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org/acsaelm Review

Recent Progress on the Performance of Zn-Ion Battery Using Various

Electrolyte Salt and Solvent Concentrations
Prakas Samanta, Souvik Ghosh, Aniruddha Kundu, Pranab Samanta, Naresh Chandra Murmu,
and Tapas Kuila*

Cite This: ACS Appl. Electron. Mater. 2023, 5, 100−116 Read Online

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ABSTRACT: Rechargeable aqueous Zn-ion batteries (ZiBs) have attracted extensive

Downloaded via PRAKAS SAMANTA on February 23, 2023 at 05:24:47 (UTC).

attention in the field of large-scale electrical grid energy storage owing to their high level
of safety, high volumetric energy density, and low cost. The usage of water as solvent
facilitates the intrinsic properties. However, the battery performance is impeded by the
narrow electrochemical stability window of the aqueous electrolyte, sluggish Zn2+-ion kinetics
association with free water molecules, and undesired side reaction with cathode and anode
materials. The viability of practical ZiBs largely depends on suitable electrolyte formulation.
This review aims to provide a comprehensive understanding on the electrolyte formulation in
association with basic characteristics, electrode/electrolyte interface mechanics, and their
optimization strategies. The choice of suitable electrolyte salt, solvent, and other parameters
related to the electrolyte along with their electrochemical performances are discussed. Finally,
advanced strategies to modulate the suitable electrolyte and future perspectives are discussed
to mitigate the issues for advanced ZiBs development.
KEYWORDS: electrolyte engineering, Zn-ion battery, electrode/electrolyte interface, electrochemical stability window,
solid electrolyte interphase

1. INTRODUCTION the Zn dendrite formation and corrosion of the Zn anode in

Severe environmental pollution and a continuous increase in
the average temperature of the atmosphere have promoted the
transition from fossil fuels to renewable energy sources such as
geothermal, wind, and solar energy. However, these renewable
energy sources are irregular in nature. Rechargeable batteries
are considered as the most promising energy storage device for
portable electronic applications.1,2 The most studied energy
storage systems have been Li-ion batteries since the 1990s due
to their high energy output, and they are dominating the
energy sector from portable electronics to electric vehicles.
Nevertheless, their high cost and safety issues have limited
their practical applications in daily life.3,4 In these regards,
rechargeable Zn-ion batteries (ZiBs) are considered as the
most promising energy storage devices due to their low redox
potential (−0.763 V vs standard hydrogen electrode (SHE)),
high gravimetric and volumetric capacities (820 mAh g−1 and
5855 mAh cm−3), the compatibility of Zn metal with water
leading to high safety and environmental friendliness, the
abundance of Zn on earth, and the facile device assembly
process.3−6 Nowadays extensive efforts have been made on
ZiBs for commercialization. However, ZiBs still face several
challenges such as low electrochemical stability window
(ESW), low stability, capacity fading, etc. that hinder practical
applications.6−8 The irreversible Zn plating/striping caused by
aqueous electrolyte affects ZiB performance.6−8
The electrolyte plays an important role in determining the
electrochemical performance of ZiBs, since the electrolyte
provides the Zn2+ cation migration between the two electrodes
and determines the ESW, ionic conductivity, reversibility, and
charge storage mechanism of the device.9 Furthermore,
appropriate electrolyte selection is an important parameter
for the accurate evaluation of electrode performance. ZnSO4
and Zn(OTf)2 salt based electrolytes are commonly used in
ZiBs owing to their superior compatibility with electrode
materials.4,9,10 However, the rechargeable ZiB based on these
electrolytes still suffer from the poor cycling stability resulting
from the cathode dissolution and Zn dendrite formation owing
to the limited salt solubility in water.11,12 The free water
molecules in “salt-in-water” (SiW) electrolytes easily decom-
posed under applied potential, and water related undesired side
reactions occurred near the electrode surface. Therefore, more
attention should be paid to electrolyte engineering strategies to
Received: October 7, 2022
Accepted: December 4, 2022
Published: December 23, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acsaelm.2c01355

