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Materials chemistry for rechargeable zinc-ion batteries

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Chem Soc Rev
TUTORIAL REVIEW

Materials chemistry for rechargeable zinc-ion

batteries†
Cite this: Chem. Soc. Rev., 2020,
49, 4203 ab
Ning Zhang, Xuyong Chen,a Meng Yu,a Zhiqiang Niu, a
Fangyi Cheng *a
a
and Jun Chen

Received 15th November 2019
DOI: 10.1039/c9cs00349e
rsc.li/chem-soc-rev
Rechargeable zinc-ion batteries (ZIBs) are promising for large scale energy storage and portable
electronic applications due to their low cost, material abundance, high safety, acceptable energy density
and environmental friendliness. This tutorial review presents an introduction to the fundamentals,
challenges, recent advances and prospects related to ZIBs. Firstly, the intrinsic chemical properties,
challenges and strategies of metallic zinc anodes are underscored. Then, the multiple types of cathode
materials are classified and comparatively discussed in terms of their structural and electrochemical
properties, issues and remedies. Specific attention is paid to the mechanistic understanding and
structural transformation of cathode materials based on Zn ion-(de)intercalation chemistry. After that,
the widely investigated electrolytes are elaborated by discussing their effect on Zn plating/stripping
behaviours, reaction kinetics, electrode/electrolyte interface chemistries, and cell performances. Finally,
the remaining challenges and future perspectives are outlined for the development of ZIBs.

Key learning points

(1) Operation principles and characteristics of rechargeable zinc-ion batteries.
(2) Intrinsic properties and challenges of Zn electrodes and strategies to enhance the Zn plating/stripping performances and suppress dendrite issues.
(3) Classifications, structural features, electrochemical performances, design principles and Zn-storage reaction mechanisms of cathode materials.
(4) Chemical and physical properties, electrochemical behaviours and electrode compatibility of electrolytes for Zn storage and Zn-ion intercalation.
(5) Remaining challenges and perspectives of rechargeable zinc-ion batteries.

1. Introduction attention.1–3 Rechargeable zinc-ion batteries (ZIBs) hold great

The utilization of renewable energy resources such as solar and wind
has come under global spotlight in light of the looming concerns
regarding climatic deterioration and environmental pollution,
which motivates the pursuit of safe, economical, sustainable
and efficient electrochemical energy storage and conversion tech-
nologies. Among various options, lithium-ion batteries (LIBs) with
high energy density have been widely applied in portable electro-
nics and considered for electric vehicles, but the limited lithium
reservoir, fluctuant price and safety issues impede their large-scale
deployment. As alternatives, battery chemistries based on more
abundant elements (e.g., Na, K, Mg, Al, Zn) have received extensive
a
Renewable Energy Conversion and Storage Center, Key Laboratory of Advanced
Energy Materials Chemistry (Ministry of Education), College of Chemistry,
Nankai University, Tianjin 300071, China. E-mail: fycheng@nankai.edu.cn
b
College of Chemistry & Environmental Science, Hebei University, Baoding 071002,
China
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c9cs00349e
promise for large-scale energy storage applications owing to the
merits of Zn including higher ambient stability and lower cost of
Zn (BUS$2.4 kg1) than alkali metals (e.g., Li B US$19.2 kg1;
Na B US$3.1 kg1; K B US$13.1 kg1), good compatibility with
aqueous electrolytes, nontoxicity, facile material processing and
battery manufacturing.2,4,5 In addition, the price of typical cathode
materials such as MnO2 (BUS$1.7 kg1) and V2O5 (BUS$5.5 kg1)
for ZIBs is much cheaper than that of LIBs (e.g., LiCoO2,
BUS$55 kg1 and Li(NiMnCo)O2, BUS$34 kg1).2,3,6 Moreover,
the generally used aqueous electrolyte for ZIBs is inexpensive
with high safety and high ionic conductivity (0.1–6 S cm1)
when compared to the flammable organic electrolytes in LIBs
(103–102 S cm1). The estimated cost of ZIBs based on a Zn
anode, a vanadium oxide cathode and an aqueous ZnSO4 electro-
lyte is below $65 per kW h, much cheaper than that of current LIBs
(B$300 per kW h).3 Due to these advantages (Fig. 1a) ZIBs have
promising prospects for practical applications.
Historically, metallic zinc was employed as anode material
of the first battery invented in 1799 (Volta Pile). Nowadays zinc

This journal is © The Royal Society of Chemistry 2020 Chem. Soc. Rev., 2020, 49, 4203--4219 | 4203
Tutorial Review
Fig. 1 (a) Multi-angle comparison of zinc-ion and lithium-ion batteries.
(b) Schematic illustration of the working principle of rechargeable zinc-ion
batteries.
has been widely used in various battery technologies, including
Zn–MnO2, Zn–NiOOH, Zn–Ag2O, Zn–air batteries, etc.
Among them, alkaline Zn–MnO2 batteries dominate the
primary battery market since their commercialization.7 Earlier
Ning Zhang received his BS degree
in Chemistry from Hebei University
in 2012 and then obtained his PhD
in Inorganic Chemistry from Nankai
University in 2017. He is now an
associate professor in the College of
Chemistry & Environmental Science
at Hebei University. His current
research focuses on the design and
synthesis of functional materials for
applications in energy storage and
conversion (lithium/sodium-ion
Ning Zhang batteries and aqueous zinc-ion
batteries).
Xuyong Chen received his
bachelor’s degree (2016) in
Metallurgical Engineering from
Wuhan University of Science and
Technology, and MS degree
(2019) in Chemical Engineering
from Nankai University
supervised by Prof. Fangyi
Cheng. His research is focused
on aqueous zinc-ion batteries.
Xuyong Chen
4204 | Chem. Soc. Rev., 2020, 49, 4203--4219
Chem Soc Rev
attempts to develop rechargeable Zn-based batteries are pla-
gued by the fast capacity fading and poor coulombic efficiency
(CE), mainly due to the uncontrollable growth of Zn dendrites
and the formation of insulating, irreversible by-products (e.g.,
ZnO) in alkaline electrolytes (e.g., concentrated KOH solution).8
Studies on rechargeable ZIBs slowed down until 2012 when
Kang and co-workers revisited zinc-ion battery chemistries
with mildly acidic aqueous electrolytes.9 As shown in Fig. 1b,
a rechargeable ZIB generally consists of a metallic Zn anode, a
Zn2+ storage cathode and a Zn2+-salt electrolyte, operating via
the reversible Zn2+ intercalation/deintercalation (cathode) and
Zn plating/stripping (anode) upon discharging/charging.
To date, extensive studies have been reported for ZIBs,
covering metallic Zn anodes, cathode materials, electrolytes and
potential applications. Fig. 2 outlines the brief development
history of ZIBs. The zinc anode features good compatibility with
aqueous and non-aqueous electrolytes. Recently investigated neu-
tral and mildly acidic aqueous electrolytes are shown to minimize
the formation of Zn dendrites and inactive species that often occur
in alkaline media.4,10 However, the CE of Zn plating/stripping and
utilization of hostless Zn anodes remain unsatisfactory. The
electrolyte/electrode interfacial chemistry and electrochemical
behaviours of Zn anodes in non-aqueous electrolyte require further
investigations. For cathodes, manganese dioxides with different
polymorphs were initially investigated as Zn-insertion hosts,
following a logic shift from primary to rechargeable Zn–MnO2
batteries. Subsequently, Prussian blue analogues, spinels,
vanadium-based oxides and organic compounds have been
explored as cathode materials as well.3,10–12
Although the ionic radius of Zn2+ (0.074 nm) is close to that of Li+
(0.076 nm), electrode performances of most Zn-storage materials are
far from satisfactory due to sluggish Zn2+ insertion kinetics because
of the high mass and high charge/radius ratio of Zn2+ with large
solvation sheaths and high electrostatic repulsion.13,14 In addition,
the reaction mechanisms in ZIBs are elusive and often under debate.
Fangyi Cheng received his BS
(2003) and PhD (2009) from
Nankai University. He was
appointed as assistant professor
in 2009 and has been full
professor since 2016 in the
College of Chemistry, Nankai
University. He stayed for one
year (2015–2016) at UCLA as a
visiting scholar. His group has
broad interest in materials
chemistry and energy storage
Fangyi Cheng technologies. His particular research
efforts encompass the design,
synthesis, and mechanism understanding of nonstoichiometric
metal oxides and alloys for rechargeable batteries, oxygen electro-
catalysis, and nitrogen fixation. He is among the Clarivate Highly
Cited Researcher (2018 and 2019).
This journal is © The Royal Society of Chemistry 2020
Chem Soc Rev
Fig. 2 A brief development history of rechargeable zinc-ion batteries.
Taking manganese dioxide cathodes as an example, three electrode
mechanisms have been reported: (1) Zn2+ insertion/extraction reac-
tions; (2) H+/Zn2+ co-insertion/extraction reactions; and (3) conver-
sion reactions. For mechanistic studies, developing and applying
multiple electrochemical methods, advanced characterization tech-
niques, and theoretical calculations are in progress. To date, electro-
lytes of ZIBs are dominated by near neutral aqueous solutions,
which are much safer, greener, and more ionically conductive
compared to organic counterparts. Meanwhile, near neutral aqueous
electrolytes generally have high stability and compatibility with
metallic Zn. However, more effort is needed to be made to gain
deep insight into the device chemistry. On the one hand, it remains
necessary to further explore the effects of zinc salts, solvents,
additives and their concentrations on the electrochemical perfor-
mance and energy storage mechanism of electrodes, as well as the
interface chemistry between electrolyte and electrode. On the other
hand, the rapid development of ZIBs accelerates their wide applica-
tion in flexible and wearable energy storage devices. Efforts should
be intensified toward unearthing functional gel or solid-state elec-
trolytes and improving the performance of flexible ZIBs.
Herein, we aim to provide an overall introduction to the
fundamentals and significant scientific progress made in ZIBs.
To start with, the intrinsic chemical properties, challenges and
improvement strategies of metallic Zn anodes are briefly intro-
duced, followed by summarization of the current progress
in multiple types of cathode materials as well as their
chemical reaction mechanisms, concerns and feasible solu-
tions. Subsequently, we present the discussion of electrolyte
chemistries and their effects on Zn-ion diffusion and intercala-
tion. Lastly, we share our views on the current challenges and
future opportunities in this emerging battery technology and
the practical applications.
2. Metallic zinc anodes
2.1 Intrinsic property of Zn electrodes
Metallic zinc is an ideal material for aqueous batteries because
of its chemical stability in water, high abundance, high theore-
tical specific capacity (gravimetric and volumetric capacities of
This journal is © The Royal Society of Chemistry 2020
Tutorial Review
820 mA h g1 and 5855 mA h cm3, respectively), low potential
(0.76 V vs. SHE), low toxicity and intrinsic safety.15–17 The
charge storage of Zn in ZIBs relies on reversible electrochemical
Zn plating/stripping on discharging/charging.
Different reactions are involved for Zn in aqueous media, as
shown in a Pourbaix diagram18 that plots the equilibrium
potential against the solution pH (Fig. 3a). Metallic Zn can be
oxidized to dissolved forms of Zn2+, Zn(OH)2, HZnO2, and
ZnO22, where specific chemical reactions depend on the
pH values. The notations of HZnO2 and ZnO22 correspond to
zinc complexes of Zn(OH)3 and Zn(OH)42 in most cell equa-
tions. The formation of these complex ions occurs at slightly
different pH values. In conventional alkaline media, Zn(OH)42 is
the charge carrier (Zn + 4OH 2 Zn(OH)42 + 2e), but deep
discharging will result in the irreversible formation of insulating
ZnO (Zn(OH)42 2 ZnO + 2H2O + 2OH) and thereby causes
capacity loss. Unlike the case in an alkaline system, Zn2+, the
major soluble form, can serve as the charge carrier with reversible
anodic chemical reaction in neutral or mildly acidic electrolytes
(Zn 2 Zn2+ + 2e). In non-aqueous electrolytes, zincate could be
the charge carrier species as well.16
Zinc in metallic form can directly work in aqueous solutions
due to its high overpotential for hydrogen evolution.3 In con-
trast, metallic Mg and Al anodes in aqueous electrolytes face
problems such as limited anodic stability and passivation.
Aqueous alkali metal ion batteries (i.e., Li+, Na+, and K+)
necessarily employ intercalation-type anode materials because
of the high chemical activity of alkali metals with water. In
addition, Zn-based battery chemistry could rival the commer-
cialized aqueous Pb-based acid and Ni-based alkaline batteries
that suffer from low energy density, poor cycling life, high
corrosivity, or toxicity.8,9
2.2 Challenges of Zn electrodes and design strategies
Early developments of Zn anodes in alkaline solutions were
hindered by issues including dendrite growth, hydrogen evolu-
tion, consumption of the electrolyte and by-product formation
(e.g., ZnO), resulting in severe polarization, capacity decay and
poor CE (Fig. 3b).4 In recent attempts to use near neutral
Chem. Soc. Rev., 2020, 49, 4203--4219 | 4205
Tutorial Review Chem Soc Rev

