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Title: Recent Progress in the Electrolytes of Aqueous Zinc-Ion Batteries

Authors: Shuo Huang, Jiacai Zhu, Jinlei Tian, and Zhiqiang Niu

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Chemistry - A European Journal 10.1002/chem.201902660

MINIREVIEW

Recent Progress in the Electrolytes of Aqueous Zinc-Ion Batteries

Shuo Huang,† Jiacai Zhu,† Jinlei Tian and Zhiqiang Niu*

Dedicated to 100th Anniversary of Nankai University

Accepted Manuscript

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Chemistry - A European Journal 10.1002/chem.201902660

MINIREVIEW

Abstract: Rechargeable aqueous zinc-ion batteries (ZIBs) have

garnered tremendous attention in the next energy storage
devices due to their high safety, low cost, abundant resources
and eco-friendliness. As an important component of zinc-ion
battery, electrolyte plays a vital role in the electrochemical
properties of zinc-ion battery since it will provide a pathway for
the migrations of the zinc ions between the cathode and anode,
and determine the ionic conductivity, electrochemically stable
potential window and reaction mechanism. In this minireview, a
brief introduction of electrochemical principles of the aqueous
ZIBs is discussed and the recent advances of various aqueous
electrolytes for ZIBs, including liquid, gel, and multifunctional

Accepted Manuscript
hydrogel electrolytes are also summarized. Furthermore, the
remaining challenges and future directions of electrolytes in
aqueous ZIBs are also discussed, which could provide clues for
the following development.

1. Introduction

Lithium-ion batteries (LIBs) have been widely used in portable

electronics and considered for electric vehicles as well as Figure 1. Overview of electrolytes for aqueous ZIBs, including liquid, gel, and
multifunctional electrolytes.
large-scale energy storage systems due to their high energy
density.[1] However, the increasing concerns about cost, safety,
limited lithium resources as well as environmental impact
their excellent and compatibility with the electrodes. [3b, 7]
motivate the search of alternative battery systems.[2] Compared
Nevertheless, rechargeable ZIBs based on these aqueous
with traditional organic electrolytes-based LIBs, aqueous
electrolytes often suffer from poor Coulombic Efficiency (CE) and
metal-ion batteries are promising for large-scale energy storages
rapid capacity fading due to the dissolution of cathode materials
since aqueous electrolyte possesses more safety, lower cost,
in the electrolytes and the irreversible side reactions on both
easier processing, and higher ionic conductivity in comparison
cathodes and anodes.[8] In addition, the recent development of
with the that of organic electrolyte.[3] Among various aqueous
flexible and wearable electronic devices requires energy storage
metal-ion batteries, aqueous zinc-ion batteries (ZIBs) are of high
devices to be flexible, thin, and high performance. Obviously,
interest because of the unique advantages of Zn, such as high
conventional ZIBs are not able to meet these demands and thus
theoretical capacity (820 mAh g-1 and 5855 mAh cm-3), low redox
unconventional ZIBs such as flexible and/or stretchable devices
potential (-0.76 V vs. standard hydrogen electrode), high safety,
with light, thin and integrated configurations have to be
high abundance (about 300 times higher than lithium) and
considered and developed.[9] Therefore, some strategies of
environmental friendliness.[4]
designing solid state (gel) electrolytes, and/or adding functional
As an important component of zinc-ion battery (ZIB),
additives into electrolytes have been developed to overcome the
electrolyte plays a vital role in the electrochemical properties of
issues of conventional ZIBs and meet the demand of flexible
ZIB since electrolyte will provide a pathway for the migrations of
ZIBs. However, it is noted that a comprehensive review with the
the zinc ions between the cathode and anode, and determine the
focus on the electrolytes of ZIBs is still absent.
electrochemically stable potential window (ESPW), t he
Up to now, the development of electrolytes for ZIBs is still in
reversibility of Zn plating/stripping processes, the reaction
its infancy stage and more in-depth understanding of the effect of
mechanisms, and the ionic conductivity.[5] Furthermore, the
electrolytes on the electrochemical performance is required. This
selection of electrolytes is vital important to the accurate
minireview presents the electrochemical principles of the
evaluation of electrode materials and the achievement of
aqueous ZIBs and summarizes the recent achievements of
superior electrochemical performance.[6] The common aqueous
various aqueous electrolytes for ZIBs, including liquid, gel, and
electrolytes of ZIBs are ZnSO4 and Zn(CF3SO3)2 solution due to
multifunctional hydrogel electrolytes (Figure 1). Furthermore, the
remaining challenges and prospects of electrolytes in aqueous
S. Huang, J. Zhu, Prof. J. Tian, Prof. Z. Niu
ZIBs are also discussed, which could shed light on the R&D of
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of ZIBs.
Education), Renewable Energy Conversion and Storage Center, College of
Chemistry
Nankai University
Tianjin, 300071, P. R. China
E-mail: zqniu@nankai.edu.cn.

†These authors contributed equally to this work.

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Chemistry - A European Journal
MINIREVIEW
Shuo Huang received her M.S. degree in
polymer materials from Beijing University of
Chemical Technology in 2017. She then
joined the Key Laboratory of Advanced
Energy Materials Chemistry in
University under the supervision of Prof.
Zhiqiang Niu. Her research focuses on the
design and fabrication of smart hydrogel
electrolytes for aqueous zinc-ion batteries.
Jiacai Zhu received his B.S. degree in
chemistry from Nankai University in 2017. He
then joined the Key Laboratory of Advanced
Energy Materials Chemistry in
University under the supervision of Prof.
Zhiqiang Niu. His research focuses on the
development for multifunctional
zinc-ion batteries.
Jinlei Tian received his B.S. and M.S.
degrees from Lanzhou University in 1998 and
2001, respectively, and his Ph.D. from Nankai
University in 2004 under the supervision of
Prof. Shi-Ping Yan. He then joined the faculty
at Nankai University and was promoted to
associate professor in 2008.
published over 100 SCI index papers with
co-authors. His current research works focus
on Metal-based anticancer drugs and MOF
functional materials.
Zhiqiang Niu is a Professor at the College of
Chemistry, Nankai University. He received his
Ph.D. degree from the Institute of Physics,
Chinese Academy of Sciences in 2010 under
the supervision of Prof. Sishen Xie. After his
postdoctoral research in the School
Materials Science and Engineering, Nanyang
Technological University (Singapore,
co-supervisor: Prof. Xiaodong Chen), he
started his independent research career in
Nankai University in 2014. He has been
awarded the National Youth Thousand
Talents of China (2015). He has published more than 70 peer-reviewed
journal papers. His research interests include advanced energy storage
materials and devices.
10.1002/chem.201902660
2. Electrochemical Principles of Aqueous
Zinc-Ion Batteries
Generally, a zinc-ion battery (ZIB) is typically composed of a
cathode of Zn2+ storage material, a separator, a Zn anode as well
Nankai as an aqueous electrolyte. Its energy storage mechanism
depends on the selection of the cathode materials and the
electrolytes.
In the alkaline electrolyte solution, the Zn anode often occurs
a stripping/plating process while the cathode (e.g. MnO2, Ni(OH)2,
Ag2O, air electrode) occurs a H+-induced conversion reaction.[7a,
10]
For instance, the reaction mechanism of conventional alkaline
Zn-MnO2 battery (ZMB) could be expressed as follows:
Accepted Manuscript
Anode:
- -
n n e- (1)
Nankai Cathode:
-
n e- n (2)
However, since alkaline ZMB is a primary system, its utilization
aqueous
efficiency of resources is low. Furthermore, the irreversible side
reactions on both manganese oxide cathodes and Zn anode
result in the poor Coulombic efficiency and rapid capacity fading.
In addition, the conventional energy storage mechanism of
the ZIBs in the neutral or mild acidic electrolyte is the reversible
insertion/extraction of Zn2+.[11] During the discharge process, the
Zn in the anode is oxidized to soluble Zn2+ and migrates to the
electrolyte, while the Zn2+ in the electrolyte can insert into the
cathode. Inversely, during the charge process, the Zn 2+ extracts
from the cathode to the electrolyte, and the Zn2+ in the electrolyte
gains electrons and plates on the surface of the Zn anode. For
He has example, the electrochemical reaction mechanism of
rechargeable IBs based on the α-MnO2 cathode could be
formulated as follows:
Anode:
n n e- (3)
Cathode:
n e- α- n n n (4)
Overall:
n α- n n n (5)
Apart from the typical Zn2+, H+ can also participate in the
electrochemical reaction of ZIBs as the charge carrier, resulting
in the co-insertion/extraction of dual carriers (H + and Zn2+).
of
However, the ion insertion sequence of Zn2+ and H+ relies on the
component or crystal structure of active materials and the
Figure 2. Electrochemical principles of a) alkaline zinc-based batteries. b) the
rechargeable aqueous ZIBs.
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Chemistry - A European Journal 10.1002/chem.201902660