100 ACS Appl. Electron. Mater. 2023, 5, 100−116
ACS Applied Electronic Materials
achieve a high performance ZiB. Recently, most of the
electrolyte engineering strategies belong to the following two
aspects: (i) increasing the salt concentration and (ii)
introducing the functional additives.13,14 As a result, (i) the
cycling stability of the ZiB is enhanced significantly by
improving the Zn striping/plating efficiency and restricting
the cathode dissolution into the electrolytes; (ii) a high ESW is
created by reducing the free water molecules from the primary
solvation sheath; (iii) superior specific capacity and energy
density of the ZiB are found; (iv) and the undesired water
related side reaction and byproduct generation are minimized
(Figure 1).13−15
Figure 1. Overview of various electrolyte engineering strategies for
aqueous ZiB.
Unlike other reviews, this article provides a comprehensive
overview on the ZiB performance using various electrolyte salts
and solvent concentrations. Herein, comprehensive discussions
on the cathode/electrolyte interface and anode/electrolyte
interface in aqueous electrolyte are included. The undesired
side reaction takes place in aqueous rechargeable ZiBs as
discussed thoroughly including their electrochemical perform-
ance. Different electrolyte engineering strategies are discussed
for better insight. The basic characteristics of the electrolyte
were taken into consideration which influenced the ZiB
performance. Finally, the salt and solvent dependency on ZiB
performance are summarized and future scopes are proposed.
2. BASIC CHARACTERISTICS OF ELECTROLYTE
The electrolyte acts as an ionic conductor in an electro-
chemical cell in which the electrolyte provides ionic current to
support the cell reaction and significantly influences the
electrochemical performance. Therefore, the basic character-
istics of the electrolyte include ionic conductivity, ion
transference number, ESW, etc. and are highly desired to be
explored simultaneously with their difficulties to optimize the
strategies to achieve high performance ZiBs.
2.1. Ionic Conductivity. The ionic conductivity of an
electrolyte highly influences the electrochemical performance
of ZiBs.16 The ionic conductivity of the electrolyte can be
expressed with the help of the Arrhenius equation and Vogel−
Tammann−Fulcher theory which are generally applicable for
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solid-state ZiBs.17 However, the widely used ionic conductivity
calculation is as follows: σ = L/RA, where R represents the
resistance, which is obtained from the AC impedance
spectroscopy in ohms, A is the active area and L is the
thickness.18 Generally, the aqueous electrolytes possess higher
ionic conductivity compared to the ionic liquid and organic
electrolytes due to the low viscosity of water.18 Generally, the
ionic conductivity of an electrolyte can be expressed as σ =
c(ν+λ0+ + ν―λ0―), Where c is the electrolyte concentration,
ν+ and ν― represent the mole number of cations and anions
that dissociate in 1 mol of electrolyte, and λ0+ and λ0―
demonstrate the cation and anion limiting molar conductivity,
respectively.19 Several Zn salts are employed as Zn-ion
electrolytes for fabricating ZiBs. Among these Zn salts,
ZnSO4, Zn(OTf)2 and Zn(TFSI)2 salt based electrolytes are
widely used owing to their good compatibility with water, wide
potential anion stability, suitable ionic conductivity, etc.16
However, the ionic conductivity of the electrolyte varies with
salt concentration and additive salt/solvent. For example,
ZnSO4 electrolyte exhibits 13.31 and 25.74 mS cm―1 ionic
conductivity at low and high salt concentration.20 Another
report stated that the ionic conductivity is enhanced from 4 to
6 S cm―1 by introducing Mn2+ salt additive into ZnSO4
based electrolyte.21 Importantly, the OTf― based electrolytes
displayed higher ionic conductivity (4 S cm―1) compared to
the ZnSO4 based electrolyte. Further, the Mn(OTf)2 additive
into the Zn(OTf)2 electrolyte increased the ionic conductivity
to a large extent (6 S cm―1).21 This is due to the fact that the
number of conductive ions increased in the electrolyte. As
discussed earlier, the ionic conductivity of electrolyte is
influenced not only by the solubility but also by the types of
anions and cations. The number of cations anions is enhanced
in the electrolyte with increasing the salt concentration.21 In
addition, the ion transference number, viscosity and solvation
effect greatly influenced the ionic conductivity of the
electrolyte, which were governed by the salt concentration
and solvent. For example, the electrolyte viscosity and ionic
conductivity were reduced with increasing the Zn(OTf)2 salt
concentration.19 Therefore, the effect of the salt concentration
on viscosity should not be ignored. Furthermore, the cation
solvation effect greatly tailored the ionic conductivity of the
electrolyte. The ionic conductivity increased with decreasing
the interaction among the cations and anions.22 The ionic
conductivity also increased with the deterioration of the
desolvation energy. The hexacoordinated ion solvation sphere
is observed with low desolvation energy in dilute Zn(TFSI)2
electrolyte, while the Zn(TFSI)3 solvation sphere is formed in
highly concentrated “water-in-salt” (WiS) 1 M Zn(TFSI)2 + 20
M LiTFSI mixed electrolyte.23 Therefore, it is necessary to
explore the ionic conductivity and solvation effect relationship
to achieve the superior electrochemical performance of ZiBs.
2.2. Ion Transference Number. A good ZiB electrolyte
should have high transference number which effectively
suppresses the concentration polarization and minimizes the
zinc dendritic growth.24 The applied electric field will tailor the
ion transference number of the electrolyte cations and anions
during the charge/discharge (GCD) process. The individual
cation (tc) and anion (ta) migration into the electrolyte can be
determined by employing the following equation: tc = μ+/(μ+
+ μ−) where μ+ and μ− are the current carried by cations and
anions, respectively.25 The high charge transfer efficiency of
the electrolyte possesses the unit cation and anion transference
numbers.25 A hexacoordinated Zn2+-ion solvation sphere by
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Figure 2. (a) Positive and negative potential stabilities of electrolytes and their HOMO, LUMO energy levels. (b) ESW of the bisalt and monosalt
electrolytes at 10 mV S−1 scan rate, with the enlarged regions near the anodic and cathodic extremes of the electrochemical windows. Adapted with
permission from ref 34. Copyright 2020 American Chemical Society.
water molecules is formed in conventional ZnSO4 electrolyte
where anions are hardly solvated by water molecules and limits
the Zn2+-ion migration.10,12,16 The anion accumulation on the
cathode surface is observed and creates a concentration
gradient which causes concentration polarization. As a result, a
limited ESW, cathode dissolution into the electrolyte, and a
low energy and power density are obtained.26 It is possible to
get a higher Zn2+-ion transference number by reducing the
coordination number to some large extent. For example, the
highly concentrated LiTFSI salt provides a 0.7 Li+-ion
transference number.26 The unique solvation structure in a
highly concentrated electrolyte restricted the anionic move-
ment while the cations are less affected.26 The femtosecond