Fig. 3 (a) A Pourbaix diagram of Zn in aqueous solution. (b) Zn plating/stripping from Zn/Zn symmetrical cells in an alkaline electrolyte and a mild ZnSO4
aqueous electrolyte, respectively. The insets are optical images of cycled Zn anodes in different electrolytes. Reproduced with permission from ref. 4.
Copyright 2016, Nature Publishing Group. (c) Schematic diagram of the issues for Zn anodes in aqueous electrolytes. (d) Cyclic voltammograms of
Zn plating/stripping in a 20 M LiTFSI + 1 M Zn(TFSI)2 electrolyte. Reproduced with permission from ref. 8. Copyright 2018, Nature Publishing Group.
(e) Galvanostatic cycling of Zn/Zn cells in a non-aqueous TMP-based electrolyte. The inset is the SEM image of the Zn anode after 500 cycles.
Reproduced with permission from ref. 22. Copyright 2020, Royal Society of Chemistry. (f) Schematic illustration of the desolvation process of the
Zn2+–H2O ion complex on the super-saturated front surface of the Zn anode realized by MOF coating. Reproduced with permission from ref. 28.
Copyright 2020, Wiley-VCH. (g–j) Observation of hydrogen evolution in Zn/Zn symmetric cells using bare Zn plates and coated Zn plates. Reproduced
with permission from ref. 29. Copyright 2019, Royal Society of Chemistry. (k) Schematic illustration of Zn deposition on carbon cloth (CC) and carbon
nanotube (CNT) electrodes. Reproduced with permission from ref. 30. Copyright 2019, Wiley-VCH. (l) SEM image of lamella-nanostructured eutectic
Zn–Al alloys with the corresponding EDS element mapping. Scale bar, 2 mm. Reproduced with permission from ref. 32. Copyright 2020, Nature
Publishing Group. (m) Schematic illustration of epitaxial metal electrodeposition. The inset is the SEM image of Zn deposits on graphene-coated stainless
steel. Reproduced with permission from ref. 17. Copyright 2019, American Association for the Advancement of Science.

electrolytes, a good reversibility of Zn electrodes is attainable
by minimizing Zn dendritic formation and suppressing
the inactive by-products. However, the homogeneous plating/
stripping of Zn anodes with high CE and suppressed hydrogen
evolution is still challenging.8,15 The uneven nucleation and
growth of Zn anodes lead to dendrite formation, which would
increase surface-dependent side reactions and worsen self-
discharging. Meanwhile, the decreased pH in acidic aqueous
electrolytes will induce H2 evolution more easily, resulting in
lower CE and increased internal pressure of a sealed cell.
Moreover, the localized H2 evolution at active sites results in
pH elevation (2H2O + 2e - H2 + 2OH), which would generate
Zn hydroxides or zincates and passivate the Zn anode. These
detrimental processes facing Zn anodes (schematically shown
in Fig. 3c) inevitably lead to consumption of the electrolyte and
underutilization of Zn. To tackle these issues, extensive efforts
have directed to electrolyte optimization such as using high salt
concentration, non-aqueous/solid-state electrolytes and electro-
lyte additives, as well as structure/morphology tailoring of the
Zn electrode with surface modification.
Electrolyte concentrating. High-concentration of electrolyte
salt with reduced free solvent molecules provides a promising
way to stabilize Zn electrodes. For instance, a hybrid 1 m
Zn(TFSI)2 + 20 m LiTFSI (TFSI: bis(trifluoromethanesulfonyl)imide,
m: mol kg1) aqueous electrolyte enables dendrite-free Zn
plating/stripping with B100% CE (Fig. 3d).8 In such a highly
concentrated electrolyte, the Zn2+ solvation sheath is occupied
primarily by TFSI instead of H2O, unlike the dilute electrolyte.
The unique Zn(TFSI)n solvate structure favours the formation of
an effective electrode/electrolyte interphase with suppressed

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Chem Soc Rev
dendrite growth and negligible hydrogen evolution at low
potentials. Similarly, a 30 m ZnCl2 water-in-salt electrolyte renders
a dendrite-free Zn metal anode and improves the average CE to
95.4% from 73.2% in a dilute 5 m ZnCl2 electrolyte.15 Other systems
such as 0.5 m Zn(CF3SO3)2 + 18 m NaClO4 and 1 M Zn(CF3SO3)2 +
21 M LiTFSI (M: mol L1) are also found to be effective.8,19
Non-aqueous solvent. The use of an organic solvent is an
alternative route for conquering Zn anodic issues in water-
based electrolytes. Highly reversible and stable Zn anodes have
been demonstrated in aprotic electrolytes. Due to the high
thermodynamic stability of Zn anodes towards organic
solvents, side-reactions accompanied with dendritic Zn growth
and low CE issues can be intrinsically mitigated in non-
aqueous media.20–22 For example, 0.5 M Zn(TFSI)2 in an aceto-
nitrile electrolyte affords near 99% CE of the Zn anode without
evident Zn dendrite formation.21 The recently developed non-
flammable phosphate-based electrolyte consisting of 0.5 M
Zn2+ and 1.0 M Na+ in trimethyl phosphate (TMP) solvent
permits a high CE (99.8%) cycling of the Zn anode over
5000 cycles.22 Moreover, the Zn deposits show a porous inter-
connected Zn network, favouring electric contact and ionic
diffusion (Fig. 3e). Besides, deep eutectic solvents (DESs) offer
the merits of stabilizing Zn plating/stripping, as demonstrated
in the choline chloride/urea (ChCl/urea) hybrid with 0.3 M
ZnCl2.16 In this combination, chlorozincate ([ZnCl4]2) rather
than Zn2+ serves as the charge carrier and small grain-like Zn
deposits are observed.
Electrolyte additives. Additives in electrolytes can alter the
surface properties of Zn anodes through adsorbing on the Zn
electrode surface, shielding charge, or complexing with metal
ions. As Zn nuclei prefer to grow on the surface with lowest
energy, it is feasible to control the size, morphology, crystal-
lographic structure and orientation of plated Zn. Additives
investigated for aqueous and non-aqueous electrolytes include
organic compounds such as branched polyethyleneimine (BPEI),
cetyltrimethylammonium bromide (CTAB), poly(ethyleneglycol)
(PEG), sodium dodecyl sulfate (SDS), and thiourea and inorganic
salts such as Na2SO4, MnSO4, Mn(CF3SO3)2, and Ni(CF3SO3)2.4,5,23,24
For example, addition of SDS endows the electroplated Zn
electrode with lower corrosion rate, reduced dendrite formation,
weak float current and high capacity retention.23 The presence of
Na2SO4 in aqueous ZnSO4 solution also restricts the formation of
Zn dendrites, which can be explained by an electrostatic shield
mechanism.24 With a lower reduction potential than Zn2+, Na+
can shield the charge around the initial Zn protrusions and
suppress further dendrite growth.
Solid-state electrolytes. Solid-state electrolytes (SSEs) are
effective in achieving compact and homogeneous Zn deposition
as the cation transportation can be regulated by the solid
microporous electrolyte membrane. Along this line, a crystalline
single-ion Zn2+ SSE was reported by modifying the precursor
metal–organic framework (MOF) with a fixed anionic micro-
porous host and mobilizable Zn2+ ions.25 Stable Zn plating/
stripping performance with a uniform and compact Zn deposi-
tion layer was identified and attributed to the guided and
restricted Zn deposition arising from the nanowetted Zn/SSE
This journal is © The Royal Society of Chemistry 2020
Tutorial Review
interface, confinement of Zn(H2O)62+ ions within the anionic
MOF host and good compatibility between SSE and Zn anode.
A biomimetic SSE composed of Zn(CF3SO3)2 salt, branched
aramid nanofibers (BANFs) and poly(ethylene oxide) (PEO),
where the high stiffness of BANF networks combines with the
high ionic conductivity of soft PEO, is also found to effectively
suppress dendrites and promote Zn2+ transport.26 Besides, quasi
solid-state hydrogel electrolytes are proposed to inhibit Zn
dendrite formation because of the interaction between Zn2+ and
negatively charged groups in gel that improves the even distribu-
tion of Zn2+ during plating.27 Although solid-state or gel electro-
lytes can suppress the water-induced side reactions, their ionic
conductivity should be further improved to lower the Zn2+ trans-
portation barrier at a high current density.
Surface modification. Protecting Zn anodes via coating a
functionalized protective layer such as reduced graphene oxide
(rGO), carbon black, active carbon, porous nano-CaCO3/SiO2,
TiO2 and polymers has proved effective to decrease the
polarization, restrain the dendrite formation and enhance
the interfacial stability. Recently, a metal–organic framework
(MOF) coating layer was found to enable a super-saturated
electrolyte front surface on Zn via a partial desolvation process
inside MOF channels in advance prior to the final reduction of
Zn2+ (Fig. 3f), resulting in less water passivation and conse-
quently less by-product accumulating on the Zn surface.28
A brightener-inspired polyamide coating layer on the Zn anode
was shown to elevate the Zn nucleation barrier and restrict
Zn ion flux, thus regulating the Zn electrodeposition.29 This
polymeric buffer layer isolates Zn from the bulk electrolyte and
suppresses free water/O2-induced passivation and H2 evolution
(Fig. 3g–j). While a conductive coating layer (e.g., carbonaceous
materials) uniformizes the facial electric-field distribution on
the Zn anode, Zn deposition may occur to grow dendrites that
puncture the modified layers. Non-conductive protective layers
disfavour the rate performance of the Zn anode. Alternatively,
in situ building a protective solid electrolyte interface (SEI) on
metallic Zn deserves more attention.
Structured electrodes. Compared to planar Zn, 3D Zn
architectures with a high surface area and an interconnected
skeleton favour electron transport and electrolyte contact, con-
tributing to a dendrite-free cycling behaviour. For nanostruc-
tured Zn electrodes, a short ion diffusion length and more
electroactive sites permit fast Zn2+/Zn redox kinetics and high
rate capability. Recently, 3D conductive substrates such as
N-doped porous carbon cloth, carbon fiber-graphite felt, carbon
nanotube paper/yarns, graphene foam, stainless steel mesh,
and porous copper foam have been employed as light-weight
backbones for in situ electroplating of 3D structured Zn anodes.
For example, a flexible 3D CNT framework with a high specific
surface area and good electric conductivity is introduced for Zn
plating to diminish dendrite formation (Fig. 3k).30 Composite
Zn anodes by mixing Zn powder with layered double hydroxides
(LDH), conductive carbon additives, and binders have also been
proposed to alleviate the dendrite issues and improve the
kinetics of Zn anodes. The formation of a compact Zn deposi-
tion and the elimination of potential drop at the beginning of
Chem. Soc. Rev., 2020, 49, 4203--4219 | 4207
Tutorial Review Chem Soc Rev