MINIREVIEW

selection of the electrolytes. The consequent Zn2+ and H+
insertion/extraction mechanism was illustrated in the case of
α-MnO2 nanoflakes, where the H+ first inserts into the α-MnO2
cathode and then the Zn2+.[12] Different from this two-step
reaction process, a simultaneous Zn2+ and
co-insertion/extraction mechanism is also clarified in
Zn/NaV3O8·1.5H2O system with Na2SO4/ZnSO4 electrolyte.
During the discharge process, the H+ and Zn2+ could
simultaneously insert into the NaV3O8·1.5H2O nanobelts
accompanied by the formation of Zn4SO4(OH)6·4H2O.
Furthermore, since the existence of H+ could promote the
transfer of the Zn2+, the Zn/NaV3O8·1.5H2O battery displays an
enhanced electrochemical performance. In addition, a
However, the practical application of ZIBs based on alkaline
electrolytes is usually hindered by the low plating/stripping
Coulombic efficiency of Zn anode as well as the formation of zinc
dendrites and ZnO by-products, leading to fast capacity fading
H+ and low Coulombic efficiency (<50%).[14] Compared with the
alkaline electrolyte, a neutral or mild acidic aqueous electrolyte is
preferred for ZIBs, but it also suffers from the issue that Zn anode
and current collector would be corroded by the acidic electrolyte.
To resolve the issue, many research efforts have been focused
on electrolyte optimization by adding the functional additives in
electrolyte. In this section, alkaline, neutral or mild acidic
electrolytes and the additives in electrolytes will be discussed
respectively (Table 1).

conversion reaction mechanism is also observed in the Zn/MnO2
system with ZnSO4 electrolyte. In this system, H+ reacted with
the α-MnO2 to form MnOOH, while the OH- could react with the
ZnSO4 electrolyte to from Zn4SO4(OH)6·xH2O.[13]
As discussed above, the electrolyte also plays a significant
role in the electrochemical mechanisms of ZIBs. In the following
sections, we will discuss the relationship between the electrolyte
and electrochemical performance of the ZIBs.
3. Liquid Electrolytes
Aqueous liquid electrolytes are dominating the research of ZIBs
due to the unique merits of aqueous solutions, including low cost,
high security, environmental friendliness, and excellent ionic
conductivity.[7b] Early attempts were made in alkaline electrolytes.
Table 1. The Comparison of electrochemical performance of aqueous liquid electrolytes.
Accepted Manuscript
3.1 Alkaline Electrolytes
Alkaline electrolytes were widely applied in Zn-based batteries at
the earlier stage, such as alkaline Zn/MnO2, Zn/Ni, Zn/Ag, and
Zn/air batteries.[27] Generally, these Zn-based batteries possess
a similar configuration, which consists of a Zn anode, an
aqueous alkaline electrolyte, and a functional cathode (e.g. MnO 2,
Ni(OH)2, Ag2O, and air diffusion electrode). The electrolytes
containing lithium hydroxide (LiOH), sodium hydroxide (NaOH),
or potassium hydroxide (KOH) have been used in the Zn-based
batteries.[27] Among them, potassium hydroxide (KOH) solution is
the most extensively used due to the high solubility of zinc salts
(e.g. ZnO or Zn(OH)42-) and fast electrochemical reaction kinetics.
Since K+ possesses a lower dissociation heat, the higher ionic

Category Electrolytes Solubility [15] Concentration Ionic conductivity ESPW (V) Cost CE of Ref.
g/100 g H2O (S cm-1) Zn anode

Alkaline Electrolytes KOH 121 1M ~0.5 ~2 Low <50% [16]

Oxidative Zinc Salt Zn(NO3)2 120 1M - 1.5 V Low - [16a]

Electrolytes
-3
Zn(ClO4)2 121.3 0.5 M 7.14×10 - Low - [17]

Zinc Halide Electrolytes ZnF2 1.55 86 mM - - Low - [18]

-1
ZnCl2 408 1-5 M ~10 <1.6 V Low <73.2% [16a, 19]
-2
ZnCl2 408 18 M 1.5×10 (30 °C) High ~99% [20]
-2
ZnCl2 408 30 M 2.9×10 2.3 V High 95.4% [19b]

Zinc Sulfate Electrolytes ZnSO4 57.7 3M ~2.4 V Low ~75% [16a,16c, 21]

Organic Zinc Salt Zn(CF3SO3)2 14.6 1M ~5.9 2.4 V High 100% [16a]
Electrolytes
Zn(CF3SO3)2 14.6 3M 3.47 2.5 V High ~100% [16a, 22]

Zn(CH3COO)2 30.0 2M Low 80% [11a]

Zn(TFSI)2 - 1M - - High - [23]

Electrolytes with 3 M ZnSO4/0.1 M MnSO4 1.9 - Low - [12]

Functional Additives
1 M ZnSO4/1 M Na2SO4 - - Low - [24]

2 M ZnSO4/0.2 M CoSO4 - 2.26 V Low ~100% [25]a

3 M Zn(CF3SO3)2/0.1 M Mn(CF3SO3)2 ~6 - High ~93% [22]

1 m Zn(TFSI)2+20 m LiTFSI - - High 99.5% [16c]

1 m Zn(CF3SO3)2+21 m LiTFSI - 2.60 V High 100% [26]

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Chemistry - A European Journal 10.1002/chem.201902660

MINIREVIEW

conductivity (73.5 S cm-2) is obtained compared with Li+ (~38 S
cm-2) or Na+ (~50 S cm-2), resulting in a better transportation
kinetics. In addition to the selection of alkaline salts, the
concentration of electrolyte is another key for Zn-based batteries.
As discussed above, the electrochemical reaction mechanism of
traditional alkaline Zn-based batteries is based on the
dissolution/deposition processes at the Zn anode and H+-induced
conversion reactions at the cathode. However, if the batteries
continued to discharge, the cathode and the anode would be
further irreversibly reduced. The following steps could be
formulized as follows:[28]
Anode:
-
n n e -
n e-
(6)
concentrated electrolyte could bring some problems, such as the
formation of zinc dendrites, dissolution of cathode material, and
corrosion of current collector, resulting in severe capacity
degradation and poor Coulombic efficiency (Figure 3b).
Furthermore, the high corrosive alkaline electrolyte is
environmental unfriendly and exists a safety hazard. These
knotty issues limit the development of the alkaline electrolytes in
Zn-based batteries.
3.2 Neutral or Mild Acidic Electrolytes
The Zn is an amphoteric metal, which can react with OH - or H+
species. In the conventional corrosive alkaline electrolytes (pH of