Raman spectroscopy of ZnCl2 demonstrated that the Zn2+-ion
solvation structure transformed to tetrahedral [ZnCl4]2−
coordination structure from octahedral [Zn(OH2)2Cl4]2 with
increasing salt concentration from 5 to 30 M ZnCl 2
electrolyte.27 As a result, 30 M ZnCl2 electrolyte exhibited
higher ion transference number compared to 5 M ZnCl2
electrolyte.27 The polymer gel electrolyte exhibited lower
Zn2+-ion transference number compared to anion transference
number. This is due to the fact that the Zn2+ ions strongly
interacted with Lewis basic polar groups of polymers.28 In this
regard, the zwitterionic polymer network provides higher Zn2+-
ion transference number leading to the smooth Zn deposition/
dissolution and restricts Zn dendrite growth.29 However, there
are only a few reports to improve the Zn2+-ion transference
number of electrolytes.26−29
2.3. Electrochemical Stability Window. The ESW of the
electrolytes between cathode and anode determines the voltage
window of the ZiB. The highest occupied molecular orbital
(HOMO) and lowest unoccupied molecular orbital (LUMO)
theory derived from the electronic structure of isolated
molecules and their energy levels were widely used to explain
the ESW of electrolytes in batteries.10 It is well-known that the
thermodynamic ESW of water is ∼1.23 V due to the hydrogen
evolution at −4.02 eV and oxygen evolution at −5.25 eV at
neutral pH and standard band gap of ∼8.7 eV. On the
contrary, the organic solvent exhibits higher ESW due to the
higher HOMO and LUMO energy gap. For example, the
HOMO and LUMO energy gaps for ethylene carbonate and
dimethylcarbonate are −7.87 eV and −7.07 eV, respectively.24
The thermodynamic ESW of the electrolyte can be determined
by differentiating the oxidation and reduction potential
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energies.30 The electrons in the electrolyte are captured by
the cathode material when the HOMO energy level of the
electrolyte is higher than that of the cathode material. Thus,
the cathode materials were oxidized by electrolyte and
polarized at lower electrochemical potential.31 Similarly, the
electrons in the anode material were captured by the
electrolyte when the anode electrochemical potential was
higher than that of the LUMO of the electrolyte (Figure 2a).31
Therefore, the electrolyte was reduced under applied potential
and the reaction product resulted to form a solid electrolyte
interphase (SEI) on the electrode surface. The ESW of the ZiB
was largely dependent on the salt concentration and solvents.
It is well-known that the ESW of the nonaqueous electrolyte
was higher compared to that of the aqueous electrolyte.
However, there are several drawbacks of nonaqueous ZiBs.
The highly soluble ZnCl2 electrolyte based ZiB exhibits poor
electrochemical performance due to the narrow anodic
potential and Cl―-ion instability. On the contrary, the
NO3― ion in Zn(NO3)2 salt is a strong oxidizing agent which
leads to cathode and anode corrosion.30,31 The ZnSO4,
Zn(OTf)2 and Zn(TFSI)2 aqueous electrolytes are the most
stable aqueous electrolytes for ZiBs.31,32 In addition, some
functional asymmetric additives in aqueous electrolyte
enhanced the ESW of ZiBs by forming an SEI on the electrode
surface.34,35 The WiS electrolyte enhanced the hydrogen
evolution reaction (HER) and oxygen evolution reaction
(OER) overpotential to a larger extent in aqueous electrolyte
(Figure 2b).36−40 With increasing the salt concentration, the
availability of free water molecules is reduced in the primary
solvation sheath. This is due to the fact that the bulky anion
groups of Zn(OTf)2 and Zn(TFSI)2 salts are accumulated at
the electrode interface forming a hydrophobic layer on the
electrode surface that prevented electrode/water direct
contact. Furthermore, the reductive decomposition of bulky
anions results in the generation of an SEI on the electrode
surface which delayed the HER and OER.41 In addition, the
fluorine rich SEI acted as an electron barrier that prevented
further electrolyte reduction at high ESW. Controlling the pH
of the electrolyte favors the ESW of the ZiB as the HER and
OER overpotential is higher for alkaline and acidic electro-
lytes.42
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3. ELECTRODE/ELECTROLYTE INTERFACE
Electrochemical energy storage devices store charge through
an electron transfer process accompanied by ion transfer at the
electrode/electrolyte interface.43,44 The electrode/electrolyte
interface of any energy storage device strongly depends on the
electrolyte environment, which plays a crucial role in
determining the electrochemical performance of the de-
vice.43,44 Therefore, a systematic understanding of the
electrode/electrolyte interface and electrolyte is of great
significance. This section evaluates some important elec-
trode/electrolyte interface properties and discusses their
correspondence with related strategies (Figure 3).
Figure 3. Systematic illustration of the electrode/electrolyte interface
interaction.
3.1. Interfacial Characteristics. The interfacial fluidity
and compatibility of the liquid electrolyte with the electrode
exhibit excellent physical contact. The compact electrode−
electrolyte contact ensures high ionic and electrical con-
ductivity of the ZiB, leading to the long-term cyclic
stability.11,33 However, such good contact may be loosed in
the case of gel and solid electrolytes. On the contrary, the gel
electrolyte exhibited high flexibility ensuring good physical
contact at the electrode/electrolyte interface.33 Therefore,
development of all-solid-state ZiBs is a big challenge in the
recent scenario of energy research. Point-to-point contacts are
essentially sensitive to the formation and propagation of cracks
which lead to damage of ZiBs.45 It has been reported that the
choice of an appropriate electrolyte can regulate the electrode/
Figure 4. Thermodynamic working window of ZiB chemistry regarding the pH value. Overlay of Pourbaix diagrams and zoom and pH-potential
plot of the cell cycling path of the battery cell with the standard electrolyte composition. Adapted with the permission from ref 48. Copyright 2020
The Electrochemical Society.
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electrolyte interfacial chemistry of ZiBs.11,32,45 In conventional
alkaline electrolyte, the OH− ions will attack the Zn anode
causing dendrite growth on the anode surface. On the contrary,
a mild acidic electrolyte (ZnSO4, Zn(OTf)2) does not favor
dendrite formation.46 However, a supersoluble Zn salt results
in low ionic conductivity and restricts the electrochemical
performance. In contrast, the polymer gel electrolytes display
superior electrochemical performance due to the presence of
trapped water molecules in the polymer framework.47,48
Moreover, Zn anode corrosion and cathode dissolution into
the electrolyte will also result in poor interfacial characteristics.
Therefore, proper interfacial characteristics study with
appropriate modification including electrode and electrolyte
optimization is the convenient solution for developing the next
generation ZiBs.
3.2. Cathode/Electrolyte Interface. The OER is
observed at the cathode surface as the voltage increases to
more positive values during the charging process (6H2O → O2
+ 4H3O+ + 4e−; Eo = +1.23 V vs SHE).48 The transition metal
oxides reached the borderline condition where the OER starts