Zn2+ reduction improves the plating/stripping CE of Zn anodes

from 85 to 98%.31 Besides, constructing lamella-nanostructured
eutectic Zn–Al alloys has recently been proposed to guide Zn2+
electrodeposition and protect against irreversible by-products of
ZnO or Zn(OH)2, and thus enables a stable and dendrite-free Zn
plating/stripping behaviour (Fig. 3l).32 Interestingly, reversible
epitaxial electrodeposition of Zn is attained by selecting a
graphene-based substrate (Fig. 3m).17 Graphene with a low
lattice mismatch for Zn can effectively drive the Zn deposition
with a locked crystallographic orientation relation, rendering
cyclability over thousands of cycles. The substrate effect offers
plenty of room to guide the nucleation and deposition of Zn for a
stable electrode structure.

3. Cathode materials
Cathode materials provide Zn-storage sites and largely deter-
mine the voltage and capacity of ZIBs. Extensive efforts have
been devoted to searching for new cathode materials with
higher capacity and better cyclability. Cathode materials can
be mainly categorized into manganese or vanadium-based
oxides, Prussian blue analogues, spinel-structured oxides,
organic materials, Chevrel phase compounds, layered sulfides,
polyanionic compounds, and a few others. Fig. 4a and Table S1
(ESI†) show representative cathode materials in ZIBs, which
will be selectively discussed in this section. The unique features
of structures and morphologies for cathodes are mainly respon-
sible for their different electrochemical performances and
energy storage mechanisms (Fig. 4b).
3.1 Manganese-based oxides
Manganese-based oxides have received extensive interest in
electrochemical energy storage and conversion due to their
high natural abundance, low cost, environmental compatibility
and particularly rich redox chemistry of Mn.4–6,9,33 Recently,
binary manganese oxides including MnO2, Mn2O3, and Mn3O4
have been explored as cathodes for ZIBs. Among them, MnO2 is
attractive due to its high specific capacity (308 mA h g1 based
on one electron redox Mn4+/Mn3+) and moderate discharge
potential (B1.35 V). Different crystallographic polymorphs
are built up with MnO6 octahedral units linked via edge and/
or corners. As shown in Fig. 5a, MnO2 polymorphs can be
divided into three categories of (i) tunnel type such as a-, b-, g-,
and todorokite-MnO2 with 2  2, 1  1, 1  1 and 1  2, 3  3
tunnels, respectively, (ii) layered forms such as d-MnO2, and
(iii) spinel-type structures such as l-MnO2. Most of these
polymorphs are investigated as Zn insertion electrodes.
In aqueous electrolytes, MnO2 cathodes suffer from severe
capacity fading mainly due to the structural transformation and
dissolution of active materials via the Mn3+ disproportionation
reaction (2Mn3+ - Mn2+ + Mn4+). Pre-addition of Mn2+ salts
into the electrolyte is proposed to suppress this side reaction.
A significant improvement on the robustness of the a-MnO2
cathode (92% capacity retention after 5000 cycles) was demon-
strated by introducing 0.1 M MnSO4 in a 2 M ZnSO4 electrolyte.4
Fig. 4 (a) Operation voltages versus specific capacities of representative
cathode materials for ZIBs. Energy densities are based on the mass of cathode
materials. (b) Reaction mechanisms of typical cathode materials for ZIBs.
For b-MnO2 previously believed to be unfavourable for Zn
intercalation, a high reversible capacity of 225 mA h g1 was
attained at 0.65C by formulating a 3 M Zn(CF3SO3)2 + 0.1 M
Mn(CF3SO3)2 electrolyte (Fig. 5b). The addition of Mn2+ accom-
modates the equilibrium between Mn2+ dissolution and reoxida-
tion and helps to form a uniform amorphous MnOx protective
layer on the cathode surface to maintain the electrode integrity.5
Other strategies like structure engineering (e.g., generating oxygen
vacancies or introducing guest pillars in the layered structure),
cation doping (e.g., Al, V, and Ti), and coupling with carbon
materials have been proposed to improve the electrochemical
performance of MnO2-based cathodes. Using the ZnSO4 + MnSO4 +
H2SO4 aqueous electrolyte with initial MnO2 in situ electrode-
posited on carbon fiber cloth, an electrolytic Zn–MnO2 battery
exhibited a high voltage (1.95 V) and extended stability due to the
two-electron redox reaction of Mn4+/Mn2+ enabled by the hybrid
electrolyte.6 Another limitation of MnO2 is the low intrinsic
electronic conductivity. A common remedy includes making
MnO2-based composites with conductive materials (e.g., nano-
structured carbon and graphitic carbon).6,30,34,35 Not surprisingly,
MnO2 in situ supported on graphite fake exhibits superior rate
capability with a lower charge-transfer resistance compared to the
pristine counterpart.35

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Chem Soc Rev Tutorial Review

Fig. 5 (a) Crystal structures of representative MnO2 polymorphs. (b) Comparison of the cycling performance of Zn–MnO2 cells with electrolytes of
45 wt% KOH, 3 M ZnSO4, 3 M Zn(CF3SO3)2, and 3 M Zn(CF3SO3)2 + 0.1 M Mn(CF3SO3)2. Reproduced with permission from ref. 5. Copyright 2017, Nature
Publishing Group. (c) CVs of the Zn anode (red line) and the a-MnO2 cathode (blue line) in the ZnSO4 aqueous electrolyte. Reproduced with permission
from ref. 9. Copyright 2012, Wiley-VCH. (d) Schematic illustration of the rechargeable Zn–MnO2 chemistry using a CF3SO3-based electrolyte.
Reproduced with permission from ref. 5. Copyright 2017, Nature Publishing Group. (e) Diagram showing the sequential insertion of H+ and Zn2+ in a
layered MnO2. Reproduced with permission from ref. 33. Copyright 2018, Nature Publishing Group. (f) XRD pattern and (g) STEM elemental mapping
images of the a-MnO2 cathode after full discharging. Reproduced with permission from ref. 4. Copyright 2016, Nature Publishing Group.