Accepted Manuscript
Cathode: about 14), the existence of a large amount of OH - can seriously
- attack the Zn anode to form by-products Zn(OH)42- or ZnO
n e- n (7) - - -
species ( n n e- n e- ).
The continuous formation of ZnO, Zn(OH)2, and Mn(OH)2
Therefore, the conventional alkaline electrolyte displays an
by-products leads to severe capacity degradation and poor
unsatisfactory compatibility with Zn anode. As compared to the
Coulombic efficiency in Zn-based batteries. Therefore, a high
alkaline electrolytes, owing to the existence of a small amount of
concentrated KOH electrolyte is required to improve the solubility
H+, the mild acidic electrolytes (pH of 3.6~6.0) can alleviate the
of by-products since ZnO could transform to Zn(OH)42- species in
formation of the by-products, therefore showing better
such high concentrated electrolyte by the coordinated
compatibility with Zn anode. Up to now, various zinc salts, such
complexation reaction. In addition, with the increase of the
as oxidative zinc salts (e.g. Zn(NO3)2, Zn(ClO4)2), zinc halides
concentration of KOH electrolyte, the exchange current density
(e.g. ZnCl2, ZnF2), zinc sulfate (ZnSO4), and organic zinc salts
increases while the electrode potential decreases, suggesting
(Zn(CF3SO3)2, Zn(CH3COO)2, Zn(BF4)2·xH2O, and Zn(TFSI)2)
that the electrochemical reaction kinetics improves. Nevertheless,
were used to prepare ZIB electrolytes and show different
the concentration of the KOH electrolyte could not surpass 6 M
electrochemical properties.[29]
because the ionic conductivity of the electrolyte would get worse
At the earlier stage of developing neutral or mild acidic
(Figure 3a). Thus, the aqueous alkaline electrolyte is often 6 M
electrolytes, the aqueous Zn(NO3)2 solution was introduced in
KOH solution.
aqueous Zn/CuHCF battery. [30] The copper hexacyanoferrate
Although high concentrated KOH electrolyte can enhance
(CuHCF) is a Prussian Blue Analogs (PBAs)-based cathode
the reaction kinetics of Zn-based batteries, the use of high

Figure 3. a) Performance and properties of alkaline electrolytes as function of KOH concentration. Reproduced with permission.[27] Copyright 2009 Elsevier. b)
Pourbaix diagram of zinc in alkaline electrolyte at 25 °C. Reproduced with permission. [27] Copyright 2009 Elsevier. c) Cyclic voltammograms of Zn electrode in 1 M
aqueous ZnCl2 electrolyte. Reproduced with permission.[16a] Copyright 2016 American Chemical Society. Structure of and cyclic voltammograms of Zn electrode in
aqueous electrolyte of d) 1 M ZnSO4 and e) 1 M Zn(CF3SO3)2. Reproduced with permission.[16a] Copyright 2016 American Chemical Society. f) The Coulombic
Efficiency of ZIB with ZMO/C cathode in different concentrations (1-4 M) Zn(CF3SO3)2. Reproduced with permission.[16a] Copyright 2016 American Chemical
Society.

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Chemistry - A European Journal
MINIREVIEW
material with an open framework structure. Owing to its unique
crystal structure, the reversible Zn2+ insertion/extraction is
observed in the typical cubic CuHCF cathode. However, their
cycle performance was unsatisfactory in the case of NO3- anions,
especially at the high-voltage region.[18] It is noted that the NO3-
anions are strongly oxidants and could attack the electrodes,
leading to the serious corrosions of the Zn foil and CuHCF the
cathode material. Similarly, Zn(ClO4)2 is another zinc salt,
which is also concerned as an oxidant since the Cl atom
possesses a high valence state (+7) and can be easily reduced
to low valence state (e.g. -1 for Cl-). However, ClO4- has a stable
structure, where four O atoms are tetrahedrally coordinated with
central Cl atom, resulting in a low reaction activity. Thus, owing to
the relatively weak oxidizing species, the CuHCF material in
Zn(ClO4)2 electrolyte possesses a high reversible specific charge
retention of 95% than the case of 21% in Zn(NO3)2 electrolyte.
However, such Zn(ClO4)2 solution is not suitable as an ideal
electrolyte of ZIBs due to high overpotential, which caused by the
formation of by-products (e.g. a ZnO thin layer on the Zn foil),
leading to the decrease of reaction kinetics in ZIBs.[17-18]
Compared with conventional oxidative zinc salts, zinc halides
(e.g. ZnCl2 and ZnF2) are often more compatibility with Zn anode
due to the less side reactions with the existence the low oxidative
Cl- and F- ion. However, the application of ZnF2 electrolyte is
restricted by the low solubility of 86 mM in water.[18] Therefore,
ZIB with low concentrated ZnF2 solution achieves a poor cycle
performance due to the insufficient Zn2+ moieties. In contrast, it is
known that ZnCl2 is one of the most water-soluble inorganic zinc
salts.[31] However, the drawbacks of the narrow anodic
electrochemically stable potential window (~0.75 V for 1 M ZnCl2
solution) and the continuous side reactions limit its feasibility in
high performance aqueous ZIBs (Figure 3c).[16a]
Different from zinc salt electrolytes mentioned above, mild
acidic ZnSO4 aqueous electrolyte is widely used in the ZIBs due
to its low cost and good compatibility. The SO42- group
possesses a regular tetrahedron structure that four O atoms
locate at the vertex while the S atom stands at the body-centered
of the tetrahedron (Figure 3d). Besides, four S-O bonds show a
similar chemical property, indicating that the SO 42- has an
extremely stable structure. Thus, remarkable electrochemical
performances of ZIBs have been realized based on ZnSO4
aqueous electrolytes. It is worth noting that Zn anode has high
dissolution/deposition reaction kinetics, slight dendritic growth,
and weak corrosions in such mild ZnSO4 electrolytes.[3a] However,
the mechanisms of aqueous ZIBs with ZnSO4 electrolytes are
still debating, which are caused by the formations of
Zn4(OH)6SO4·nH2O (ZHS).[32] ZHS was generally regulated by
the pH changes of the electrolytes during the discharge process,
which could be formulized as:
- -
n n (8)
The ZHS would participate in the electrochemical reaction during
the discharge and charge processes and realize reversible
dissolution/deposition processes. Furthermore, the ZHS can be
directly used as the cathode of ZIBs and the obtained ZIBs
display a good the electrochemical reversibility.[33] However, in
the ZHS-based ZIBs, pH value increases at the discharge state
and then decreases at the charge state, which could result in the
instability of ZIB systems and reduce the Coulombic efficiency.
This article is protected by copyright. All rights reserved.
10.1002/chem.201902660
However, in some cases, ZHS was just a by-product, which
formed at the surface of the cathode, leading to the capacity
fading in the initial several cycles.[12] Thus, more efforts have to
be made to in-depth understand the mechanisms of the systems
with mild acidic ZnSO4 electrolytes and improve the recyclability
of ZIBs.
In general, traditional inorganic zinc salt electrolytes suffer
from their intrinsically limited solubility and zinc plating/stripping
Coulombic efficiency of less than 75%. To avoid these issues,
recently an organic zinc salt Zn(CF3SO3)2 electrolyte was
developed for ZIBs and exhibited an excellent electrochemical
performance, including the superior Coulombic efficiency of Zn
dissolution/deposition Coulombic efficiency, low polarization, and
Accepted Manuscript
high recyclability. Such excellent electrochemical performance is
ascribed to the bulky CF3SO3- moieties, which could reduce the
coordination number of H2O molecules surrounding Zn2+ cations
and decrease the solvation effect (Figure 3e).[16a] Therefore, it
could accelerate the Zn2+ the migration, reaction kinetics, and
charge transfer rate of Zn2+. It is noted that the electrochemical
performance of ZIBs depends on the concentration of
Zn(CF3SO3)2 electrolytes (Figure 3f). The highly concentrated
salt electrolytes could endow the ZMO/C cathode with an
excellent cycle performance and high Coulombic efficiency of
about 100% due to the low solvation effect. In addition, the
Zn/ZnMn2O4 batteries with 3 M Zn(CF3SO3)2 electrolyte could
exhibit a high specific capacity of 150 mAh g-1 with an
unprecedented capacity retention of 94% even after 500 cycles.
However, although Zn(CF3SO3)2 electrolyte could develop high
performance rechargeable ZIBs, the price of Zn(CF3SO3)2 salt is
about 18 times more expensive than the traditional inorganic salt
of ZnSO4, which could not realize the industrial-scale
manufacture.[3b]
Recently, a variety of V-based compounds were also
developed as the cathode materials in ZIBs due to their low cost,
abundant crystal structures, and high theoretical capacity.
Among various cathode materials, V-based cathodes often show
higher specific capacity (up to 400 mAh g-1), better rate capability
(up to 300 C), and longer cycle life.[11a-d] To improve the
biodegradability and biocompatibility with environment,
Zn(CH3COO)2 electrolyte was developed in the V-based ZIBs. [11a,
34]
However, the electrochemical performance of such ZIBs is
similar to the case with the electrolytes based on inorganic zinc
salts (e.g. ZnSO4). Furthermore, the organic redox-active groups
often suffer from high solubility, leading to the capacity fading in
the Zn-organic batteries. Thus, zinc salt hydrate Zn(BF4)·xH2O
electrolyte was developed for the Zn-organic batteries. The ZIBs
show the enhanced stability and rate performance since the
dissolution of active material exTTF is inhibited. [35] Moreover,
recently, a novel organic zinc salt Zn(TFSI)2 solution was
developed and also exhibited an excellent cycle performance
due to the larger TFSI- anion, which could reduce the solvation
effect. In general, traditional organic zinc salt exhibits good
electrochemical properties, such as low solvation effect and high
compatibility with Zn anode.[23]
As mentioned above, Zn(NO3)2 and Zn(ClO4)2 electrolytes
often suffer from the serious side reactions caused by the
oxidative ions. ZnF2 displays the low solubility (~86 mM) in water
solution and ZnCl2 electrolytes with low concentration exhibits a
narrow anodic potential window of 1.6 V. Therefore, the ZIBs
Chemistry - A European Journal 10.1002/chem.201902660