to become thermodynamically favorable. Therefore, the OER
under applied current can lead to battery damage.48 In
addition, the cathode dissolution into the electrolyte leads to a
capacity fading during operation. In mild acidic electrolyte,
cathode materials were unstable during the GCD process.
Moreover, cathode dissolution was observed when the battery
was overcharged to a very high potential (Figure 4).48 In
addition, the phase transformation of the parent cathode
material to a new phase results in poor cycling stability.49 For
example, proton insertion into the cathode material leads to
the formation of a new phase which contributes additional
capacity to the device. Proton insertion into the cathode host
elevates the local pH to the more basic pH of the electrolyte.50
As a result, the Zn salt is participating in the formation of
byproduct on the cathode surface. Therefore, the reversible
cation insertion/extraction is affected, resulting in poor cycling
stability. The byproduct formation on the cathode surface
leads to several issues including salt concentration loss, water
solvent loss leading to water crystallization and device damage,
increased charge transfer resistance of the device, etc.50
Substantial efforts are required to understand the mechanism
of byproduct formation and its effects on electrochemical
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Figure 5. (a) Energy barrier of the zinc nucleation process. (b) Typical voltage profile during zinc deposition. Adapted with permission from ref 61.
Copyright 2017 American Chemical Society. (c) Simulation of the ion distribution on the anode surface under different conditions. Adapted with
the permission from ref 64. Copyright 2019 Wiley-VCH.
performance. The electrolyte engineering and surface coating
will be the effective ways for preventing the byproduct
formation.
All types of cathode materials undergo dissolution in
aqueous electrolytes during the GCD process and device
fabrication.48,51,52 Dissolution of the cathode is mainly
attributed to the three following factors: (i) the cathode
materials became unstable under applied potential in aqueous
electrolyte;51 (ii) the battery became overcharged at higher
potential;48 and (iii) the cathode materials were chemically
unstable.52 Aqueous solvent interacts with the cathode material
under applied potential, resulting in undesired side reaction
and cathode dissolution into the electrolyte.51 For the Zn//
MnO2 device, the cathode dissolution undergoes a >1.7 V
potential window. At higher potential window, the OER
process takes place and the local pH at the cathode/electrolyte
vicinity was more acidic.48 Furthermore, the cathode materials
were dissolved in aqueous electrolyte when they came in
contact with the aqueous electrolyte before device fabrica-
tion.52
3.3. Anode/Electrolyte Interface. There are some
unexpected reactions that occur at the anode/electrolyte
interface during the battery operation triggering some severe
issues such as Zn corrosion, dendrite formation, passivation,
HER, etc. The Zn anode exhibits different behaviors on
electrolyte pH regulation.50,53 Most of the electrolytes used for
ZiBs are mild acidic electrolytes with pH values lying in
between 3−7.50,53 Generally, the SiW electrolytes demonstrate
as hydrated [Zn(H2O)6]2+ cation spheres. The central Zn2+
cations acted as a Lewis acid to hydrolyze the coordinated
water molecules for the generation of H+ ions.50,54 According
to the Pourbaix diagram, the Zn metal anodes are
thermodynamically unstable in these mild acidic electro-
lytes50,53 (Figure 4). The Zn metal will be oxidized to Zn2+
ion in mild acidic electrolyte, and H+ ion will be reduced to H2
via the HER. The redox processes occurring in mild acidic
electrolyte result in corrosion of the Zn metal. It has been
observed that the Zn metal is corroded in ZnSO4 aqueous
electrolyte.55 However, there is no corrosion in mild acidic
electrolyte due to the high corrosion reaction overpotential of
Zn metal.50,54,55 Moreover, the HER process is accelerated
under applied potential during the Zn deposition process. The
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continuous evolution of H2 gas via the HER process leads to
ZiB damage.54 In addition, the local electrolyte pH is increased
by the continuous evolution of H2 gas near the Zn anode
surface resulting in the precipitation of byproducts such as
Zn4SO4(OH)6·xH2O and Zn4ClO4(OH)7 in aqueous ZnSO4
and ZnClO4 electrolytes, respectively.55,56 The Zn2+-ion
transfer rate decreased at the anode/electrolyte interface due
to the formation of byproducts.55−57
The Zn2+-ion deposition on the Zn anode surface during
operation is driven by two factors: namely, Zn nucleation and
growth.58 The Zn nucleation and growth are mainly driven by
the electric field.59 The nucleation energy exists for the
formation of a new solid phase by the Zn reduction reaction
(Figure 5a). After the initial reduction, Zn continued to be
plated on the initially deposited Zn layer.60,61 On the contrary,
the diffusion-controlled Zn growth is influenced by the
electrolyte concentration and applied electric field. The Zn
cluster is generated on the Zn anode surface during Zn
nucleation, and Zn atoms are deposited on the existing Zn
cluster in the growth process.61 During the nucleation process,
the minimum size of the Zn nuclei should be rcrit = 2γVm/Fηn
for a stable Zn nucleus to form on the Zn anode surface, where
γ is the Zn anode/electrolyte interface energy, ηn is the
nucleation overpotential, and Vm is the molar volume of Zn,
respectively.61 A smaller rcrit during the nucleation process
implied a uniform Zn deposition where the Zn cluster is stable,
and a larger rcrit demonstrated nonuniform Zn deposition for
an unstable big Zn cluster.61 The Zn deposition quality can be
judged by determining the nucleation overpotential and
plateau overpotential. The nucleation overpotential is defined
as the tip potential and subsequent stable potential difference.
On the contrary, the plateau overpotential is the Zn growth
after initial nucleation (Figure 5b).61 Uniform Zn deposition
can be obtained by lowering the plateau overpotential and
nucleation overpotential. Moreover, a controlled electric field
at the anode/electrolyte interface results in uniform Zn
deposition.62 The finite-difference simulation demonstrated
that the Zn growth after initial nucleation is strongly influenced
by the ion distribution and electric field. The electrons and
ions are accumulated at the initially generated Zn tip seeds and
accelerate the Zn growth (Figure 5c).63,64 However, the
difference in ion distribution is not obvious at the anode/
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Figure 6. (a) Electrochemical performance of Ca0.20V2O5·0.80H2O as an ZiB cathode. GCD potential profiles at 50 mA g−1 in three-electrode cells,
wherein zinc foil and Ag/AgCl serve as the counter electrode and reference electrode. (b) CV curves from the fifth cycle with a scan rate of 0.5 mV
s−1. Adapted with the permission from ref 69. Copyright 2019 Wiley-VCH, (c) Comparison of the CV curves of the Fc/C anode and the
Zn3[Fe(CN)6]2 cathode in ZnCl2 electrolytes. (d) Voltage changes of full cells of rocking chair batteries, a dual-ion battery, and a reversible dual-
ion battery in ZnCl2 electrolytes. Adapted with the permission from ref 75. Copyright 2019 American Chemical Society.