Note that the reaction mechanism of manganese oxides for
ZIBs is still elusive in different cases and can be summarized
as (i) Zn2+ intercalation, (ii) H+ and Zn2+ co-insertion, and
(iii) chemical conversion mechanism.
Zn2+ intercalation. Early investigations of zinc-ion chemistry
suggested reversible insertion/extraction of Zn2+ into/from the
tunnel-type a-MnO2 cathode in a mild ZnSO4 aqueous electro-
lyte (Fig. 5c),9 according to the following equation:
Zn2+ + 2e + 2MnO2 2 ZnMn2O4 (1)
2+
Diverse Zn intercalation reactions and complex phase transfor-
mation are reported for manganese oxides involving discharge
products of spinel-type ZnMn2O4, Zn-buserite, Zn-birnessite,
tunnel-type ZnxMnO2, and Mn2+ species. For example, complex
structural transformation occurs in g-MnO2.37 With continuous
Zn2+ insertion on discharging, the initial tunnel-type g-MnO2 was
gradually converted into multiple phases composed of spinel-type
ZnMn2O4, tunnel-type g-ZnxMnO2 and layered-type L-ZnxMnO2.
The common electrode mechanism was observed for different
tunnel-type polymorphs (i.e., a-/g-/b-MnO2) in the Zn(CF3SO3)2-
based aqueous electrolyte.5 The exemplified b-MnO2 experiences
phase transition to the layered Zn-buserite structure at initial
discharging and subsequent reversible Zn2+ intercalation in the
buserite interphase (Fig. 5d). Reversible Zn2+ (de)intercalation into
layered d-MnO2 was also reported recently.35
H+ and Zn2+ co-insertion mechanism. Given the smaller size
and weaker electrostatic interaction of H+ relative to Zn2+, the
proton intercalation into host materials with an open tunnel or
layered framework may occur in aqueous media. For example,
consequent H+ and Zn2+ co-insertion was demonstrated in the
e-MnO2 cathode using a 2 M ZnSO4 + 0.2 M MnSO4 electrolyte.34
Consecutive discharge products of MnOOH and ZnMn2O4 were
observed when the electrode was discharged to 1.3 and 1.0 V,
respectively. Similarly, the co-insertion mechanism of H+ and
Zn2+ has been proposed in polyaniline (PANI)-intercalated
layered MnO2 with a self-regulating function in a ZnSO4-based
electrolyte. The proton insertion during discharge leads to the
increase of local OH concentration, inducing the formation of
flake-like zinc hydroxide sulfate hydrate (Zn4(OH)6SO4nH2O) on
the cathode surface (Fig. 5e).33 A recent study also suggested
that a solid-solution type proton intercalation without Zn2+
co-insertion dominates the charge storage in a-MnO2 because
the hydroxyl/water-terminated oxide interface preferentially aids
in the desolvation and intercalation of protons.37 Regardless
of different mechanisms, proton insertion is believed to be a
beneficial factor for rate performance of manganese oxides.
Conversion reaction mechanism. In addition to the popular
intercalation mechanisms, a chemical conversion reaction path
between a-MnO2 and MnOOH was proposed as well.4 During
discharging, MnO2 reacts with H+ from water to form MnOOH,
and the generated OH reacts with ZnSO4 and H2O to form
ZnSO4[Zn(OH)2]3xH2O (Fig. 5f). This process is reversible as
the original a-MnO2 electrode is recovered after charging. The
cathode reactions can be formulated as
H2O 2 H+ + OH (2)

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Tutorial Review Chem Soc Rev

MnO2 + H+ + e 2 MnOOH (3)

3Zn 2+
+ 6OH + ZnSO4 + xH2O 2 ZnSO4[Zn(OH)2]3xH2O


(4)

Collecting the above discussions, the fundamental reactions

are complex and may vary with the crystallographic phases of
manganese oxides (e.g., tunnel type versus layered form) and
electrolytes (e.g., acidic, alkaline, and aprotic conditions). To
clarify the mechanisms of manganese oxides calls for more
precise experiments and comprehensive analytic methods.

3.2 Spinel-structured oxides

Spinel oxides with the formula of AB2O4 (A and B represent
metal ions that respectively occupy the centers of tetrahedral
and octahedral metal–oxygen polyhedra) have been extensively
employed in metal-ion batteries. Spinels such as ZnMn2O4,
MgMn2O4, ZnCo2O4, and LiMn2O4 are explored as cathodes
for aqueous/nonaqueous ZIBs with considerable specific capa-
city and working voltage (Table S1, ESI†).10,38
Inspired by the success of reversible electrochemical
extraction/insertion of Li+ from the spinel LiMn2O4, the spinel
analogue of ZnMn2O4 was considered as a promising cathode
for ZIBs. However, the ideal spinel structure was unfit for Zn2+
(de)intercalation as proved by difficult chemical extraction
of Zn2+ from ZnMn2O4 spinel due to the high electrostatic
repulsion for lattice Zn2+ diffusion. Instead, defects including
cation or oxygen vacancies are introduced to facilitate the
migration of divalent ions. Previous studies demonstrated that
a cation-defective spinel (ZnMn1.86O4) delivered a capacity of
150 mA h g1 at a current density of 50 mA g1 and a capacity
retention of 94% after 500 cycles at 500 mA g1.10 Moreover, the
diffusion coefficient of Zn2+ in Mn-vacant ZnMn2O4 calculated
from GITT is around 1011 cm2 s1, which is much higher than
that in stoichiometric spinel (ca. 1013 cm2 s1) and compar-
able to the Li diffusivity of spinel oxides.10 The remarkable
electrochemical performance was attributed to facile Zn2+
intercalation and mitigated neighbouring cation repulsion in
the defective spinel framework (Fig. 6a and b).
Compared with manganese-based oxides, spinel ZnCo2O4
with Co4+/Co3+ redox couple affords a higher working voltage
(1.7 vs. 1.35 V). Motivated by the cation doping strategy to
improve the working voltage and structural stability of LiCoO2,
a series of spinel ZnAlxCo2xO4 and ZnNixMnxCo22xO4 were
reported by doping Al or Ni/Mn into ZnCo2O4. The exemplified
ZnNi1/2Mn1/2CoO4 showed a discharge capacity of 174 mA h g1
with an average voltage of 1.7 V over 200 cycles in aprotic
electrolytes.38 Mechanistic analyses demonstrated reversible
Zn2+ intercalation in spinel and concomitant compositional
transformation involving multiple conversion between
Co4+/Co3+, Ni4+/Ni3+/Ni2+, and Mn4+/Mn3+ redox states (Fig. 6c).
These studies affirm the benefits of doping chemistry to boost
the multivalent ion insertion in spinels.
3.3 Vanadium-based oxides
Together with manganese oxides, vanadium-based oxides are
particularly interesting cathode materials for ZIBs owing to
Fig. 6 (a) Schematic illustration of Zn2+ insertion/extraction in an
extended 3D Mn-defective ZnMn2O4 spinel framework. (b) Proposed
Zn2+ diffusion pathway in ZnMn2O4 spinel without and with Mn vacancies.
Reproduced with permission from ref. 10. Copyright 2016, American
Chemical Society. (c) Schematic charge and discharge processes for the
ZnNi1/2Mn1/2CoO4 electrode. Reproduced with permission from ref. 38.
Copyright 2018, Wiley-VCH.
their multi-electron redox reaction accompanied with accessible
V oxidation states (i.e., V2+, V3+, V4+ and V5+), high capacity
(4300 mA h g1), and large ion transfer channel.3,39,40 Gener-
ally, their working voltage is around 0.8 V vs. Zn2+/Zn, which
limits the energy density to some extent. Different from the
octahedral MnO6 unit in manganese-based oxides, the V–O
polyhedra occur in diverse formats from VO4 tetrahedron, VO5
square pyramid and trigonal bipyramid to distorted and regular
VO6 octahedron (Fig. 7a). These polyhedra link to form chains,
layers or 3D frameworks that further assemble into different
phases of vanadium oxides. Most of them contain interlayer
cations (e.g., NH4+, Li+, Na+, K+, Zn2+, Mg2+, Ca2+, etc.) and/or
water molecules to stabilize the crystal structure.
Structures. A series of vanadium-based oxides with or with-
out structural waters have been reported as cathode materials
for ZIBs, mainly including (1) MxV2O5yH2O (M = NH4+ or metal
ions) consisting of VO5 square pyramids or VO6 octahedra with
single or double vanadium oxide layers. Typical compounds
include V2O5, V2O5nH2O, Zn0.25V2O5nH2O, LixV2O5nH2O,
Na0.33V2O5, MgxV2O5nH2O, Ca0.25V2O5nH2O, V5O126H2O and
NH4V4O10. (2) MxV3O8yH2O (M = NH4+ or metal cations)
consisting of VO5 square pyramids (or VO5 trigonal bipyramids)
and VO6 octahedra sharing corners. Examples are V3O7H2O
(equivalent H2V3O8), LiV3O8, NaV3O81.5H2O, NaV3O81.35H2O
and NH4V3O8. (3) MxV6O16yH2O based on V3O8 layers
comprising VO6 octahedron and VO5 square pyramid