MINIREVIEW

based these electrolytes show the unsatisfactory electrochemical
performance. Different from above electrolytes, ZnSO 4
electrolyte was widely used in the aqueous ZIBs due to its low
cost, good compatibility and excellent electrochemical stability.
Furthermore, enhanced performances were achieved in ZnSO 4
electrolyte-based aqueous ZIBs. However, some by-products
such as Zn4(OH)6SO4·nH2O (ZHS) are observed and the energy
storage mechanisms in these ZIBs is complicated. Compared
with conventional neutral or mild acidic electrolytes, bulky-anion
zinc salts aqueous electrolytes, such as Zn(CF 3SO3)2 and
Zn(TFSI)2 electrolytes were also developed in aqueous ZIBs.
Since the bulky anions could reduce the solvation effect of Zn2+
cations and facilitate their migrations and charge transfer, the
solve these issues, recently, many research efforts have been
focused on electrolyte optimization by adding the functional
additives into the electrolyte. It is noted that the selection of the
additives mainly depends on the cathode materials and the zinc
salts. It is known that the “common ion effect” usually exists in
acid/base equilibrium and precipitation/dissolution equilibrium.
According to “common ion effect”, for Mn-based cathode material,
MnSO4 was often added into the ZnSO4 electrolyte. The addition
of Mn2+ could change the dissolution equilibrium of Mn2+ from
MnO2 cathode and impede the dissolution of MnO2.[12] Since the
loss of active MnO2 materials was alleviated, the cycle
performance of the ZIBs is significantly improved with a low
capacity decay rate of 0.007%. Similar effect was also illustrated

high ionic conductivity, good compatibility and excellent
electrochemical stability were achieved. However, these
electrolytes are often more expensive than conventional
electrolytes, which limit their industrial-scale applications.
3.3 Electrolytes with Functional Additives
Although substantial progress in the area of ZIBs with mild
electrolytes has been achieved, there are still suffer from the
issues that Zn anode or current collector would be continuously
corroded and the cathode material would be dissolved into the
acidic electrolyte, resulting in a poor Coulombic efficiency. [3b] To
Accepted Manuscript
in the case of β-MnO2 material with the addition of Mn(CF3SO3)2
in Zn(CF3SO3)2 electrolyte.[22] The mixed electrolyte with
saturated 0.1 M Mn(CF3SO3)2 could achieve a high ionic
conductivity and the addition of saturated 0.1 M Mn(CF3SO3)2
endows ZIBs with high Coulombic efficiency of 100%, as well as
an excellent specific capacity of 258 mAh g-1 at a current density
of 0.65 C (Figure 4c). Besides, recently, a similar experimental
phenomenon was also demonstrated with the presence of Na + in
Zn/NaV3O8·1.5H2O system based on the ZnSO4 electrolytes. A
large amount of Na+ ions were added into the ZnSO4 electrolytes
to alleviate the dissolution of NaV3O8·1.5H2O (NVO) nanobelts.[24]

Figure 4. a) Cycling performance of NVO electrode in ZnSO4 electrolyte. Reproduced with permission.[24] Copyright 2018 Nature Publishing Group. b) Schematic
diagram: Na2SO4 additive suppresses the dissolution of NVO nanobelts and the formation of Zn dendrites. Reproduced with permission. [24] Copyright 2018 Nature
Publishing Group. c) Comparison of the cycling performance of Zn-MnO2 batteries with electrolytes of 45 wt% KOH, 3 M ZnSO4, 3 M Zn(CF3SO3)2, and 3 M
Zn(CF3SO3)2 with 0.1 M Mn(CF3SO3)2 additive. Reproduced with permission.[22] Copyright 2018 Nature Publishing Group. d) Representative Zn2+-solvation
structures in the electrolytes with 1 M Zn(TFSI)2 and two concentrations of LiTFSI (5 m and 20 m). Reproduced with permission.[16c] Copyright 2018 Nature
Publishing Group. e) Molarity of the ZnCl2-H2O binary system as functions of the weight ratio of ZnCl 2 to H2O. Reproduced with permission.[20] Copyright 2019
Wiley-VCH. f) Schematic illustration of Zn deposition in conventional electrolytes and a molten hydrate electrolyte. Reproduced with permission.[20] Copyright 2019
Wiley-VCH. g) SEM images of Zn deposits. Reproduced with permission.[20] Copyright 2019 Wiley-VCH.