electrolyte interface, but a controlled current density 4. ELECTROLYTE ENGINEERING STRATEGIES TO

distribution is more important for uniform Zn deposition.
Under low applied current density, Zn deposition occurred in a
controlled way. On the contrary, ion transfer is restricted and
Zn deposition preferentially occurred at Zn tip seeds at high
applied current density.60,61 Similarly, uncontrolled Zn
deposition was observed for the high capacity of the Zn
anode. Therefore, Zn deposition is more uniform under low
capacity and current density.63,64 However, the design of the
Zn anode should meet the requirement of both high current
and high capacity.
Uniform Zn deposition can be maintained by tailoring the
electrolyte salt concentration at the anode/electrolyte inter-
face. For example, Na2SO4 additive into the ZnSO4 electrolyte
reduces Zn dendrite growth by forming a protecting layer on
the Zn surface.65 Similarly, LiTFSI additive in Zn(TFSI)2
electrolyte suppressed undesired side reaction of Zn anode
with the electrolyte due to the unavailability of free water
molecules.66 Moreover, the reductive decomposition of TFSI
anion under applied potential results in SEI formation on the
Zn anode surface and prevents direct contact of the anode with
water molecules.66 Moreover, organic additive in the aqueous
solvent may guide growth along a specific crystal orientation by
altering the surface energy. Diethyl ether additive in Zn(OTf)2
+ Mn(OTf)2 mixed electrolyte selectively absorbed on the Zn
tips and served as an electrostatic shield layer to impede
subsequent Zn deposition on the tips.67
105
MITIGATE UNDESIRED SIDE REACTION IN ZIB
Aqueous solvent directly or indirectly influences the overall
ZiB performance due to the undesired side reactions such as
cathode dissolution, OER, HER, byproduct generation on the
electrode surface, Zn anode corrosion, etc. The solubilities of
most of the Zn salts are ∼4 M in water, indicating the presence
of free water molecules.50 The literature survey suggested that
the water related undesired side reactions can be minimized by
reducing the free water availability in the primary solvation
sheath and reducing the electrode-water direct interaction.
Hereafter, the various electrolyte engineering strategies are
discussed to mitigate the issues of ZiBs.
4.1. Aqueous Electrolyte Engineering. 4.1.1. Symmetric
Electrolyte. Significant efforts have been made on ZiB
electrolyte modulation for extending the ESW and minimizing
the water related side reaction. In particular, the WiS
electrolyte usage for ZiBs where the mass and volume of
salts are higher than those of water have shown extraordinary
properties. For example, the open framework NH4+-ion
intercalated vanadium pentoxide ((NH4)xV2O5·nH2O) cath-
ode displays the high capacity of 372 mAh g−1 with 273 Wh
kg−1 energy density in 3 M Zn(OTf)2 WiS electrolyte.68 On
the contrary, other conventional electrolytes such as 1 M
Zn(OTf)2, 1 M ZnSO4, 1 M Zn(OAc)2, and 1 M Zn(NO3)2
exhibited 224, 158, 108, and 92 mAh g−1 discharge capacities
at 0.2 A g−1 current density, respectively. The high salt
concentration reduced the presence of free water molecules in
the solvation sheath, leading to the enhanced capacity of the
ZiBs. Furthermore, the WiS electrolyte exhibited higher Zn2+-
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ion transference number than conventionally used electrolyte,
demonstrating highly reversible insertion/extraction of Zn2+
ion into/from the cathode.68 The Zn2+ ion owns a large
electric field and generates strong electrostatic interaction with
the water molecules through H-bonding due to the multiple
valence charge and small radius. The hydrogen-bonds increase
the salt concentration and exhibit a moderate reduction of
water related side reactions.69 For example, ∼7.5 M ZnCl2
electrolyte generated Zn(H2O)2Cl42−, ZnCl+ and Zn(H2O)62+
in bulk electrolyte while ZnCl42− and Zn−Cl polynuclear
aggregates were observed in 30 M ZnCl2 WiS electrolyte.69
The capacity fading of the Ca0.2V2O5·0.8H2O cathode material
is restricted to a large extent by employing 30 M ZnCl2 WiS
electrolyte. The ionic conductivities of 1 and 30 M electrolytes
are found to be 101 and 12.7 mS cm−1, respectively. The
capacity and working potential window of the Zn//Ca0.2V2O5·
0.8H2O ZiB device are increased from 296 to 496 mAh g−1 and
0.45 to 1.2 V (vs Ag/AgCl) upon increasing the salt
concentration from 1 to 30 M (Figure 6a−b).69 The higher
capacity and cutoff potential are observed in WiS electrolyte
due to the raised onset OER potential. The cathode redox
peaks shifted to a positive potential by 0.4 V in 30 M WiS
electrolyte because of the ion activity change in WiS electrolyte
according to the Nernst equation.69 In addition, the capacity
retention increased from 8.4 to 51.1% after 100 cycles at the
low current density of 50 mA g−1 using WiS electrolyte. The
Zn//Ca0.2V2O5·0.8H2O ZiB device exhibited ∼70% capacity
retention with ∼99.6% Coulombic efficiency after 1000
cycles. 69 Ex-situ XRD revealed that a new phase of
Zn3(OH)2V2O7·2H2O was generated in dilute electrolyte
which was absent in WiS electrolyte, indicating the active
cathode material was dissolved in diluted electrolyte. A larger
time span is required to generate this new phase in dilute
electrolyte, leading to the capacity fading of the ZiB. On the
contrary, the Zn5(OH)8Cl2·H2O phase was formed in WiS
electrolyte and disappeared during the GCD process, resulting
in a high Coulombic efficiency of the ZiB. Such dissolution and
formation of a new phase in WiS electrolyte do not involve the
Ca0.2V2O5·0.8H2O cathode, which is not pertinent to the
capacity fading.70 Similarly, N-doped microcrystalline graphene
like carbon based ZiB exhibited ∼134 mAh g−1 capacity and
1.9 V ESW using 30 M ZnCl2 WiS electrolyte.71 Irreversible
oxidation/reduction was observed using 10 M ZnCl2 electro-
lyte due to the OER process. However, reversible (ZnClx)2−x
ion insertion/extraction is observed in 20 and 30 M ZnCl2 WiS
electrolyte, suggesting the water related side reaction is
restricted in WiS electrolyte. Ex-situ analysis suggested that
both the cation and anion reversibly took part in the charge
storage process and performed the role of a dual-ion battery.71
The Zn//MoO3 ZiB exhibited superior electrochemical
performance using 30 M ZnCl2 WiS electrolyte. Both the
cathode dissolution and dendrite formation were reduced
while using WiS electrolyte by forming a Zn5(OH)8Cl2·H2O
phase SEI on the electrode surface.72 The HER and OER
overpotential were enhanced using WiS electrolyte due to the
low water content. The H+- and Zn2+-ion co-insertion
mechanism into the MoO3 cathode was observed during the
GCD process.72 Similarly, the V2O5 cathode phase transition
and swelling in diluted 1 M ZnSO4 electrolyte were restricted
using 30 M ZnCl2 WiS electrolyte. In WiS electrolyte all the
water molecules were strongly coordinated with the Zn2+ ion
and stabilize the interfacial electrochemistry of ZiBs.73 A few
free water molecules were present in WiS electrolyte to
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coordinate with the active material that inhibits the vanadium
dissolution into the electrolyte.73 The alter linking polypyrene
organic cathode with narrow band gap was shown to be an
excellent electrolyte anion host in 30 M ZnCl2 based WiS
electrolyte and delivered ∼180 mAh g−1 specific capacity.74
The polypyrene cathode got oxidized to form a positive radical
on the conjugated polymer by losing delocalized π-electrons,
and electrolyte Cl− ions were inserted. The Zn dual-ion battery
showed extremely high cycling stability as 38,000 cycles with
96.4% capacity retention and showed a low self-discharge rate
with ∼90% capacity retention after resting the device for 28
days.74 Similarly, the (Fc/C)//Zn3[Fe(CN)6]2 reverse dual-
ion battery exhibited superior electrochemical performance in
30 M ZnCl2 WiS electrolyte.75 Dual-ion batteries store charge
via inserting/extracting electrolyte cations and anions in their
respective cathode and anode (the cathode operates on anion
insertion and the anode relies on cation insertion). If this
phenomenon is switched by designing a cathode and anode for
accepting electrolyte cations and anions, the electrochemical
performance of the dual-ion battery can be enhanced. Herein,
the cations were inserted in the cathode and anions were
inserted in the anode during the charging process and acted as
a “reverse” dual-ion battery (the cathode takes in cations and
the anode hosts anions).75 The WiS electrolyte maximized the
cation insertion potential and minimized the anion insertion
potential, leading to the elevated ESW up to 0.35 V compared
to diluted electrolyte of the reverse dual-ion battery (Figure
6c).75 Importantly, the ESW of the reversible dual-ion battery
increased with increasing the electrolyte salt concentration,
whereas the reverse phenomenon was observed for the dual-
ion battery (Figure 6d).75 Furthermore, the WiS electrolyte
reduced the cathode dissolution tendency into the electrolyte,
resulting in high cycling stability.75
4.1.2. Asymmetric Additive Electrolyte. The intensive
growth of Zn dendrite during plating/striping is controlled
using ZnSO4 + MnSO4 mixed electrolyte which enhanced the
Coulombic efficiency and life cycles and reduced the cathode
dissolution into the electrolyte.76 For example, the MnO2
cathode exhibited a dissolution/deposition mechanism in
ZnSO4 + MnSO4 mixed electrolyte during the GCD process.
The dissolution/deposition mechanism can be expressed as77
Cathode reaction, First cycle:
3MnO2 + 6H 2O + 6e 3Mn 2 + + 12OH
E = 1.41 V (vs Zn 2 +/Zn) (discharging process)
3Mn 2 + + 12OH 6e
3 MnO2 + 6H 2O (charging process)
Subsequent cycles:
3 MnO2 + 6H 2O + 6e 3Mn 2 + + 12OH
Side reaction:
12OH + SO4 2 + 8Zn 2 + + 6H 2O
2Zn4(OH)6 SO4 ·4H 2O
Anode reaction:
3Zn 6e 3Zn 2 +
The MnO2 dissolution occurs due to the conversion of Mn4+
(s) to Mn2+ (l), and in an another reaction OH− ions react
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Figure 7. (a and b) Radial distribution functions (solid line), g(r), and the corresponding integrals of coordination number CN (dashed line), for
(a) Zn−OH and (b) Zn−OS with salt concentration from 1 M (black) to 4 M (red) at 300 K. Adapted with the permission from ref 76. Copyright
2020 American Chemical Society. (c) Wettability of the V2O3@C cathode with different electrolytes. Adapted with the permission from ref 80.
Copyright 2022 Wiley-VCH. (d) CV curves of Zn electrodes in different electrolytes. (e) First charge/discharge curves of Zn/VOPO4 batteries
based on different electrolytes. Adapted with the permission from ref 82. Copyright 2019 Wiley-VCH.

