
1702551.
[103] Q. Pang, C. Sun, Y. Yu, K. Zhao, Z. Zhang, P.M. Voyles, G. Chen, Y. Wei, X. Wang,
Adv. Energy Mater. 8 (2018) 1800144.
[104] D. Kundu, S. Hosseini Vajargah, L. Wan, B. Adams, D. Prendergast, L.F. Nazar,
Energy Environ. Sci. 11 (2018) 881–892.
[105] H. Jiang, Y. Zhang, Z. Pan, L. Xu, J. Zheng, Z. Gao, T. Hu, C. Meng, J. Wang,
Mater. Chem. Front. 4 (2020) 1434–1443.
[106] P.Y. Zavalij, F. Zhang, M.S. Whittingham, Acta Crystallogr. C 53 (1997) 1738–
1739.
[107] C. Xia, J. Guo, Y. Lei, H. Liang, C. Zhao, Adv. Mater. 30 (2018) 1705580.
[108] B. Sambandam, V. Soundharrajan, S. Kim, M.H. Alfaruqi, J. Jo, S. Kim, V.
Mathew, Y.-K. Sun, J. Kim, J. Mater. Chem. A 6 (2018) 3850–3856.
[109] L. Chen, Z. Yang, J. Wu, H. Chen, J. Meng, Electrochim. Acta 330 (2020)
135347.
[110] J.H. Jo, Y.-K. Sun, S.-T. Myung, J. Mater. Chem. A 5 (2017) 8367–8375.
[111] Z. Li, S. Ganapathy, Y. Xu, Z. Zhou, M. Sarilar, M. Wagemaker, Adv. Energy
Mater. 9 (2019) 1900237.
[112] F. Cui, J. Zhao, D. Zhang, Y. Fang, F. Hu, K. Zhu, Chem. Eng. J. 390 (2020)
124118.
[113] Y. Liu, Q. Li, K. Ma, G. Yang, C. Wang, ACS Nano 13 (2019) 12081–12089.
[114] X. Yu, F. Hu, F. Cui, J. Zhao, C. Guan, K. Zhu, Dalton Trans. 49 (2020) 1048–
1055.
[115] D. Chao, C. Zhu, M. Song, P. Liang, X. Zhang, N.H. Tiep, H. Zhao, J. Wang, R.
Wang, H. Zhang, H.J. Fan, Adv. Mater. 30 (2018) 1803181.
[116] G. Li, Z. Yang, Y. Jiang, C. Jin, W. Huang, X. Ding, Y. Huang, Nano Energy 25
(2016) 211–217.
[117] W. Li, K. Wang, S. Cheng, K. Jiang, Energy Stor. Mater. 15 (2018) 14–21.
[118] P. He, M. Yan, G. Zhang, R. Sun, L. Chen, Q. An, L. Mai, Adv. Energy Mater. 7
(2017) 1601920.
[119] G. Fang, S. Liang, Z. Chen, P. Cui, X. Zheng, A. Pan, B. Lu, X. Lu, J. Zhou, Adv.
Funct. Mater. 29 (2019) 1905267.
[120] H. Geng, M. Cheng, B. Wang, Y. Yang, Y. Zhang, C.C. Li, Adv. Funct. Mater. 30
(2020) 1907684.
[121] J. Li, K. McColl, X. Lu, S. Sathasivam, H. Dong, L. Kang, Z. Li, S. Zhao, A.G.
Kafizas, R. Wang, D.J.L. Brett, P.R. Shearing, F. Corà, G. He, C.J. Carmalt, I.P.
Parkin, Adv. Energy Mater. 10 (2020) 2000058.
[122] S. Liu, H. Zhu, B. Zhang, G. Li, H. Zhu, Y. Ren, H. Geng, Y. Yang, Q. Liu, C.C. Li,
Adv. Mater. 32 (2020) 2001113.
[123] C. Liu, Z. Neale, J. Zheng, X. Jia, J. Huang, M. Yan, M. Tian, M. Wang, J. Yang, G.
Cao, Energy Environ. Sci. 12 (2019) 2273–2285.
[124] M. Tian, C. Liu, J. Zheng, X. Jia, E.P. Jahrman, G.T. Seidler, D. Long, M. Atif, M.
Alsalhi, G. Cao, Energy Stor. Mater. 29 (2020) 9–16.
[125] L. Xu, Y. Zhang, H. Jiang, J. Zheng, X. Dong, T. Hu, C. Meng, Colloids Surf. A
Physicochem. Eng. Asp. 593 (2020) 124621.
[126] C. Shen, X. Li, N. Li, K. Xie, J.-G. Wang, X. Liu, B. Wei, ACS Appl. Mater.
Interfaces 10 (2018) 25446–25453.
[127] X. Dai, F. Wan, L. Zhang, H. Cao, Z. Niu, Energy Stor. Mater. 17 (2019) 143–
150.
[128] J. Ding, Z. Du, L. Gu, B. Li, L. Wang, S. Wang, Y. Gong, S. Yang, Adv. Mater. 30
(2018) 1800762.
[129] D. Jia, K. Zheng, M. Song, H. Tan, A. Zhang, L. Wang, L. Yue, D. Li, C. Li, J. Liu,
Nano Res. 13 (2020) 215–224.
[130] Q. Li, Y. Liu, K. Ma, G. Yang, C. Wang, Small Methods 3 (2019) 1900637.
[131] H. Jiang, Y. Zhang, Z. Pan, L. Xu, J. Zheng, Z. Gao, T. Hu, C. Meng, Electrochim.
Acta 332 (2020) 135506.
[132] W. Liu, J. Hao, C. Xu, J. Mou, L. Dong, F. Jiang, Z. Kang, J. Wu, B. Jiang, F. Kang,
ChemComm 53 (2017) 6872–6874.
[133] W. Xu, K. Zhao, Y. Wang, Energy Stor. Mater. 15 (2018) 374–379.
[134] C. Pan, R.G. Nuzzo, A.A. Gewirth, Chem. Mater. 29 (2017) 9351–9359.
[135] C. Pan, R. Zhang, R.G. Nuzzo, A.A. Gewirth, Adv. Energy Mater. 8 (2018)
1800589.
[136] L. Zhang, L. Chen, X. Zhou, Z. Liu, Sci. Rep. 5 (2015) 18263.
[137] Z. Jia, B. Wang, Y. Wang, C. Mater, Chem. Phys. 149–150 (2015) 601–606.
Y. Zhou, F. Chen, H. Arandiyan et al. Journal of Energy Chemistry 57 (2021) 516–542

[138] Z. Liu, G. Pulletikurthi, F. Endres, ACS Appl. Mater. Interfaces 8 (2016) 12158–
12164.
[139] Q. Zhao, W. Huang, Z. Luo, L. Liu, Y. Lu, Y. Li, L. Li, J. Hu, H. Ma, J. Chen, Sci. Adv.
4 (2018) eaao1761.
[140] M.S. Chae, J.W. Heo, S.-C. Lim, S.-T. Hong, Inorg. Chem. 55 (2016) 3294–3301.
[141] F. Wang, O. Borodin, T. Gao, X. Fan, W. Sun, F. Han, A. Faraone, J.A. Dura, K. Xu,
C. Wang, Nat. Mater. 17 (2018) 543–549.
[142] A. Naveed, H. Yang, Y. Shao, J. Yang, N. Yanna, J. Liu, S. Shi, L. Zhang, A. Ye, B.
He, J. Wang, Adv. Mater. 31 (2019) 1900668.

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