This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
MINIREVIEW
wing to the “common ion effect”, the continuous loss of active
materials NVO was suppressed (Figure 4a). Furthermore, Na+
has a lower reduction potential than Zn2+, so that the additive Na+
could form a positively electrostatic shield around the Zn
protuberances, according to the electrostatic shield mechanism.
As a result, the additive Na+ could also effectively limit the
formation of zinc dendrites (Figure 4b). Therefore, the resultant
ZIBs exhibit a good reversibility of carrier insertion/extraction,
rapid zinc plating/stripping kinetics, and a high capacity of 221
mAh g-1, even after 100 cycles at a current density of 1 A g-1.
In the conventional electrolyte, the free water in electrolytes
could attack the Zn anode to produce H2, leading to a poor
Coulombic efficiency (e.g. n n ). Besides,
in aqueous solution, Zn2+ ions could be solvated to form
Zn-(H2O)62+ due to the enough H2O molecules available. And
then, a deprotonation process would occur and generate an
acidic solution with a series of deprotonated monomeric species
(e.g. Zn-(H2O)62+, Zn(OH)2 or even ZnO). The general
deprotonation process could be formulized as follow: [36]
- the organic zinc salts (e.g. Zn(CF3SO3)2 and Zn(TFSI)2), which
n → n (9)
The formation of inactive Zn(OH)2 or ZnO by-products will
degrade the electrochemical performance of aqueous ZIBs with
conventional salt-in-water electrolytes. To overcome this
drawback, the novel highly concentrated electrolyte, which is
called water-in-salt electrolyte and consists of 20 m LiTFSI and 1
m Zn(TFSI)2 (where TFSI- is considered as
bis(trifluoromethanesulfonyl)imide), was developed. In such
highly concentrated electrolyte, the Zn2+ has a unique
solvation-sheath structure that could significantly form close ion
pairs (Zn-TFSI)+ rather than Zn-(H2O)6+ with the surrounding of
the abundant anions (Figure 4d).[16c] Such water-in-salt
electrolyte not only displays nearly 100% Coulombic efficiency
without the growth of dendrites during Zn plating/stripping
process, but also suppresses the consumption of water in the
open atmosphere. In addition, the highly concentrated
electrolytes of 21 m LiTFSI and 1 m Zn(CF3SO3)2 solution could
also expand the electrochemically stable voltage windows to
approximately 2.60 V in comparison with the case of
conventional ZnSO4 electrolyte of 2.4 V.[26] Therefore, the
assembled Zn/VOPO4 battery could operate at the high voltage
of about 2.1 V. In addition, owing to the existence of PO43-
polyanions, the VOPO4 nanosheet displays a higher average
operating voltage (~1.56 V). Furthermore, since the electron
density of the oxygen in VxOy polyhedral was increased due to
the introduction of P-O covalence, the oxygen redox is observed
in Zn/VOPO4 battery. The oxygen redox chemistry can provide
additional capacity of about 27% at high voltage region, leading
to an increase of the energy density. Besides, to broaden the
electrochemically stable potential window of ZnCl2 electrolytes,
30 M highly concentrated ZnCl2 electrolyte was developed.[19] It
could withstand a high voltage of 2.3 V in the case of the
existence of [ZnCl4]2-. The mechanism of the corresponding
batteries depends on both the cathode materials and the
components of electrolyte. In addition to reversible Zn2+
insertion/extraction, a reversible Li+ insertion/extraction is also
observed in the Zn/V2O5 battery with water-in-salt electrolyte (21
m LiTFSI and 1 m Zn(CF3SO3)2).[37] Besides, in the case of
LiMn0.8Fe0.2PO4 nanoflowers cathode and mixed aqueous 21 m
This article is protected by copyright. All rights reserved.
10.1002/chem.201902660
LiTFSI and 0.5 M ZnSO4 electrolyte, the reversible Li+
insertion/extraction process is also observed.[38] Therefore, the
highly concentrated electrolytes open up an avenue for the
advanced multivalent ions electrochemical energy storage with
stable electrochemical performance.
Apart from water-in-salt electrolytes, the extremely
concentrated electrolyte ZnCl2·2.33H2O was also developed,
where all water molecules were trapped in the hydration shells to
further reduce free water of zinc salt electrolytes, which is
regarded as the zinc molten hydrate (Figure 4e-g).[20] The
electrochemical behavior of such electrolyte is similar to the ionic
liquid. This unique electrolyte could achieve a dendrite-free zinc
deposition/dissolution process with a high Coulombic efficiency
Accepted Manuscript
of 99%. In addition, owing to the mild acidity, the ZnCl2·2.33H2O
electrolyte could inhibit the CO2 poisoning compared with the
case of KOH electrolyte, which will be attacked by the CO2
atmosphere, leading to the accumulation of carbonate
by-products and the degradation of the electrolyte. Furthermore,
it is noted that the inorganic zinc salt ZnCl2 is much cheaper than
would be promising for large-scale energy storage devices.
4. Gel Electrolytes
Liquid electrolytes are widely used in aqueous energy storage
devices due to their high ionic conductivity, which reaches up to
7-60 mS cm-1.[39] However, liquid electrolytes often display some
issues in the practical application. For instance, the
liquid-electrolyte-based devices would suffer from the possible
leakage of harmful electrolytes and undesired dislocation under
strain.[40] To avoid these issues, some hydrophilic polymers or
inorganic components can be introduced into the Zn-containing
salt solutions to achieve gel electrolytes.[41] Compared with liquid
electrolytes, the gel electrolytes exhibit relatively lower ionic
conductivity, inferior electrode/electrolyte interfaces, and high
overpotential. However, gel electrolytes possess high physical
flexibility, desirable electrochemical properties and excellent
mechanical integrity, which could serve as both electrolyte and
separator simultaneously. Furthermore, in some cases, gel
electrolytes can also inhibit the Zn dendrite growth and enhance
electrochemical stability. As a result, gel electrolytes are
preferred in the fabrication of flexible ZIBs. Typical gel
electrolytes include the case without cross-linking, hydrogel
electrolytes with physical cross-linking and/or chemical
cross-linking network (Table 2).
4.1. Gel Electrolytes without Cross-Linking
The gel electrolytes without cross-linking are amorphous and
viscous, which contain Zn-containing salt solution and polymers
or inorganic components (Figure 5a). The polymers that were
used in gel electrolytes include polyvinyl alcohol (PVA), xanthan
gum, carboxymethyl cellulose sodium (CMC) and fumed silica.
Among them, PVA-based gel electrolytes are the most
commonly utilized.[31, 43] In PVA chain segments, hydroxyl side
groups are hydrophilic. As a result, the polymer molecules can
dissolve in water easily. The hydrogen bonds between the PVA
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Table 2. Features of the gel electrolytes.

Electrolyte Synthesis method, Ionic conductivity Features and function Ref.