with ZnSO4 electrolyte to produce a 2Zn4(OH)6SO4·4H2O
new phase in the discharge process. The reverse phenomenon
is observed in the charging process. The reversible formation
and disappearance of the 2Zn 4(OH)6SO4·4H2O phase
enhances the local pH of the electrolyte.78 In addition, the
MnSO4 additive efficiently enhances the amount of reaction
leading to higher Coulombic efficiency and higher stability.77
Initially, the MnO2 cathode reacts with H2O molecule to
produce Mn2+ and OH− ions in the electrolyte. Immediately,
the ZnSO4 molecules reacted with OH− ions to generate
2Zn4(OH)6SO4·4H2O which will effectively consume H2O
molecules. A lack of active H2O molecules will suppress the
subsequent dissolution of the MnO2 cathode into the
electrolyte.77 The Zn//Cu symmetric device using concen-
trated 4.2 M ZnSO4 + 0.1 M MnSO4 mixed electrolyte
displayed ∼99.21% Coulombic efficiency retention after 1000
h at 0.2 mA cm−2 current density. On the contrary, the
frequently used dilute 2 M ZnSO4 + 0.1 M MnSO4 mixed
electrolyte failed to exhibit such a life cycle and Coulombic
efficiency. The concentrated electrolyte with a strong ion-pair
aggregate showed an electrostatic shielding effect and
enhanced cycling stability.76 At diluted mixed electrolyte, the
Zn2+ ion dominantly interacted with water molecules in the
first solvation sheath, while the water dominated oxygen atom
is partially replaced by a sulfur oxygen atom in the first
coordination sphere, demonstrating the Zn2+ ion is partially
solvated by the SO42− ions (Figure 7a−b).76 The in-situ
formed SEI is composed of S−O species from SO42− ions
which effectively suppressed the water related side reaction on
the anode surface and promoted for better electrochemical
107
performance.76 Similarly, the reversible co-insertion/extraction
of Zn2+/Li+ ions and Zn deposition/dissolution were observed
in Zn//LiMn0.8Fe0.2PO4 ZiB using 21 M LiTFSI + 0.5 M
ZnSO4 WiS electrolyte.79 The ZiB showed ∼140 mAh g−1
specific capacity with 1.8 V ESW and 183 Wh kg−1 energy
density with minimum capacity fading. Moreover, such WiS
electrolyte maintained the electrolyte pH for attending a highly
reversible insertion/extraction process.79
A medium concentrated WiS electrolyte based on a 6 M
LiTFSI + 3 M Zn(OTf)2 mixed electrolyte was capable of
reducing Zn dendrite formation and cathode dissolution.80
The mixed electrolyte released more and uniform Zn2+ ions
during the cycling process, which lead to smooth Zn
deposition and reduced dendrite formation. The WiS electro-
lyte exhibited a lower contact angle than diluted electrolyte
(ZnSO4 and Zn(OTf)2), suggesting the WiS electrolyte greatly
improved the V2O3@C cathode wettability and facilitated
Zn2+-ion transfer kinetics (Figure 7c).80 In addition, the redox
peaks were shifted to higher potential than those for diluted
electrolyte. 80 Moreover, it is evident that the highly
concentrated WiS electrolyte based on 21 M LiTFSI + 0.43
M Zn(OTf)2, which contained almost no free water molecules,
exhibited comparatively lower electrochemical performance
than 6 M LiTFSI + 3 M Zn(OTf)2 WiS electrolyte. This result
suggested that an appropriate amount of free water molecules
is required in electrolyte to exhibit high electrochemical
performance.80 The reductive decomposition of salt anion
formed an SEI on the electrode, facilitated smooth extraction/
insertion of Zn2+ ions, reduced the tendency of cathode
dissolution into the electrolyte.80 The ESW and cycling
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stability of the Zn//V2O5 ZiB device improved to a larger
extent using 21 M LiTFSI + 1 M Zn(OTf)2 mixed
electrolyte.81 Two pairs of oxidation/reduction peaks (charge
(∼1.06 and ∼1.23 V) and discharge (∼0.90 and ∼1.10 V))
were observed during the GCD process in mixed electrolyte
which are ascribed to the dual Li+-/Zn2+-ion insertion/
extraction. The interlayer spacing of V2O5 planes increased
by ∼2.43% from its original spacing during the GCD process,
suggesting the dual Li+-/Zn2+-ion insertion/extraction is highly
reversible, as confirmed from the ex-situ/in-situ XRD pattern
and ex-situ HR-TEM image analysis. Importantly, the reductive
decomposition of bulky TFSI− and OTf− anions in mixed WiS
electrolyte generated an SEI on the electrode surface leading to
improved cycling stability and ∼80% initial capacity retention
after 2000 GCD cycles.81
Generally, most of the cathode materials and electrolyte ions
predominantly took part in the capacity contribution by the
cationic redox process. Therefore, ZiB exhibited low capacity
compared to the other one. The ZiB capacity was enhanced by
introducing the anodic redox process of the cathode material.82
The VOPO4 cathode displayed an anionic redox contribution
which improved the capacity and energy density of the ZiB
using 21 M LiTFSI + 1 M Zn(OTf)2 mixed WiS electrolyte.
The VxOy polyhedron contains only V−O covalence, which
had stronger binding energy. By incorporating the P−O in the
VxOy polyhedron, the P−O covalence exhibited weaker
binding energy. As a result, the oxygen electron density in
the VxOy polyhedron was increased and exhibited oxygen
redox chemistry.82 In addition, the oxygen redox chemistry
enhanced the ESW of ∼2.6 V (0.8−2.1 vs Zn2+/Zn) in WiS
electrolyte by enhancing the OER overpotential and reversibly
took part in the capacity contribution (Figure 7d−e).82
Moreover, the WiS electrolyte can also restrain the cathode
dissolution into the electrolyte and Zn anode corrosion.82 The
O 1s XPS spectra demonstrated that the O2− is oxidized to O−
during charging, and a reversible phenomenon was observed in
the discharge process in the 1.7 to 2.1 V voltage region.82 The
extended anodic potential limit of 2.6 V can be achieve using
21 M LiTFSI + 3 M Zn(OTf)2 mixed WiS electrolyte. The
multiple cation coordination with TFSI− and OTf− anion
provided higher anode oxidation potential.83 The WiS
electrolyte exhibited 7 mS cm−1 ionic conductivity. Both the
TFSI− and OTf− anions from the electrolyte reversibly
extracted/inserted from/into the cathode during the charg-
ing/discharging process while the Zn2+ ions reduced to
metallic Zn on the anode surface. The Zn//graphite ZiB
exhibited superior cycling stability in WiS electrolyte with
∼95% Coulombic efficiency retention.83 The Zn//Na2V6O16·
nH2O ZiB exhibited superior electrochemical performance in
0.5 M Zn(ClO4)2 + 18 M NaClO4 WiS electrolyte.84 The
concentrated NaClO4 efficiently adjusted the solvation
structure and electronic state. The WiS electrolyte offered
high conductivity (98.5 mS cm−1), low viscosity (8.16 mPa s),
reversible plating/striping chemistry, high HER and OER
overpotential, and reduced cathode dissolution. The ClO4− ion
took part in the cation solvation sphere and generated a
cation−anion aggregate, which is beneficial to anion reduction
on the anode surface under applied potential rather than water
decomposition.84 The strong coordination of water molecules
with cations in the first solvation sphere leads to a significant
ClO4−-ion orbital levels (both HOMO and LUMO) down-
shift. As a result, the ClO4− ions are predominantly reduced to
yield a protective SEI (ZnCl2) on the electrode surface, thus
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ensuring a fast Zn plating/striping process and reduced
cathode dissolution.84 The water adsorption energy on the
ZnCl2 SEI is lower compared to that of the Zn metal anode.
The water molecules interacted with the Zn anode by electron
depletion around the oxygen atom and ZnCl2 salt by electron
accumulation. Thus, the SEI inhibits capture of electrons from
the Zn anode surface, thus making it kinetically sluggish for the
HER to proceed.84 The water related side reaction is effectively
reduced due to unavailability of free water molecules.
The Na3V2(PO4)2O1.6F1.4 cathode exhibited superior elec-
trochemical performance in 25 M ZnCl2 + 5 M NH4Cl mixed
WiS electrolyte. The redox peaks shifted to a higher potential
with increasing salt concentration from 5 to 30 M ZnCl2 WiS
electrolyte. Interestingly, the cathode exhibited similar redox
peaks in 25 M ZnCl2 + 5 M NH4Cl mixed WiS electrolyte, as
observed in 30 M ZnCl2 WiS electrolyte.85 The mixed
electrolyte effectively suppressed OER activity. The capacity
fading was more likely in acidic 30 M ZnCl2 WiS electrolyte
while the capacity fading was effectively reduced in neutral
mixed 25 M ZnCl2 + 5 M NH4Cl electrolyte.85 In addition,
proton insertion into the cathode material is observed, leading
to Zn5(OH)8Cl2·H2O new phase precipitation in WiS
electrolyte and contributed additional capacity. The reaction
mechanism can be expressed as85
First charge,
Na3V2(PO4 )2 O1.6F1.4
Na3 xV2(PO4 )2 O1.6F1.4 + xNa + + xe
The subsequent GCD cycles
Na3 xZnyV2(PO4 )2 O1.6 F1.8
Na3 xV2(PO4 )2 O1.6F1.8 + yZn 2 + + 2ye
H 2O H+ + OH
HzNa3 xZnyV2(PO4 )2 O1.6 F1.8
Na3 xZnyV2(PO4 )2 O1.6 F1.8 + zH+ + ze
Anode:
(y + 1/2z)Zn (y + 1/2y)Zn 2 + + (2y + z)e
The neutral WiS electrolyte promoted better cycling stability
without cathode capacity fading. The Zn//
Na3V2(PO4)2O1.6F1.4 ZiB in WiS electrolyte displayed ∼155
mAh g−1 capacity at 50 mA g−1 current density in 2.1 V (0.4−
2.1 V vs Zn2+/Zn) ESW and stable cyclability after 7000 GCD
cycles at 2 A g−1 current density.85 The solubility limit of Zn
salt is enhanced by mixing ∼9.2 g of ZnCl2, 5.06 g of ZnBr2,
and 0.36 g of Zn(OAc)2 salt, resulting a 75 M “water-in-trisalt”
electrolyte. The acetate capped water-salt oligomer bridge by
Br−/Cl−-H and Br−/Cl−/O−Zn2+-ion interactions is attributed
to the higher solubility of the Zn salt.86 The 75 M “water-in-
trisalt” electrolyte exhibited 1.28 mS cm−1 ionic conductivity.
The Zn2+-ion hydration number gradually decreased from 5.51
to 1.15 with increasing salt concentration, thus avoiding the
side reaction occurring in aqueous medium, and improved the
cyclic stability of the ZiB by suppressing the dendrite
formation.86 The Br− ions were oxidized to near-zero the Br
oxidation state and intercalated into the graphite cathode
during the charging process, and the reverse phenomenon is
observed in the discharge process. With increasing the salt
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Figure 8. Investigation of the charge storage mechanism in the Mn-VS4 electrode during the charging/discharging process. (a) Ex-situ XRD analysis
of Mn-doped VS4 cathode. (b and c) Ex-situ XPS analysis of the Mn-doped VS4 cathode after full discharge (b) and charge (c) potential cycles of S
2p. Adapted with the permission from ref 93. Copyright 2021 American Chemical Society. (d) CV curves of the Zn//MoS2@δ-MnO2 “H” cell and
coin cell. (e) GCD curves of the Zn//MoS2@δ-MnO2 “H” cell and coin cell. (f) Stability plot of the Zn//MoS2@δ-MnO2 “H” cell at 1 A g−1
current density. Adapted with permission from ref 94. Copyright 2022 American Chemical Society.