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Chem Soc Rev
Fig. 7 (a) Typical vanadium coordination polyhedra. (b) Crystal structures of representative vanadium-based materials for ZIBs. Schematic illustrations of
the reaction chemistry for vanadium oxide cathodes in terms of (c) Zn2+ insertion, H2O and Zn2+ co-insertion, and (d) H+ and Zn2+ co-insertion
mechanisms. (e) Oxygen and vanadium redox chemistry in a polyanionic VOPO4 cathode. Reproduced with permission from ref. 19. Copyright 2019,
Wiley-VCH.
units with interstitial hydrated M cations. This category con-
tains Na2V6O16nH2O, K2V6O161.57H2O and CaV6O163H2O.
(4) MxV2O7yH2O composed of [V2O7] groups with VO4 tetra-
hedral coordination along the z-axis, such as Zn2V2O7 and
Zn3V2O7(OH)22H2O. (5) V6O13 and V6O13yH2O composed of
corner and edge-sharing distorted VO6 octahedra to form
alternating single and double vanadium oxide layers by sharing
corners. (6) Other types such as VO2, K2V8O21, Zn2(OH)VO4, etc.
Fig. 7b shows the typical crystal structures of representative
vanadium-based oxides of interest for ZIBs.
The presence of cations and H2O as pillars in the interlayers
may modify the layered structure and significantly affect the
intercalation chemistries and electrode performances of vanadium-
based oxides. For example, the interlayer Zn2+ and water molecules
in a layered vanadium oxide bronze (Zn0.25V2O5nH2O, ZVO) help to
sustain structural stability on cycling.3 This cathode delivered
reversible capacities of 282 and 220 mA h g1 at 1 and
15C, respectively, with 80% capacity retention after 1000 cycles
at 8C. Other layered vanadium oxides pillared by various cations
include LixV2O5nH2O, NaV3O8nH2O, and Ca0.25V2O5nH2O
(Table S1, ESI†). In addition to vanadium oxide itself, compo-
nents such as conducting agent and electrolyte play an impor-
tant role in the performance improvement of vanadium oxides.
Remarkably, a composite of V2O5nH2O/graphene exhibits superior
Zn-storage performance with reversible capacities of 372 and
319 mA h g1 at 0.3 and 15 A g1 respectively, owing to the
synergistic merits of the structural features of V2O5nH2O
nanowires and the high conductivity of the graphene network.40
This journal is © The Royal Society of Chemistry 2020
Tutorial Review
Electrolyte optimization of salt, concentration and additives is
an attractive strategy to improve the stability of vanadium
oxides, particularly by restraining vanadium loss. For example,
a concentrated 3 M Zn(CF3SO3)2 electrolyte prevents the dis-
solution of the V2O5 cathode to sustain extended cycling
stability.39 The addition of Na+ into the ZnSO4 electrolyte
impedes the dissolution of NaV3O81.5H2O (NVO) via shifting
the dissolution equilibrium of sodium vanadate.24 There are other
performance-enhancement approaches such as constructing vana-
dium oxides with more stable V–O bonds by cation doping, using gel
or solid-state electrolytes, and designing functional separators.
Similar to manganese-based oxides, the reactions involved
in vanadium-based oxides are complex. Mechanisms of Zn
storage in vanadium oxides mainly include (i) Zn2+ insertion/
extraction mechanism (Fig. 7c), (ii) H2O and Zn2+ co-insertion
mechanism (Fig. 7c), and (iii) H+ and Zn2+ co-insertion mecha-
nism (Fig. 7d).
Zn2+ insertion/extraction mechanism. Vanadium-based oxides
are mainly layered/tunnel frameworks with a large void space
favouring Zn2+ insertion. In a milestone study, a reversible Zn2+
insertion mechanism of Zn0.25V2O5nH2O (eqn (5)) was revealed by
combining operando X-ray diffraction and X-ray photoelectron
spectroscopy analyses.3 Similar Zn2+ (de)intercalation storage pro-
cesses have been demonstrated in most of the reported vanadium-
based cathodes such as VO2, V5O126H2O, Na2V6O163H2O,
Zn3V2O7(OH)22H2O, LixV2O5nH2O, and Ca0.25V2O5nH2O.1,2,39
Most vanadium oxides can maintain a stable crystal framework
via V evolution of oxidation states from V5+ to V4+ or even V3+,
Chem. Soc. Rev., 2020, 49, 4203--4219 | 4211
Tutorial Review
adapting to Zn2+ intercalation. Irreversible phase transitions
were also observed in examples of NaV3O8-type compounds like
Na5V12O32, which experiences structural destruction and phase
transition and thus capacity degradation.2 In addition to the
diffusion-controlled faradaic process, intercalation pseudo-
capacitance behaviours were also identified in V-based oxide
cathodes (e.g., VO2, V2O5nH2O, NaV3O8nH2O, etc.) and were
believed as a contribution to ultrafast Zn-intercalation
kinetics.24,39,40 The pseudocapacitive response of battery chemistry
can be characterized by the relationship between scan rate v
and current i in cyclic voltammetry (i = avb or log i = b  log v +
log a, where a and b are adjustable parameters), as shown in
Fig. S1 (ESI†).39 When b is close to 0.5, the reaction process is
controlled by ionic diffusion; when b approaches 1.0, pseudo-
capacitive contribution dominates and higher b indicates faster
charge transfer kinetics.
Zn0.25V2O5nH2O + 1.1Zn2+ + 2.2e 2 Zn1.35V2O5nH2O.
(5)
H2O and Zn2+ co-insertion mechanism. With interlayer
cations and/or structural waters, vanadium-based oxides usually
feature an expanded layered architecture and favour hydrated
Zn2+ intercalation. The solvating H2O acts as a charge shield
to buffer the high charge density of divalent Zn2+ and thus
promotes Zn2+ transport.40 In a concentrated triflate electrolyte,
the V2O5 cathode exhibits a capacity of 470 mA h g1 at 0.2 A g1,
a high energy density of 274 W h kg1 at 7100 W kg1 and a
superior cyclability with 91% capacity retention over 4000 cycles.39
Similar co-intercalation chemistry of water molecules and Zn ions
upon discharge is often observed in other vanadium oxides such
as V6O13 and H2V3O8.13
H+ and Zn2+ co-insertion mechanism. The co-insertion
process of H+ and Zn2+ is also observed in vanadium-based
oxides. Recently, a simultaneous H+ and Zn2+ co-intercalation
model was proposed in the NaV3O81.5H2O cathode using the
1 M ZnSO4 + 1 M Na2SO4 electrolyte.24 The corresponding
reactions could be formulated as eqn (6)–(8):
3.9H2O 2 3.9H+ + 3.9OH (6)
1.95Zn2+ + 0.65ZnSO4 + 3.9OH + 2.6H2O
2 0.65Zn4SO4(OH)64H2O (7)
NaZn0.1V3O81.5H2O + 3.9H+ + 0.4Zn2+ + 4.7e
- H3.9NaZn0.5V3O81.5H2O (8)
The presence of small and lightweight protons is suggested to
promote the diffusion of Zn2+ and improve insertion kinetics.
The simultaneous H+ and Zn2+ insertion/extraction process
in NaV3O81.5H2O is different from the case of MnO2 showing
two-step H+ and Zn2+ intercalation behaviour.34 Note that the
proton intercalation upon discharge generally leads to the
precipitation of layered double hydroxide on the cathode
surface, formed by the reaction of OH (H2O = H+ + OH),
Zn2+, and electrolyte anions (Fig. 7d). Other vanadium oxide
cathodes (e.g., V3O7H2O) could also enable the H+ and Zn2+
4212 | Chem. Soc. Rev., 2020, 49, 4203--4219
Chem Soc Rev
co-intercalation chemistry.37 However, the position of H+ or
hydronium in vanadium oxides remains unclear, and the
influence of protons on Zn plating/stripping and ionic transfer
requires further investigations.
Other vanadium-based compounds. Vanadium-based poly-
anionic materials such as Li3V2(PO4)3, Na3V2(PO4)3 (NVP) and
Na3V2(PO4)2F3 (NVPF), previously utilized in lithium-ion or
sodium-ion batteries, are employed in ZIBs due to their stable
framework at delithiated or desodiated states. Taking Na3V2(PO4)3
as an example, its Na superionic conductor (NASICON) structure
allows Na+ extraction on the first charging and reversible Zn2+
(de)intercalation during subsequent cycles.41 However, in a non-
aqueous system, only Na+ is found to reversibly intercalate into
the polyanionic phosphate (e.g., Na3V2(PO)2O2F (NVPOF)) without
Zn2+ co-insertion.22 In addition, the introduction of highly elec-
tronegative F anions in the phosphate lattice can improve the
average operation voltage of the Na3V2(PO4)3-based material from
around 1.1 to 1.7 V (vs. Zn2+/Zn). However, the capacity of
vanadium-based polyanionic cathodes is relatively low (generally
below 100 mA h g1) because of their large molecular mass.
Further investigations should focus on the structural design, such
as defect engineering and electrochemically active cation doping
(e.g., Mn, Ni, etc.), to achieve a high energy density. Besides
the active reaction based on sites of 3d metals, a recent study
has proposed a reversible oxygen-involved redox mechanism in
polymeric VOPO4 where the anionic redox not only contributes
to B27% additional capacity but also increases the average
voltage to 1.56 V (Fig. 7e).19 Recently, a simultaneous cationic
(V3+ 2 V2+) and anionic (N3 2 N2) redox reaction has been
achieved in a surface-oxidized vanadium nitride (VNxOy) cathode,
rendering a high reversible capacity of 200 mA h g1 at 30 A g1
and fast kinetics.42 A stable polymeric crystal structure marrying
anionic redox chemistry may open up a new avenue for exploiting
new ZIB cathodes.
3.4 Prussian blue analogues
Prussian blue analogues (PBAs) have been widely investigated
as metal-ion battery hosts, which adopt 3D open-framework
structures with abundant redox-active sites and considerable
structural stability.11,43–45 The nominal chemical formula of PBAs
can be described as AxM[M 0 (CN)6]yzH2O, in which A represents
alkali metal ions (i.e., Na+ and K+) while M and M0 are transition
metal ions (i.e., Fe, Co, Ni, Cu, and Zn). Fig. 8a illustrates the
typical crystal structure of PBAs, where M and M0 locate on
alternate corners in a corner-shared octahedron cube bridged by
cyanide CN ligands and M 0 and M bond with C and N atoms to
form octahedral M 0 C6 and MN6, respectively. The electrochemical
properties of PBAs could be tuned by not only the type and ratio of
M and M0 ions but also the coordination sites (C or N to metals).
To date, PBAs including cubic copper hexacyanoferrate (CuHCF),
nickel hexacyanoferrate (NiHCF), cobalt hexacyanoferrate (CoHCF),
iron hexacyanoferrate (FeHCF) and zinc hexacyanoferrate (ZnHCF)
with a rhombohedral structure have been employed as cathode
materials for ZIBs (Table S1, ESI†).
Taking CuHCF as an example, Fig. 8b shows the typical
charge and discharge profiles of a PBA cathode for ZIBs.
This journal is © The Royal Society of Chemistry 2020
Chem Soc Rev
This compound delivers a capacity of 55 mA h g1 at 60 mA g1
and an average voltage of 1.73 V (vs. Zn), with a capacity
retention of 96.3% after 100 cycles.11 The intercalation chemistry
of CuHCF is based on reversible insertion/extraction of Zn2+
into/from the A sites of the crystal lattice (Fig. 8a), according to
the following equation:
xZn2+ + 2xe + CuHCF 2 ZnxCuHCF (9)
Further investigations revealed the large effect of the electrolyte
and current rate on the aging of the CuHCF cathode during
battery operation.43 The aging occurs at a shorter number of
cycles when the electrolyte concentration is higher and the
current density is lower, as identified through the simultaneous
appearance of a second phase and decrease of the main redox
peak upon cycling. Understanding the aging mechanism of
PBAs helps in the rational modification of active materials to