-1
cross-linking manner (ms cm )
and gel state

Fumed silica (FS) Simple dissolution, ≈8.1 Prohibition of dendrite growth [42]
no cross-linking,
flow-ability

PVA Simple dissolution, 8.97 Flexible, [31, 43]

no cross-linking, variable shape
certain flow-ability

CMC Simple dissolution, - Flexible [44]

no cross-linking,

Accepted Manuscript
certain flow-ability

Xanthan gum Simple dissolution, 16.5 Flexible, [45]

no cross-linking, prohibition of dendrite growth
certain flow-ability

Gelatin Dissolution gelation, 6.1 Flexible, [24, 46]

physical cross-linking, Stretchability(50-80%),
solid state prohibition of dendrite growth

PAM Free-radical 17.3-22.8 Self-standing, [25, 47]

polymerization, Stretchability(1400-3000%),
chemcial cross-linking, Compressibility(0-80%),
solid state High-tolerant under various severe conditions

chain segments and water molecules will result in the increase of
the viscosity of the gel electrolyte system.[48] High viscosity
facilitates not only the contact between the electrolyte and
electrode materials, but also the excellent interface wettability.
Owing to the above advantages, PVA-based gel can serve as the
electrolytes of flexible ZIBs. For instance, PVA/ZnCl2/MnSO4 gel
electrolyte was designed and flexible Zn/MnO2@PEDOT battery
was fabricated based on them (Figure 5b).[31] Owing to an
ultraslow capacity decay rate and high Coulombic efficiency, the
resultant flexible Zn/MnO2@PEDOT battery could retain more
than 77.7% or 61.5% of its initial capacity after 300 or 1000
cycles, respectively. Moreover, the flexible Zn/MnO2@PEDOT
battery exhibits stable electrochemical performance under
arbitrary bending or twisting states. Furthermore, Zn/MnO2
micro-battery and cable-type battery could also be fabricated by
PVA-based gel electrolytes.[43b, 43d] Apart from PVA, CMC, which
is a widely used biomaterial, are also used to design gel
electrolyte.[44] Compared with liquid electrolyte, the ionic diffusion
of gel electrolyte is slower due to the restriction of CMC
molecules. However, owing to its strong adhesive, CMC-based
gel electrolyte could coat on the electrodes integrally. By
combining with novel coaxial structure and spherical spherical
zinc hexacyanoferrate (ZnHCF) nanomaterials, fiber Zn/ZnHCF
battery could be assembled and could tie into a knot without
damage (Figure 5c). Furthermore, it remains up to 93.2% of its
initial capacity (100.2 mAh cm-3) after bending 3000 times with
the angle of 90 o.
As mentioned before, ZnSO4 solution is a common and
low-cost electrolyte for aqueous ZIBs. But unfortunately, SO42-
ions have a very strong ability to precipitate PVA or CMC chains
according to the Hofmeister Series. [45, 49] Therefore, it is a
challenge to achieve a gel electrolyte containing highly
concentrated zinc sulfate salt in conventional polymer dispersion.
Xanthan gum is a special high-salt-tolerant biopolymer. When
the zinc sulfates were added into xanthan gum gel, there is an
interaction between carboxylate groups of xanthan gum and Zn2+,
which eliminates the salting-out and leads to the formation of
highly concentrated zinc sulfate gel electrolyte. [50] The xanthan
gum electrolyte, including 2 M ZnSO4 and 0.1 M MnSO4, is very
stable and uniform (Figure 5d).[45] Owing to the high ionic
conductivity and long-term stability of the xanthan gum
electrolyte, the assembled flexible Zn/MnO2 battery shows high
durability (a retention rate of 95%) after bending 100 cycles.
Apart from polymer gel electrolytes, fumed silica/ZnSO4
electrolyte also presents a gel state.[42a] By designing
Zn2(OH)VO4 cathode and Zn anode, the all-array
quasi-solid-state ZIBs display high rate performance and
ultrastable long-term performance. The capacity retains more
than 125 mAh g-1 (a retention rate of 89%) at 20 C after 2000
cycles. Additionally, flexible ZIBs could be bent over 100 times
without significant capacity degradation (a retention rate of 96%).
Furthermore, combining with functional additives, the gel
electrolytes can be further modified, such as inhibiting the
formation of dendrites.[42b]
4.2. Hydrogel Electrolytes with Physical Cross-Linking
The mechanical properties of gel electrolytes without
cross-linking are often unsatisfactory. Under extra forces, these
electrolytes would be damaged and deformed. As a result,
separators are still required for the corresponding devices in
most cases.[31, 43a, 43d] As we all know, a hydrogel electrolyte is
constructed from polymer network, where a large amount of salt
solution exists. [5, 52] In these hydrogel electrolyte systems,
hydrophilic groups bind to water molecules, while the polymer
chain segments swell and overlap connecting to form a

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Chemistry - A European Journal 10.1002/chem.201902660

MINIREVIEW

Accepted Manuscript
Figure 5. a) Schematic diagrams of a gel electrolyte. Reproduced with permission.[51] Copyright 2015 Royal Society of Chemistry. b) Schematic illustration
structure of flexible n/MnO2@PEDOT battery based on PVA electrolyte. Reproduced with permission.[31] Copyright 2017 Wiley-VCH. c) SEM image of the fiber
Zn/ZnHCF tied into a knot. Reproduced with permission.[44] Copyright 2019 American Chemical Society. d) Photograph showing that the xanthan gum electrolyte is
uniform and sticky. Reproduced with permission.[45] Copyright 2018 Royal Society of Chemistry. e) Optical image of gelation/ZnSO4 hydrogel electrolyte.
Reproduced with permission.[24] Copyright 2018 Nature Publishing Group. f) Schematic of the fabrication of different structures batteries based on gelatin hydrogel
electrolyte. Reproduced with permission.[46a] Copyright 2018 Royal Society of Chemistry. g) Schematic diagram of the chemical cross-linked PAM based electrolyte.
Reproduced with permission.[47a] Copyright 2018 American Chemical Society. SEM images of (h) PAM and (i) NFC/PAM hydrogels after freeze-drying. Scale bars:
(h) 10 μm and (i) 100 μm. Reproduced with permission.[47b] Copyright 2018 Wiley-VCH.

framework. As a result, hydrogel electrolytes display a
self-standing solid state on a macroscopic scale and liquid-like
on the molecular scale.
Among various hydrogel electrolytes, gelatin-based hydrogel
electrolyte (GHE) is a common hydrogel in ZIBs. [46] Compared to
the gel electrolyte, GHE can form a specified shape and maintain
stronger mechanical properties. This unique structure is
attributed to the physical cross-linking of GHE.[53] In gelatin
hydrogel systems, there are different types of hydrogen bonds
interaction between –OH, –CO and –NH groups to provide
effective physical cross-linking points. In general, by simple
heating and stirring, the gelatin and Zn-containing salt solution
can achieve a homogeneous mixture. However, at high
temperature (higher than 40 °C), the hydrogen bonds were
destroyed and the cross-linking points would be not achieved.
After cooling to room temperature, the self-standing GHE was
achieved (Figure 5e). Interestingly, the GHE can reversibly melt
and gelate during the process of heating up to 40 °C and cooling
back to room temperature. Owing to its specific shape and
structure, GHE is able to effectively avoid the leakage of
electrolyte and prevent short circuits in ZIBs. In addition, the
GHE remains relatively high ionic conductivity due to the
abundance of water in the polymer framework. To the best of our
knowledge, gelatin/ZnSO4 electrolyte was first utilized to
fabricate flexible soft-packaged Zn/NVO battery, which delivers a
high capacity of 288 mAh g-1 and superior rate capability.[24]
Furthermore, owing to the high flexibility and excellent
electrochemical performance, GHE is attracting much more
attention. For example, the solid-state Zn/LiMn2O4 battery was
also fabricated and it could resist cutting, soaking in water,
bending, twisting and crimping without electrochemical
performance degradation (Figure 5f).[46a] Specifically, due to the
reversible conversion of liquid and solid state during the slight
heating/cooling process, GHE can contact tightly with electrodes
via dipping and coating.[54]
4.3. Hydrogel Electrolytes with Chemical Cross-Linking
Generally, hydrogel electrolyte with physical cross-linking
displays the poor thermal stability and can only endure small
deformation since physical cross-linking is weak. It is noted that
the bonds in chemical cross-linking are stronger compared with
the cases of physical cross-linking.[48b, 55] As a result, hydrogel
electrolytes with chemical cross-linking possess more stable
network structure.
Polyacrylamide (PAM)-based hydrogel with chemical
cross-linking is the most promising electrolyte.[14, 56] In the PAM
hydrogel matrix, the cross-linking points exist among all the chain