concentration, the Zn/Zn2+ redox potential shifted toward the
positive region and decreased the redox potential of Br/Br−. In
addition, the hydrogen and oxygen reduction potentials shifted
in the opposite direction of Zn/Zn2+ and Br/Br− redox
potentials, respectively, with decreasing the water content. The
Zn//graphite ZiB exhibited enhanced capacity from 29.5 to
605.7 mAh g−1 and 4.72 to 98.07% Coulombic efficiency
increment with increasing salt concentration.86
The relatively inexpensive acetate salt based on a 1 M
Zn(OAc)2 + 31 M KOAc WiS electrolyte displayed a 3.4 V
ESW and exhibited a total ionic conductivity of 2.96 × 10−2 S
cm−1 while the ionic conductivity of Zn2+ ions was ∼7.80 ×
10−3 S cm−1.87 Such a WiS electrolyte is considered as a mild
alkaline electrolyte with 9.76 pH which displayed a different
charge storage mechanism for the anode with Zn2+ ions and
HO− ions with the cathode as dual charge carriers. The ESW
gradually increased with increasing KOAc salt concentration
from 5 to 31 M, demonstrating that the availability of free
water molecules decreases in WiS electrolyte. ZnO dendrite
formation is favored in a strong alkaline environment with an
OH− concentration of >1 mol L−1.88 However, the OH−
concentration was 4-fold lower in WiS electrolyte, leading to
high reversibility of Zn deposition/dissolution. Zn//MnO2-
TiN/TiO2 ZiB exhibited an ∼240 mAh g−1 capacity at a 0.1
mA g−1 current density. Ex-situ analysis suggested the
formation of an MnOOH phase after full discharge, implying
the charge storage mechanism occurred through the insertion/
extraction of H+ ions in which the HO− ions acted as the
charge carrier.87 Unlike the traditional salt anion and solvent
reduction involving SEI formation on the electrode surface, the
Zn(H2PO4)2 salt additive in Zn(OTf)2 is used for the in-situ
generation of a (Zn3(PO4)2·4H2O) SEI over the Zn anode
surface.89 Due to the local pH change caused by the H2
109
evolution reaction at the Zn anode surface, a conductive and
highly dense SEI was formed. During H2 evolution, the OH−-
ion concentration increased near the Zn anode surface, which
leads to SEI formation. The SEI formation is described
below:89
2H 2O + 2e H 2 + 2OH
2H 2PO4 + 4OH + 3Zn 2 + Zn3(PO4 )2 ·4H 2O
The electrochemical parasitic side reaction causes H2
evolution and increases the OH−-ion concentration at the
electrode/electrolyte interface. The electrolyte additive Zn-
(H2PO4)2 salt reacts with OH− ions and generates a
Zn3(PO4)2·4H2O SEI on the electrode surface.79 The in-situ
formed SEI possessed high transference number, high
interfacial stability, and high conductivity. The SEI restrained
the side reaction by isolating the Zn from the bulk electrolyte
and ensured the uniform Zn deposition/dissolution reaction.89
4.2. Hybrid Electrolyte Engineering. 4.2.1. Organic
Additive Electrolyte. The addition of Et2O into the 2 M
ZnSO4 + 0.1 M MnSO4 mixed electrolyte of aqueous ZiB was
very effective to inhibit the formation and growth of Zn
dendrite.90 The highly polarized Et2O molecules in the mixed
electrolyte adsorbed on the Zn anode surface due to the high
local electric field. The Zn2+ solvation spheres were difficult to
pass throughout the hydrophobic Et2O layer, thus suppressing
the further plating of Zn2+ ions on these initially formed tips
and ensuring homogeneous Zn deposition.90 However, such
mixed electrolytes were unable to be sustained in low
temperature environments. The 2 M ZnSO4 + 0.1 M
MnSO4 mixed electrolyte with ethylene glycol additive
exhibited superior electrochemical performance at low temper-
ature. The abundant hydroxyl groups of ethylene glycol
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interacted with the water molecules by disrupting the water−
water H-bonds and exhibited high performance at low
temperature.90 The mixed additive electrolyte exhibited
∼1.29, 1.08, and 0.42 S cm−1 ionic conductivity at 25, 0, and
−10 °C, respectively. The Zn//MnO2 ZiB delivered ∼172
mAh g−1 capacity at −10 °C.90 The a 4 M ZnSO4 + 2 M LiSO4
in 1,2-dimethoxy ethane (DME)/water based WiS electrolyte
exhibited improved the cycle life with a capacity retention of
∼99.3% after 100 cycles. The amount of free water molecules
decreased and restricted the movement by forming hydrogen
bonds with the DME additive, as the DME−water binding
energy (15.32 kJ mol−1) is higher compared to the water−
water binding energy (8.5 kJ mol−1).81 The DME additive
shielded the Zn anode surface and controlled the Zn
nucleation process, making smooth Zn deposition/dissolution.
Moreover, the DME additive reduced the dynamic contact
angle, resulting in improved wettability of the electrode
materials with electrolyte.91
The Zn deposition/dissolution is highly reversible in a 20 M
LiTFSI + 1 M Zn(OTf)2 mixed salt in an ACN/water hybrid
electrolyte compared to the 1 M ZnSO4 and 1 M Zn(OTf)2
electrolyte.92 This is due to the fact that the bulky anions and
ACN solvent affect the solvation structure of the electrolyte.
Furthermore, the finest Zn particles were formed with a
spherelike shape in the hybrid electrolyte, while hexagonal
platelets of Zn particles grew in the diluted electrolyte.92
Similarly, the Mn-doped VS4 cathode exhibited an ∼547.68
mA h g−1 specific capacity at a 0.2 A g−1 current density using a
1 M Zn(OTf)2 salt in ACN/water (1:1 ration) mixed hybrid
electrolyte. Ex-situ XRD analysis suggested the formation of a
new phase Zn3(OH)2V2O7·2H2O and orthorhombic sulfur
during the GCD process, indicating that partial phase
conversion occurred in the hybrid electrolyte (Figure 8a).93
Reversible anionic redox chemistry (S22− → S2−) is observed in
the hybrid electrolyte which enhanced the capacity contribu-
tion of the ZiB (Figure 8b−c).93 Moreover, the usage of the
ACN solvent effectively prevented Zn dendrite formation and
enhanced the rate capacity of the device (97.83% initial
capacity retention after 1000 charge/discharge cycles).93 The
OER and HER overpotentials were generally higher in acidic
and alkaline electrolytes than in the neutral (pH = 7) aqueous
electrolyte. The Zn anode was used in alkaline electrolyte, and
the MoS2@δ-MnO2 cathode was used in acidic electrolyte
considering the overpotential phenomenon using the “H”-cell
configuration. The “H”-cell showed an elevated ESW ∼ 2.48 V
(vs Zn2+/Zn) using ACN/water/KOH/ZnClO4 anolyte and
ACN/water/H2SO4/ZnClO4 catholyte separated by the ion-
exchange membrane (Figure 8d−e).94 Furthermore, the ACN/
water/H2SO4 and ACN/water/KOH formed a strong water
cluster which delayed the water decomposition. The “H”-cell
displayed ∼464 mAh g−1 at a 0.2 A g−1 current density with
∼99.2% Coulombic efficiency and exhibited superior cyclic
stability with ∼93% capacity retention after 500 GCD cycles
(Figure 8f).94Ex-situ analysis suggested that both the striping/
plating of Zn and co-insertion/extraction of H+/Zn2+ ions took
place simultaneously.94
Zn plating/striping is enhanced by using a 4 M Zn(OTf)2 +
0.5 M Me3EtNOTf WiS electrolyte from 87.6 to 99.9%. The
Me3EtNOTf organic additive effectively generated hydro-
phobic fluorinated salt (ZnF2) on the anode surface by the
reductive decomposition of OTf− anions which suppressed the
HER and controlled Zn dendrite growth.95 The ZnF2 enriched
layer allowed smooth diffusion of Zn2+ ion and shielding of the
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Zn surface from water. Moreover, the WiS electrolyte enabled
exhibition of the oxygen redox chemistry of the VOPO4
cathode leading to the enhanced specific capacity of the
Zn//VOPO4 ZiB. The ZiB delivered a 136 Wh kg−1 energy
density and retained ∼88.7% capacity after 6000 GCD
cycles.95 The “water-in-deep eutectic solvent” electrolyte
based on ZnCl2-acetamide reduces the Zn2+ desolvation
energy barrier by regulating the Zn2+-ion solvation structure
to promote uniform Zn nucleation. 9 6 A [ZnCl-
(acetamide)2(H2O)]+ cation complex was formed in hybrid
electrolyte in a 1:3:1 ratio of ZnCl2:acetamide:water. The
water molecules were replaced by the acetamide from the
primary solvation sheath, resulting in reduced water related
side reaction and hindering nonuniform Zn deposition. The Zn
anode exhibited ∼98% Coulombic efficiency retention after
1000 GCD cycles for 1400 h. In addition, the Zn//phenazine
ZiB displayed ∼85.7% initial capacity retention after 10000
GCD cycles with 100% Coulombic efficiency at 10 C current
density.96 The novel hydrated eutectic electrolyte based on
hydrated salt (Zn(ClO4)2.6H2O) and a neutral ligand
(succinonitrile, SN) without water solvent showed a reversible
Zn deposition/dissolution process.97 The Lewis base SN
essentially participated in the Zn2+-ion primary solvation shell
by replacing water molecules in a manner of forming the
hydration-deficient complexes {[Zn(OH2)x(SN)y]2+} in eutec-
tic electrolyte which allowed dendrite-free Zn plating/stripping
with ∼98.4% Coulombic efficiency. The SN coordination to
Zn2+ ion in the primary solvation sheath reduces the Zn2+ ion
and water molecules interaction. As a result, the water related
parasitic reactions that occurred at the Zn-aqueous electrolyte
interface and perchlorate decomposition are suppressed.
Moreover, the cathode dissolution is restricted in eutectic
electrolyte, leading to high ZiB cycling stability over 3,500
cycles at a 0.3 C current density.97
4.2.2. Polymer Gel Electrolyte. The “water-in-gel” based on
a NaCl/ZnSO4/sodium alginate electrolyte exhibited both WiS
and polymer gel electrolyte properties in Zn//CuHCF/CNT
ZiB. The hybrid electrolyte exhibited a 2.72 V (vs Zn2+/Zn)
ESW and a dual Na+/Zn2+-ion insertion/extraction mechanism
leading to a high specific capacity of ∼260 mAh g−1 with ∼95%
initial capacity retention after 1000 GCD cycles.98 The hybrid
electrolyte displayed 62.5 mS cm−1 ionic conductivity. The free
water molecules were capped inside the polymer chains and
promoted faster ion diffusion leading to the wide ESW of the
device and restricted water related side reaction. In addition,
the Zn2+ ion internally coordinated with sodium alginate
polymer resulting in uniform Zn deposition on the anode
surface. Therefore, the Zn dendrite on the electrode surface is
restricted and exhibited high cycling stability with high
Coulombic efficiency.98 A hydrated polymer gel electrolyte
composed of adiponitrile and Zn(ClO4)·6H2O in a poly-
(ethylene glycol) dimethacrylate polymeric framework was
found to reduce the Zn dendrite growth, gas evolution, and
cathode degradation during potential cycling.99 The adiponi-
trile organic additive in the polymer gel electrolyte stabilized
the electrode/electrolyte interface and enabled smooth Zn
deposition/dissolution by reducing the water related parasitic
reaction. Furthermore, the H-bonding interaction between the
ether groups and water molecules suppressed water activity
leading to an enhanced ESW. The Zn//Zn symmetric cell with
hydrated polymer gel electrolyte can operate more than 1000 h
at 0.5 mA cm−2 and 2000 h at 0.2 mA cm−2 without short-
circuiting, indicating Zn dendrite suppression. Moreover, the
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Figure 9. (a) GCD curves of the Zn//V2O5@MnO2 device in the solid electrolyte at different bending angles. (b) Different bending states of the
Zn//V2O5@MnO2 solid-state device. (c) Hammering test, (d) weight loading test, (e) thermal safety and fire test, and (f) practicability test by
powering a 1.8 V LED light and 1.5 V DC motor connected with a fan in the normal state and under water of the Zn//V2O5@MnO2 solid-state
device. Adapted with the permission from ref 102. Copyright 2022 American Chemical Society.