boost the electrochemical stability.
Although the operating voltage of PBAs is relatively high
(about 1.7 V vs. Zn), the limited specific capacity (generally below
70 mA h g1) leads to an insufficient energy density. Besides,
unstable phase transformation upon cycling would induce capacity
decay. Strategies to address these problems include generating more
vacancy sites in the crystal framework and integrating with other
active components or constructing composite materials. Recently, a
two-species redox reaction of Co(II)/Co(III) and Fe(II)/Fe(III) was
proposed in cobalt hexacyanoferrate (Fig. 8c).45 In a concentrated
4 M Zn(CF3SO3)2 electrolyte, this CoFe(CN)6 cathode exhibits a
considerably high Zn-storage capacity of 173.4 mA h g1 with
a voltage of 1.75 V at 0.3 A g1 and an extended cycling stability
without evident capacity decay after 2200 cycles at 3.0 A g1.
3.5 Organic compounds
Organic compounds are highly appealing electrode materials
because of their high theoretical capacity, flexible structure
designability, high element abundance, environmental friendliness
Fig. 8 (a) Typical structure of Prussian blue analogues. (b) Dicharge/charge
curves of the CuHCF cathode and Zn anode at 60 mA g1. Reproduced with
permission from ref. 11. Copyright 2015, Wiley-VCH. (c) Schematic illustra-
tion of Zn2+ (de)intercalation into the CoFe(CN)6 framework. Reproduced
with permission from ref. 45. Copyright 2019, Wiley-VCH.
This journal is © The Royal Society of Chemistry 2020
Tutorial Review
and sustainability.12,46 Based on distinct redox reactions, organic
electrode materials can be classified into three types: n, p, and
bipolar. Most n-type compounds undergo first reduction and
combine with electrons and metal cations, whereas p-type organics
experience initial oxidation and bind anions from the electrolyte to
maintain an electroneutral state. Bipolar-type materials can initially
undergo either oxidation or reduction, featuring properties of both
n-type and p-type materials. Representative n-type organic materials
investigated for ZIBs mainly include quinone compounds, such
as 1,4-naphthoquinone (1,4-NQ), 9,10-anthraquinone (9,10-AQ),
calix[4]quinone (C4Q), 1,2-naphthoquinone (1,2-NQ), 9,10-
phenanthrenequinone (9,10-PQ), tetrachloro-1,4-benzoquinone
(p-chloranil), poly(benzoquinonyl sulfide) (PBQS), and pyrene-
4,5,9,10-tetraone (PTO) (Fig. 9a and Table S1, ESI†).12,46,47 Unlike
the common intercalation mechanism for inorganic materials,
quinone-based compounds with oxygen atoms in carbonyl
groups serve as active sites for Zn-storage through a coordination
reaction. Compared to aprotic electrolytes, in aqueous media the
mass dissolution problem of quinone electrodes is mitigated;
however, the Zn-containing species at discharged states are often
soluble, leading to poor cyclability. To tackle the dissolution
issues, strategies such as separator modification, polymeriza-
tion, and mesoporous matrix confinement have been applied for
quinone electrode materials.
In a recent effort of using quinone compounds for aqueous
ZIBs, a C4Q cathode was combined with a cation-selective
membrane (i.e., Nafion film) separator, which can suppress
the dissolution and crossover of the discharged ZnxC4Q to the
zinc anode side. The C4Q electrode delivered a high capacity of
335 mA h g1 at 20 mA g1, a flat operation voltage of 1.0 V, and
a low charge–discharge plateau separation of 70 mV (Fig. 9b).12
Fig. 9 (a) Structures of the representative quinone cathodes for ZIBs.
(b) Discharge/charge curves of the C4Q cathode and (c) optimized
configurations of C4Q before and after Zn ion uptake. Reproduced with
permission from ref. 12. Copyright 2018, American Association for the
Advancement of Science. (d) Rotation of p-chloranil molecular columns
upon Zn2+ insertion. Reproduced with permission from ref. 46. Copyright
2018, American Chemical Society.
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Tutorial Review
The combination of electrostatic potential (ESP) computation
and in situ spectroscopy has revealed that Zn storage occurs on
the active carbonyl groups with 6e transfer per C4Q molecule
(Fig. 9c). Similarly, a p-chloranil cathode permits reversible
and efficient Zn2+ storage with an attractive energy density of
200 W h kg1 and a CE of 95% in aqueous ZIBs. The molecular
columns in p-chloranil experience a twisted rotation to accom-
modate Zn2+, thus restricting the volume change (2.7%) upon
cycling (Fig. 9d).46 Another noteworthy carbonyl PTO has much
less solubility for both the pristine cathode and discharged
species, making it possible to employ a conventional glass fiber
separator. Binding Zn via coordination, the PTO cathode
enables an exciting specific capacity of 336 mA h g1, along
with fast kinetics and high reversibility.47 Considering the
extensive interest in organic electrode materials for alkali-
metal battery chemistry, a variety of conjugated compounds
can be expected as promising materials for Zn storage. Like-
wise, most organic cathode materials, particularly those with a
low molecular weight, are plagued by intrinsic poor electron
conductivity, which restricts the rate performance and would
lead to hybridization strategies such as anchoring organic
electrodes on carbonaceous substrates via p–p interaction.
3.6 Other cathode materials
In addition to the above cathodes for ZIBs, other reported
Zn-host materials mainly direct to transition metal chalcogenide
compounds (Table S1, ESI†). Particularly, Chevrel phase com-
pounds with the general formula of MxMo6T8 (M = metal ions;
T = S, Se, or Te) are composed of Mo6T8 unit arrays in a 3D
network containing metal ions. Each unit consists of a distorted
Mo6 octahedron surrounded by a cubic T8 unit of chalcogenide
atoms. The Chevrel compounds can host high-valent cations
with remarkable ionic and electronic transfer kinetics, but
generally show a limited energy density due to low capacity
(o100 mA h g1) and average working voltage (around 0.35 V vs.
Zn2+/Zn).48 Layered transition-metal dichalcogenides (TMDs)
such as MoS2 and VS2 also hold potential for reversible Zn
insertion because the higher polarizability of S2 relative to
O2 enables weaker electrostatics, allowing high ionic transfer.
Recent studies demonstrated that incorporation of a small
amount of oxygen (5%) in MoS2 (MoS2–O) can increase the
interlayer spacing from 6.2 to 9.5 Å and improve the hydrophi-
licity, which allows a hydrated Zn2+ intercalation and thus
significantly lowers the desolvation penalty at the electrode–
electrolyte interface (Fig. S2, ESI†).49 The resultant electrode
exhibits a high capacity of 232 mA h g1 and fast Zn2+ diffusivity
(at a magnitude of B109 cm2 s1 exceeding the Li diffusion
coefficient). The interlayer spacing and hydrophilicity engineering
can be extended to enhance the ion storage performance of other
layered intercalation hosts.
3.7 Effect of H2O on the performance of cathode materials
Compared to monovalent Li+, divalent Zn2+ typically suffers
from sluggish kinetics for diffusion within the solid electrodes
or across the electrode/electrolyte interfaces due to the stronger
electrostatic interaction between Zn2+ and its environment.14
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Water in electrolytes or host lattices plays a key role in Zn2+
insertion chemistries. The reaction mechanism as mentioned
above in manganese and vanadium oxides involves the partici-
pation of H2O in co-insertion or even in phase transition of host
materials. The function of crystal H2O in expanding the layered
galleries and shielding the charge of intercalated Zn2+ is
proposed to boost the overall electrochemical performance of
electrodes such as Zn0.25V2O5.3 Structural H2O in MnO2 or
V2O5nH2O cathodes is also shown to function like a ‘‘lubricant’’
to facilitate fast zinc-ion transport by screening the electrostatic
repulsion between Zn2+ and host anions.5,40
In addition to the solid diffusion of Zn2+, the interfacial
charge transfer process associated with the desolvation of Zn2+ is
also governed by H2O in the electrolyte. Typically, in an aqueous
system, Zn2+ cations are octahedrally coordinated with six water
molecules, such as [Zn(H2O)6]2+. Partially hydrated Zn2+ mediates
the interfacial cation transfer in an aqueous electrolyte, which
decreases the desolvation energy penalty and the repulsion at the
host surface due to the charge shielding by water molecules.13 In
contrast, a nonaqueous system (i.e., AN-based electrolyte) experi-
ences a higher desolvation penalty associated with nearly four-fold
higher activation energy, as a result of the ion pair formation.
Consequently, the V3O7H2O cathode gives a much higher capacity
of 375 mA h g1 at 375 mA g1 in an aqueous electrolyte
as compared to the nonaqueous counterpart (59 mA h g1 at
5 mA g1).13 Similarly, molecular H2O at the electrode/electrolyte
interface is also found to accelerate Zn2+ diffusion from the electro-
lyte to the electrode surface by using a model system consisting of a
layered VOPO42H2O cathode and a 0.1 M Zn(CF3SO3)2–AN electro-
lyte with different percentage of water.14 Water effects enhance
Zn-storage reaction kinetics of other cathodes such as
KCuHCF20 and MoS2.49 Further studies are required to gain
more insight into how water facilitates Zn2+ diffusion across the
bulk electrode or electrolytes and the electrode/electrolyte
interface.
4. Electrolytes
Electrolytes transport guest ions to connect the cathode with
the Zn anode, isolate electrons and define the electrochemical
window. Electrolyte formulation of salts, solvents, concentra-
tions, and additives has a profound influence on the solvation
structure, interfacial stability, cathode dissolution, safety, cost,
and overall electrochemical performance of ZIBs (Fig. 10a).
Currently, reported zinc salts include ZnSO4, Zn(CF3SO3)2,
ZnCl2, ZnF2, Zn(NO3)2, Zn(ClO4)2, Zn(CH3COO)2, Zn(BF4)2,
Zn(PF6)2, Zn(TFSI)2, etc. Investigated solvents vary from water
to organic solvents, ionic liquids and deep eutectic solvents.
For the Zn-ion chemistry, aqueous electrolytes have intrinsic
superiority, such as high safety, low cost, high conductivity and
good compatibility. Some organic or inorganic additives are
introduced into electrolytes to eliminate the critical issues of
the Zn anode and enhance the reversibility of the cathode.
Electrolytes could be roughly divided into aqueous and non-
aqueous systems according to the selection of solvents.
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Chem Soc Rev
Fig. 10 (a) Electrolyte design based on the salt, solvent, additive and
concentration, and the influence of their physicochemical properties on
both cathode material and Zn anode, including interfacial stability, active
material dissolution, and electrochemical performances. Multi-angle com-
parison of (b) conventional and concentrated aqueous electrolytes and
(c) aqueous and nonaqueous electrolytes.
The multi-angle comparison between conventional and con-
centrated aqueous electrolytes and aqueous versus nonaqueous
electrolytes is schematically shown in Fig. 10b and c,