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Chemistry - A European Journal
MINIREVIEW
segments, resulting in a highly porous framework (Figure 5g). [25,
47, 57]
Since the framework structure is connected by chain
segments, the PAM hydrogel electrolyte has excellent
mechanical properties. For PAM-based electrolyte with 2 M
ZnSO4 and 0.1 M MnSO4, the tensile strength can reach to 273
kPa and the stretch strain is higher than 3000%. [47a] In addition,
among uncross-linked regions of chain segments, hydrophilic
groups such as amide groups (−CONH2) trap the water
molecules within the PAM frame network through hydrogen
bonds. As a result, a large amount of Zn-containing solution
exists in the porous PAM frameworks. Their porous structures
bring benefit to the transportation of electrolyte ions. Therefore,
the ionic conductivity of PAM-based electrolyte is up to 17.3 mS
cm-1 at room temperature. When the hydrogel is subjected to
300% stretch strain, the ionic conductivity still retains 16.5 mS
cm-1, which is benefit from the stable PAM framework structure
and unresisted ionic transportation.
In addition, the electrochemical performance of hydrogel
electrolytes can be further improved by modifying some
functional groups on the framework. For example, nanofibrillated
cellulose (NFC) is widely used as a reinforcing agent due to the
abundant hydroxyl groups.[47b] The NFC/PAM hydrogel
electrolyte was synthesized through in situ polymerizing the
acrylamide monomers in cellulose nanofibrils dispersion. In this
case, NFC/PAM hydrogel remains a relatively high stretch strain
of 1400%. Especially, thanks to the abundance of hydrogen
bonds between hydroxyl groups and water molecules, the water
retention in NFC/PAM hydrogel electrolyte is enhanced and thus
obtains a larger porous framework structure (Figure 5h, i).
Consequently, compared to the PAM-based hydrogel electrolyte,
the NFC/PAM hydrogel electrolyte exhibits a much higher ionic
conductivity of 22.8 mS cm-1. The resultant solid-state Zn/MnO2
battery offers a stable electrochemical performance after 1000
cycles with the specific capacity of 200 mAh g-1 at 4 C.
A hierarchical polymer electrolyte (HPE) based on PAM
cross-linking framework was also developed.[25] Through free
radical polymerization, PAM molecules grafted onto the gelatin
chain segments and thus the gelatin-g-PAM hydrogel was
obtained. Furthermore, the hydrogel can be fabricated onto the
surface of the polyacrylonitrile (PAN) fiber membrane to further
enhance the mechanical strength. After that, an HPE film was
obtained. There are two types of cross-linking networks in the
HPE frameworks. The first ones belong to hydrogen bonds
connection between PAM chain segments and gelatin chain
segments. While the other cross-linking point attributes to
covalent bonds between the PAM chain segments. Combining
with well-designed electrodes, the flexible solid-state ZIBs deliver
a high specific capacity (306 mAh g-1) and a stable long-term
cycling performance (97% capacity retention after 1000 cycles).
Moreover, the ZIBs exhibit an excellent stability under different
severe conditions.
5. Multifunctional Hydrogel Electrolytes
The hydrogel electrolytes possess a porous network, which
consists of hydrophilic polymer chains filled with a high content of
zinc salt electrolytes. It is known that there are a variety of
This article is protected by copyright. All rights reserved.
10.1002/chem.201902660
functional chains in some polymer.[5, 52, 56, 58] Thus, the smart
features of hydrogel electrolytes could be endowed by
introducing the functional groups of polymer chains, including
self-protecting, self-recovery, self-healing and extreme
tolerability.
Recently, ubiquitous safety issues caused by over-charging
or short-circuiting have drawn increasing attention for various
energy storage devices since they will degrade the cycle life of
energy storage devices. Therefore, it is desired to develop the
smart electrochemical energy storage devices with in-situ
detecting or/and highly reversible self-protecting properties
without the help of external control systems.
Poly(N-isopropylacrylamide-co-acrylic acid) (PNA) is one of the
Accepted Manuscript
temperature responsive sol-gel transition polymers, which has a
sol-gel phase inflection point that is called the lower critical
solution temperature (LCST).[59] The stimuli property of such
polymer electrolytes was ascribed to the N-isopropylacrylamide
functional groups with hydrophilic -N(H)-C=O- amide groups and
hydrophobic -CH(CH3)2 (iPr) groups. By changing the ratio of the
hydrophilic/hydrophobic groups, the smart electrolytes could
achieve an excellent thermally stimuli response (Figure 6a). Thus,
the smart n/α-MnO2 battery with such electrolytes could be
triggered shutdown automatically at the gel state above the
LCST.[60] Furthermore, the electrochemical performances of the
devices could recover to the original state when cooling down,
demonstrating a good reversibility.
In addition, similar to the sol-gel transition mechanism as
mentioned above, an amphiphilic PEO-PPO-PEO (Pluronic)
hydrogel electrolyte was developed.[61] The Pluronic electrolyte is
another thermally stimuli responsive electrolyte with a sol-gel
transition temperature. At the room temperature, the electrolyte
is in a gel state, while it becomes to a flowable solution at the low
temperature about -5 °C.[62] Thus, by a cooling-recovery strategy,
the sol state electrolyte could in-situ re-wet the electrode surface
to alleviate the degradation of cycle performance of ZIBs (e.g.
Zn/LMO and Zn/LFP batteries) when they suffer from strong
bending (Figure 6b). Moreover, such ZIBs with Pluronic hydrogel
electrolytes exhibit superior electrochemical performances after
multiple folding/cooling recovery processes.
Although the hydrogel electrolyte exhibits flexibility, it can be
damaged and even broken under large deformation. To
overcome this issue, the development of functional electrolyte
with self-healing ability is also attractive. A PVA-based hydrogel
can autonomously self-heal due to the abundant hydrogen bonds
between hydroxyl side groups in chains. [63] With the introduction
of zinc salts into the PVA hydrogel matrix, the self-healing
electrolyte would be achieved via a freeze/thaw strategy. After
the freezing/thawing process, the crystallization of PVA is
enhanced. The resultant crystalline microdomains serve as
cross-links to achieve a porous network, which is beneficial to the
transportation of electrolyte ions. Furthermore, once the
PVA-based hydrogel electrolyte is damaged, the hydrogen bonds
will reestablish at the broken interface. The hydrogel electrolyte
recontacts subsequently and achieve the complete self-healing
without external stimulus (Figure 6c). Thus, the PVA-based
hydrogel electrolyte exhibits an excellent ionic conductivity even
after several cutting/self-healing cycles. Through the design of
integrated structure, an all-in-one self-healing ZIB was fabricated.
The self-healing ZIB delivered a stable electrochemical
Chemistry - A European Journal 10.1002/chem.201902660

MINIREVIEW

Accepted Manuscript
Figure 6. a) Schematic illustrating of the reversible sol-gel transition of PNA polymer. Reproduced with permission.[60] Copyright 2018 Elsevier. b) Schematic of the
cooling-recovery function by Pluronic electrolyte. Reproduced with permission.[62] Copyright 2017 Wiley-VCH. c) The self-healing behavior of the PVA-based
hydrogel electrolyte with and without rhodamine B for coloration. Reproduced with permission.[63] Copyright 2019 Wiley-VCH. d) Optical images showing that the
chemical cross-linked PAM hydrogel with good stretchability (3000% strain). Reproduced with permission.[47a] Copyright 2018 American Chemical Society. Elastic
stability of NFC/PAM hydrogel (AF-gel) at -20 °C under different states: (e) twist, (f) bent, and (g) compressed. Reproduced with permission.[64] Copyright 2019
Royal Society of Chemistry.