respectively.
4.1 Aqueous electrolytes
Aqueous electrolytes are particularly attractive in view of their
unique merits: inherent safety by avoiding the usage of flam-
mable organic compounds, high ionic conductivity (about two
orders of magnitude higher than non-aqueous ones), cost
effectiveness, and environmental friendliness.
Neutral or mildly acidic electrolytes. Considering the severe
side reactions with Zn, alkaline and strongly acidic electrolytes
are not appropriate for round-trip Zn2+ migration. Neutral or
mildly acidic aqueous electrolytes are better choices for ZIBs.
The solute salts have a significant effect on the kinetics of
Zn-ion diffusion and reaction chemistries of active materials due
to different coordination/de-association behaviours. Among zinc
salts, ZnSO4 and Zn(CF3SO3)2 (Zn(OTf)2) are most extensively
employed while ZnCl2 and Zn(NO3)2 are comparatively tested.
The aqueous Zn(CF3SO3)2 electrolyte enables wide electroche-
mical windows (up to 2.5 V), considerable ionic conductivity
(3.47 S cm1), small overpotential of Zn plating and stripping
with a near 100% CE, outperforming the counterpart ZnSO4
electrolyte.10 Poor Zn plating/stripping efficiency and a narrow
window are observed in ZnCl2 and Zn(NO3)2 solutions due to
the instability of Cl and NO3. The superior electrochemical
properties of Zn(CF3SO3)2 could be attributed to the bulky
CF3SO3 anions (vs. SO42 with double charge) that decrease
the number of water molecules surrounding Zn2+ cations and
reduce solvation effects.
This journal is © The Royal Society of Chemistry 2020
Tutorial Review
The salt concentration is another key factor to affect the
battery performance. ZIBs assembled with concentrated elec-
trolytes show higher stability compared to those assembled
with the diluted counterpart (e.g., 3 vs. 1 M Zn(CF3SO3)2
electrolyte).10 Higher salt concentration is proposed to alter
the solvation (Fig. 10a) and transfer of cations/anions as well as
reduce the water activity and water-induced side reactions. In a
recently developed highly concentrated aqueous electrolyte
consisting of 1 m Zn(TFSI)2 + 20 m LiTFSI, the Zn-solvation
sheath was occupied by TFSI instead of water, thus preventing
hydrolysis.8 While the use of concentrated electrolytes gives rise to
new interface chemistry and bring opportunity to stabilize ZIBs,
the increase of cost and viscosity and lower wettability should be
taken into account for practical applications (Fig. 10b).
Side reactions from salts in aqueous electrolytes have been
universally observed in both manganese-based and vanadium-
based cathodes, such as the layered double hydroxide (LDH)-
type Zn4(OH)6SO4nH2O (ZHS) by-product in ZnSO4-based
electrolytes.4,24,33 However, the formation mechanism and
the functionality of ZHS still remain ambiguous. Recently,
H+ intercalation in oxide cathodes during discharging was
demonstrated to cause an increase of electrolyte pH and induce
the precipitation of ZHS on the surface of the electrode, which
results from the reaction of OH (left behind after H+ inter-
calation), Zn2+, and SO42.37 The generation of ZHS in turn
buffers the electrolyte pH to sustain the H+ insertion. During
charging, the ejecting protons dissolve the ZHS into the
electrolyte. Similar to ZHS, a triflate anion-based hydroxide
precipitation was also detected in the Zn(CF3SO3)2 electrolyte,
but its exact structure and composition need further determi-
nation. It should be noted that the gradual accumulation of
these by-products upon prolonged cycling will lead to the
volume expansion of the electrode and consumption of the
electrolyte, posing challenges to battery operation. Effective
strategies to alleviate this problem include constructing elec-
trodes with a porous structure to accommodate by-product
precipitation or tuning the surface functionality of oxides to
retard H+ intercalation.
Aqueous gel polymer electrolytes. Gel polymer electrolytes
(GPEs) have a polymeric network filled with water, featuring
liquid-like ionic conductivity and solid-like stability viable for
applications in flexible and wearable ZIBs. Typically, GPEs consist
of Zn-containing salts and polymeric frameworks dissolved in
water. For example, poly(vinylidenefluoride-co-hexafluoropropylene)
(PVDF–HFP) and polyethylene oxide (PEO) based GPEs have been
explored in primary zinc batteries; however, they suffer from low
ionic conductivity, high interfacial resistance, rapid degradation
and poor mechanical strength. Hydrogel electrolytes, as hydro-
philic polymer networks swollen with a large amount of water,
have high inorganic salt solubility and provide higher ionic
conductivity. Recently, several water-soluble polymers such as
polyacrylic acid (PAA), poly(vinyl alcohol) (PVA), polyacrylamide
(PAM) and xanthan gum have been exploited to fabricate hydrogel
electrolytes, which could simultaneously replace traditional
separators and aqueous solutions and afford high chemical
stability and mechanical flexibility.24,27,30,45
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Tutorial Review
As an example, a hierarchical polymer electrolyte (HPE) was
designed by grafting PAM onto gelatin hydrogel, which was
filled in the matrix of a PAN electrospun fiber membrane.27
This flexible HPE film gave an ionic conductivity of 1.76 
102 S cm1 at room temperature while maintaining favourable
mechanical strength. Moreover, a solid-sate ZIB equipped with
HPE, flexible MnO2/CNT cathode and Zn/CNT anode exhibited
considerable flexibility and stability, even under harsh condi-
tions such as bending, hammering, washing in water and
exposure to fire.27 In addition, other functionalities such as
self-healing and anti-freezing can be also introduced into gel
electrolytes. For example, the PVA/Zn(CF3SO3)2 hydrogel elec-
trolyte was shown to exhibit an ionic conductivity of 12.6 
103 S cm1 and superior self-healing behaviour without the
need of external stimulus.2 A novel glycerol and ethylene glycol
based waterborne anionic polyurethane acrylates/polyacryla-
mide (EG-waPUA/PAM in short) hydrogel electrolyte was also
reported to show freeze-resistance and long-term stability even
at a temperature of 20 1C, benefiting from the strong hydro-
gen bonds between EG-waPUA, water and PAM in the gel.2
Exceptional flexibility and durability could be maintained
under adverse mechanical environments such as bending,
compressing and hammering. These unique properties can be
attributed to the strong cooperative interaction between the
polymer matrix and water that firmly immobilizes water mole-
cules inside the polymer chain network. Taking advantages of
the profound hydrogen-bonding effect is a useful strategy in the
design and assembly of advanced gel electrolytes for ZIBs
working in some extreme environments.
4.2 Non-aqueous electrolytes
Nonaqueous electrolytes enable a wide electrochemical window
and alleviate side reactions (like the competitive hydrogen
evolution and oxygen evolution) faced in water-based counter-
parts, thus feasibly simplifying the Zn plating/stripping electro-
chemistry and permitting high-voltage ZIBs.20–22 However,
non-aqueous ZIBs have drawn less attention, particularly concerning
the electrode/electrolyte interface compatibility, kinetics, and safety.
In this section, we selectively overview a few organic-solvent, ionic
liquid and deep eutectic solvent-based electrolytes for ZIBs.
Organic electrolytes. Typical aprotic electrolytes for ZIBs are
mainly comprised of acetonitrile (AN), propylene carbonate
(PC), diglyme (G2), N,N-dimethylformamide (DMF), and tri-
methyl and triethyl phosphate (TMP and TEP) as solvents,
and Zn(TFSI)2 and Zn(CF3SO3)2 as salts. The properties of
solvents are demonstrated to be the most important factor in
determining the anodic stability of organic electrolytes. The
exemplified AN permits highly reversible Zn plating/stripping
(499% CE) and a wide electrochemical window up to 3.8 V vs.
Zn/Zn2+.21 The Zn(CF3SO3)2–AN system can well support a
ZnNi1/2Mn1/2CoO4 cathode with a high average voltage at
around 1.7 V.38 However, organic electrolytes still suffer from
disadvantages including low ionic conductivity and sluggish
interfacial charge transfer, which lead to low deliverable capa-
city and poor rate capability of ZIBs (Fig. 10c). Recent research
on the kinetics revealed that the charge transfer resistance at
4216 | Chem. Soc. Rev., 2020, 49, 4203--4219
Chem Soc Rev
the electrode–electrolyte interface in nonaqueous media was
nearly 100 and 15 times that of aqueous values for the
Zn counter and V3O7H2O working electrode, respectively.13
Moreover, the nonaqueous charge transfer was characterized by
much higher activation energies (75 kJ mol1 for the V3O7H2O
cathode and 223 kJ mol1 for the Zn anode) compared with those
in the aqueous counterpart (20 kJ mol1 for both electrodes).
This difference arises from a large Zn2+ desolvation penalty in a
nonaqueous system in addition to strong cation–anion inter-
actions. To improve the sluggish kinetics in nonaqueous
media, promising strategies include optimizing the electrolyte
with low viscosity and weak Zn2+ coordination, tuning the
cathode surface to minimize the interfacial barrier of charge
transfer, and designing large-layered/open-framework hosts to
allow solvated Zn2+ intercalation.
Besides, organic electrolytes employing carbonate or aceto-
nitrile (AN) solvent are highly flammable/volatile and would pose
safety issues of the battery. Alkyl phosphates (e.g., TMP and TEP)
promise safe non-aqueous ZIBs due to the fire-retardant prop-
erty, high solvability of salts, low viscosity, and a wide range of
operating temperature.22 For example, a non-flammable 0.5 M
Zn(CF3SO3)2 in TEP electrolyte was demonstrated to allow stable
Zn plating/stripping with a high CE of 99.68%.20 Nonetheless,
alkyl phosphates possess intrinsic instability at high potentials,
restricting the choices of high-voltage cathode materials. To
tackle this limitation, attempt was made to regulate the solvation
structure of the electrolyte by designing a concentrated TMP-
based electrolyte with 0.5 M Zn2+ and 1.0 M Na+, which exhibited
high anodic stability up to 2.8 V (vs. Zn) that well supported the
polyanion-type cathodes.22 The enhanced oxidation stability was
attributed to the strong interaction between TMP solvents and
Zn2+/Na+ salts that reduced free solvents.
Ionic liquid electrolytes. Ionic liquids (ILs) are molten salts
in liquid state at near ambient temperature, which consist of
bulky, asymmetric organic cations and inorganic/organic anions.
Typically, ILs exhibit low vapour pressure, a large electrochemical
window, high chemical/thermal stability and non-flammability.
Nonetheless, they are generally costly and highly sensitive to
moisture, imposing difficulty in making IL-based batteries.
Fundamental studies on the zinc electrodeposition from ILs
have drawn much interest but few studies have focused on the
ZIB chemistry in IL electrolytes. Most of the reported IL-based
electrolytes for reversible Zn plating/stripping are based
on imidazolium and pyrrolidinium cations with counterions