performance and it could recover the specific capacity
completely even after several cutting/healing. The self-healing
electrolyte provides a promising way for improving the durability
and extending the lifetime of electrochemical energy storage
devices.
Elastic electronics have the ability to endure large strain
without remarkable loss in their electronic performance and
reliability. In order to power these electronics and achieve a
self-powered strain-tolerant system, stretchable or compressible
energy storage devices should be considered.[65] Therefore,
elastic functional hydrogels that possess a good toughness for
the mechanical strain without the degradation of electrochemical
performances are desired. Recently, highly elastic PAM hydrogel
electrolyte was developed. Its excellent compressibility originates
from elastomeric polymer chains at the molecular level due to the
strong covalent bonds and the weak ionic bonds or hydrogen
bonds. Based on this hydrogel electrolyte, compressible ZIBs
were assembled.[47c] The ZIBs exhibit stable electrochemical
performances under large compressional strain without
sacrificing the original capacity. Similarly, stretchable electrolytes
are also prepared by PAM-based hydrogel (Figure 6d). As
mentioned in the section of hydrogel electrolyte with chemical
cross-linking, the PAM-based electrolytes exhibit the excellent
mechanical tolerance, which is successful to apply in high flexible
ZIBs.[47a, 47b]
In addition to the utilization of hydrogel electrolyte at normal
temperature, it is also necessary to consider its use in an
extreme environment such as subzero temperature. Recently, to
improve the adaptive ability of hydrogel electrolyte at subzero,
dual cross-linked hydrogel electrolytes were achieved. The
resulting electrolyte exhibits a freeze-tolerance below -20 °C,
which consisted of EG-based waterborne anionic polyurethane
acrylates (EG-waPUA) and PAM matrix (Figure 6e-g).[64] The
mechanism of anti-freezing is contributed to the low ethylene
glycol (EG) molecule, which is usually treated as an engine
coolant. Such small EG molecules could strongly interact with
water molecules by the formation of hydrogen bonds, resulting in
a decrease of the saturated vapor pressure of the water.
Therefore, the freezing point of the hydrogel is decreased. Thus,
the assembled Zn/MnO2 batteries based on such hydrogel
electrolyte demonstrated grateful electrochemical performances
at -20 °C. Furthermore, the ZIBs show an outstanding
anti-freezing stability, even after multiple cycles of
cooling/heating process without significant capacity degradation.

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Chemistry - A European Journal
MINIREVIEW
6. Summary and Outlook
This minireview presents the recent developments of electrolytes
in aqueous ZIBs, including liquid, gel, and multifunctional
hydrogel electrolytes. The advances in liquid electrolytes mainly
include the selection of zinc salts, concentration of zinc salts and
additives. Early attempts are in alkaline electrolyte. However, the
practical applications of alkaline Zn-based batteries are usually
hindered by the low Coulombic efficiency. Compared with
alkaline aqueous electrolytes, a neutral or mildly acidic aqueous
electrolyte endows the ZIBs with high electrochemical
performance, but the continuous corrosions of Zn anode and
current collector in acidic electrolyte lead to the low cycle
performance. To enhance their electrochemical performances,
functional additives were introduced into the electrolytes. The
resultant composite electrolytes exhibit a relatively high ionic
conductivity, good compatibility with the Zn anode and the
cathode. In addition, gel electrolytes with polymers or inorganic
components were attracted more attentions. Typical gel
electrolytes include the case without cross-linking and hydrogel
electrolytes with physical and/or chemical cross-linking. The
closely linked structure and the excellent mechanical properties
are beneficial to extend their applications in aqueous ZIBs.
Furthermore, multifunctional hydrogel electrolytes are designed
by introducing various functional groups of polymer chains to
meet the demand of smart electronics.
Although great progresses have been achieved in the
selection and optimization of electrolytes, there are still many
bottlenecks and urgent needs for future advancement in aqueous
electrolytes. For instance, there is still a great amount of the free
water in most of aqueous electrolytes, even the hydrogel
electrolytes. A great amount of free water could continuously
attack the Zn anode to produce H2, resulting in a poor
compatibility. Thus, the compatibility of the electrolyte with Zn
anode has to be further considered to improve its cycle and
coulombic efficiency performance. Some novel electrolytes, such
as zinc molten hydrate or all-solid-state zinc-based electrolyte,
would be promising strategies to improve the compatibility of the
electrolyte with Zn anode. The H2O molecules in these
electrolytes are trapped into the Zn2+ hydration shells, leading to
limited side reactions. In addition, as mentioned above, the
ESPW of conventional electrolytes is low, usually less than 2.4 V.
Although water-in-salt electrolytes could improve the ESPW to
some extent, the potential window of ~2.6 V is still insufficient
compared with traditional organic electrolytes, especially for
high-voltage aqueous ZIBs. Thus, more strategies on the
optimization of the electrolyte have to be developed to increase
the ESPW. For instance, functional redox-active additives could
be introduced into the electrolytes since they could inhibit the
decomposition of electrolyte. Apart from enhancing the ESPW,
the addition of ion additives will also greatly improve the cycle
performance of ZIBs to a large extent. Therefore, the selection,
dosage, distribution of the ion additives in liquid electrolytes
should be optimized to improve the electrochemical performance
of aqueous ZIBs.
In addition, although progresses have been achieved in gel
electrolytes, much work still remains to be done. The ionic
conductivity of gel electrolyte is still relatively lower compared
with the case of liquid electrolyte, leading to a low rate
This article is protected by copyright. All rights reserved.
10.1002/chem.201902660
performance and an unsatisfied power density. Besides ionic
conductivity, high mechanical tolerance is also desired for gel
electrolytes. However, the improvement of mechanical properties
of gel electrolyte often sacrifices their ionic conductivity since the
polymer network frame structure will be reinforced. In addition,
similar with conventional liquid electrolytes, gel electrolytes are
also not able to be feasible at high operating voltage. Therefore,
the gel electrolytes with excellent ionic conductivity, enhanced
mechanical properties and high operating voltage have to
developed by selecting novel polymer matrix and suitable zinc
salts. Furthermore, smart functions of gel electrolytes are limited.
As a result, hydrogel electrolytes with various smart features
could be further designed by introducing various functional
Accepted Manuscript
groups of polymer chains.
Acknowledgements
This work was supported by National Natural Science
Foundation of China (51822205, 21573116, and 21875121),
Ministry of Science and Technology of China (2017YFA0206701),
Ministry of Education of China (B12015).
Conflict of interest
The authors declare no conflict of interest.
Keywords: electrolytes • zinc-ion batteries • gel • hydrogels •
additives
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Chemistry - A European Journal 10.1002/chem.201902660

MINIREVIEW
MINIREVIEW
† †
Electrolyte plays a vital role in the Shuo Huang, Jiacai Zhu, Jinlei Tian
electrochemical properties of zinc-ion and Zhiqiang Niu*
batteries (ZIBs). This minireview
focuses on the electrochemical Page No. – Page No.
principles of the aqueous ZIBs and
Recent Progress in the Electrolytes
the recent advances of various
of Aqueous Zinc-Ion Batteries
aqueous electrolytes for ZIBs,
including liquid, gel, and
multifunctional hydrogel electrolytes.
In addition, this minireview also
discusses the remaining challenges
and future directions of electrolytes in

Accepted Manuscript
aqueous ZIBs.

This article is protected by copyright. All rights reserved.