of TFSI, dicyanamide (DCA), and trifluoromethylsulfonate
(TfO). The Zn salts are known to be responsible for the
morphology of electrodeposited Zn. Furthermore, the rate
capability of ZIBs with IL electrolytes is inferior to that with
the aqueous counterpart. Addition of water into ILs is adapted
to enhance performance as water contributes to reduce the
activation barrier required for Zn deposition and assist in
stable cycling. In this regard, Endres et al. reported a bio-
ionic liquid–water electrolyte composed of 1 M zinc acetate
(Zn(OAc)2)/(choline acetate ([Ch]OAc) + 30 wt% water), which
endows a reversible capacity of 120 mA h g1 and a coulombic
efficiency of 99% at 10 mA g1 for the coupled FeFe(CN)6
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Chem Soc Rev
cathode.44 Further studies are required to elucidate the solva-
tion structure of Zn2+ and the surface properties of electrodes in
IL-based electrolytes.
Deep eutectic electrolytes. Deep eutectic solvents (DESs)
have recently been introduced in electrolytes of ZIBs. Typical
DESs are formed by the complexation of a quaternary ammonium
salt with a metal salt or a hydrogen-bond donor, and are often
less expensive, nontoxic, biodegradable, and easily prepared.16,50
Choline chloride (ChCl)/urea has been considered as one of the
most promising DES systems, due to its high metal-salt solubility
and a wide electrochemical window. A reported ChCl/urea + 0.3 M
ZnCl2 electrolyte, in which chlorozincate ions ([ZnCl4]2) serve as
the charge carrier ([ZnCl4]2 2 Zn2+ + 4Cl), enables reversible
Zn2+ intercalation into the MnO2 cathode with a capacity of
170 mA h g1.16 A recent study showed that an acetamide–
Zn(TFSI)2 eutectic electrolyte (ZES) could induce a zinc fluoride-
rich organic/inorganic hybrid solid electrolyte interphase (SEI) on
the Zn anode, as the TFSI-containing Zn complexes in ZES
render preferential reductive decomposition of TFSI prior to Zn
electrodeposition.50 This SEI-coated Zn anode exhibits highly
reversible (B100% CE) and dendrite-free Zn plating/stripping
performance. Research on DESs for ZIBs is in the incipient
stage and rapid advance can be expected from DESs that bring
about lower viscosity, higher ionic conductivity, and enhanced
low-temperature performance.
5. Conclusions and perspectives
Rechargeable zinc-ion batteries stand out from a variety of
todays’ battery technologies for the balance of advantages in
cost, performance, safety, environmental impact, and material
availability. In this tutorial review, we have presented an
introduction to the fundamentals and a summary of the key
material developments of ZIBs. An overview is given from the
basic Zn chemistries, to efficient strategies to realize stable Zn
anodes, design principles of high-performance cathode materials
and related Zn-storage mechanisms, and regulation of efficient
electrolytes. The past decade has witnessed substantial progress
in the field of ZIB technologies; yet there are still issues to be
addressed. We highlight here the remaining challenges and
perspectives of ZIBs.
For the anode part, though the environmentally stable
metallic Zn (e.g., foil or powdery form) could be directly used
for ZIBs, the low utilization generally poses large loss of energy
density. Loading Zn on a 3D porous conductive skeleton would
effectively improve the mass utilization of Zn anodes. Deep
charging or discharging of Zn anodes is plagued by issues
including dendrite growth, low Zn plating/stripping efficiency,
corrosion by the electrolyte, competitive hydrogen evolution
and surface passivation. To enhance the reversibility and
stability of metallic Zn anodes, different valid strategies have
been proposed from the aspects of formulating electrolytes,
tailoring Zn electrode structures, surface coating, Zn alloying,
etc. In addition, in situ building a protective solid electrolyte
interface (SEI) on the metallic Zn anode deserves more
This journal is © The Royal Society of Chemistry 2020
Tutorial Review
attention. More efforts are required to conquer all the problems
faced by Zn anodes. Notably, testing protocols in terms
of current density, plating/stripping capacity, temperature,
and battery configuration that significantly alter the Zn
anode performance should be taken into consideration when
evaluating solutions, which are important metrics in identifying
practical ZIBs.
For the cathode part, the specific capacities of reported
active materials are far from comparable with the capacity of
Zn anodes (820 mA h g1). This mismatch calls for innovative
cathode materials based on the new Zn-storage mechanism
(i.e., simultaneous cationic and anionic redox reactions) to
afford higher capacities. The divalent Zn2+ has strong electro-
static interaction with the cathode frameworks, leading to
sluggish Zn2+ diffusion. Defect chemistries (e.g., cation and
oxygen vacancies), bulk doping, enlarging interplanar spacing,
nanostructure engineering, and pre-intercalation of ions and/or
H2O are expected to enhance the Zn-storage performance. In
addition, the dissolution of active materials in aqueous electro-
lytes and large volume variation caused by phase transition are
non-negligible issues to result in rapid capacity fading. Besides,
large desolvation penalties at the electrode–electrolyte interface
impede the Zn2+ intercalation kinetics, particularly in a non-
aqueous system. Remedies may lie in modifying the electrode
surface to reduce the interfacial charge transfer barrier and
developing large-layered/open-framework materials to accom-
modate solvated Zn2+ intercalation. Furthermore, the poor
electrical conductivity of many cathode materials (in particular
organic compounds) limits their rate capability. In this regard,
strategies of electrolyte optimizing, coating or compositing
with conductive carbon-based materials (e.g., carbon black,
graphene and CNTs) and conducting polymers (e.g., PEDOT
and PANI) have proven effective to upgrade the electrode
performances. In addition to inorganic hosts, organic cathode
materials with tunable structures and abundant precursors
may be attractive candidates for both aqueous and nonaqueous
systems in the future research.
For the electrolytes, it remains a formidable challenge to
formulate a couple of zinc salt and solvents well compatible
with both Zn anode and Zn-storage cathode. The composition
of electrolytes dictates the Zn plating/stripping behaviours, the
electrochemical window, the mechanism, and the kinetics of
Zn2+ intercalation. The oxygen evolution in aqueous electrolytes
at high operating voltages (42 V vs. Zn2+/Zn) would limit the
selection of high-voltage cathodes. The use of a concentrated
salt (in the unusual case ‘solvent-in-salt’) is demonstrated to
significantly improve the anodic stability of the electrolyte and
the stability of electrodes; yet it raises concerns regarding the
increase of cost and viscosity. Electrolyte additives seem more
economic, as shown in the examples that the application of an
inexpensive surfactant (e.g., SDS) can expand the electrolyte
working window, and Mn2+ addition helps to accommodate Mn
dissolution and form a protective surface layer on MnOx
cathodes. Further studies are required to gain deep insight
into the cation solvation sheath, the role of Zn2+ de-solvation at
the solid–liquid interface, the diffusion kinetics of Zn2+, and
Chem. Soc. Rev., 2020, 49, 4203--4219 | 4217
Tutorial Review
the interfacial chemistries (e.g., the formation and function of
the anion/solvent-derived SEI) in aqueous and nonaqueous
systems. More attention will be paid to exploring an advanced
electrolyte formula that sustains large-scale applications
of ZIBs.
Other components of ZIBs such as separators, current
collectors, and binders are important likewise but have drawn
much less attention. Further optimization will go to the widely
employed separators of filter paper and glass fiber, current
collectors of titanium/steel foils and carbon paper/cloth, and
binders of polyvinylidene fluoride, polytetrafluoroethylene and
carboxymethyl cellulose. In addition to material optimization
of these key components, an in-depth understanding of the
energy conversion and storage mechanism in ZIBs should be
intensified as well. The cathode reactions often involve diverse
species such as guest ions (e.g., Zn2+ and H+), additive ions,
lattice water, and solvent molecules. This complexity, together
with elusive storage sites and ionic diffusion paths, poses
difficulty in mechanistic studies. The identification of the
competition between Zn2+ and proton intercalation in aqueous
media and its effect on performance are also important for the
design of cathode materials. Therefore, an integration of
advanced characterization (particularly operando techniques)
and simulation methods is highly desirable to gain fundamen-
tal knowledge of ZIBs.
For potential applications, the moderate energy density, low
cost, and high safety render ZIBs particularly attractive in the
field of large-scale energy storage. On the other hand, the
emerging wearable devices resort to the development of light-
weight, flexible power sources, where ZIBs will find a niche.
Although in the incipient stage, solid progress has been made
in flexible ZIBs, particularly concerning quasi-solid-state
configuration with hydrogel electrolytes. A few prototype ZIBs
show interesting stretchability and mechanical properties,
while their stability requires further improvement for practical
aspects. Building flexible ZIBs with wide-temperature tolerance,
self-healing, thermoresponsive and photoresponsive features is
fascinating in view of the huge applicability in next-generation
wearable electronics. Note that most research studies on per-
formance evaluation of ZIBs are based on lab-made cells, from
which the results may not be straightforwardly translated into
practical batteries. Testing conditions to meet industrial
requirements should be considered from aspects such as high
mass loading, minimal electrolyte usage, optimized cathode to
anode ratio, and so on. In addition, the cost analysis, areal
capacity, life span, and gravimetric/volumetric system energy
density should be rationally assessed in light of practical
applications. In conclusion, rechargeable ZIBs are currently at
the laboratory level, and the remaining challenges call for
tremendous efforts to realizing this promising electrochemical
energy storage technology.
Conflicts of interest
There are no conflicts to declare.
4218 | Chem. Soc. Rev., 2020, 49, 4203--4219
Chem Soc Rev
Acknowledgements
This work was supported by Natural Science Foundation
of Tianjin (18JCZDJC31100), MOST (2017YFA0206700), NSFC
(21871149 & 21805066), National Program for Special Support of
Eminent Professionals, MOE (B12015), Natural Science Founda-
tion of Hebei Province (B2019201160), Top Young Talents Project
of Hebei Education Department (BJ2019052), the Fundamental
Research Funds for the Central Universities, and China Postdoc-
toral Science Foundation (2019T120191).
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Chem. Soc. Rev., 2020, 49, 4203--4219 | 4219