Table 1. Comparison of Electrochemical Performances of Different Zinc Salts

Conductivity ESW Specific capacity
Electrolyte (mS cm−1) Cathode (V) (mAh g−1) Cycle stability References
ZnCl2 + triethylamine hydrochloride - MnO2 2.0 210 82.9% after 200 15
cycles
LiTFSI + ZnSO4 - LiMn0.8Fe0.2PO4 2.35 114 99.3% after 150 11
cycles
Zn(OTf)2 + Mn(OTf)2 - MnO2 1.8 225 94% after 2000 14
ZnSO4 + Li(SO4)2 - V2O5 1.6 140 100% after 300 1
Zn(TFSI)2 + LiTFSI - LiMn2O4 2.2 67 80% after4000 23
Zn(OTf)2 34.7 ZnMn2O4 2.0 150 94% after 500 19
ZnSO4 - Zn0.25V2O5.nH2O 2.4 300 80% after1000 18
ZnSO4 + MnSO4 - MnO2 1.9 265 83% after 1200 20
Al(OTf)3 + Zn(OTf)2 - MnO2 1.7 264 100% after 1000 28
Zn(ClO4)2 + SN 17.66 quinone polymer 1.5 95 86% after 3500 46
ZnSO4 + Na2SO4 - V3O8·1.5H2O 1.3 380 82% after 1000 40
ZnSO4 + MnSO4 + 0.067 MnO2 1.8 149.2 86.6% after 1500 44
poly(vinyl butyral)
Zn(OTf)2 - FeVO4 1.8 272 78.8% after 50 43
ZnCl2 - V2O5 1.6 235.6 90.5% after 300 59
ZnSO4 + MnSO4 13.31 MnO2 1.8 265 88.37% after 1200 62
ZnSO4 + LiTFSI - LiMn0.8Fe0.2PO4 1.8 137 99.3% after 150 71
Zn(OTf)2 + LiTFSI - V2O3@C 1.6 240 90.2% after 8000 72
Zn(OTf)2 + LiTFSI - V2O5 1.6 238 80% after 2000 73
Zn(OTf)2 + LiTFSI - VOPO4 2.1 140 93% after 1000 74
Zn(ClO4)2 + NaClO4 2 Na2V6O16.nH2O 1.5 250 99% after 2000 76
ZnCl2 + NH4Cl - Na3V2(PO4)2O1.6F1.4 1.46 155 73.5% after 7000 79
ZnCl2/ZnBr2/Zn(OAc)2 1.28 Graphene oxide 2.0 605.7 74.5% after 500 80

Zn//Sr-doped Na3V2(PO4)3 displays 108 mAh g−1 at 0.5 C
capacity and retains a 90 mAh g−1 capacity after 8000 cycles at
a 10 C current density.99
The Zn-ion diffusion resistance decreased in the following
order: ZnCl2 < Zn(OTf)2 < ZnSO4 < Zn(OAc)2 < Zn(NO3)2.
In addition, the ZnCl2 electrolyte exhibited faster ion exchange
rates than other electrolytes.100 The DFT study revealed that
the desolvation energy of Cl− induced [ZnCl]+-(H2O)n−1
(with n = 1−6) clusters is significantly lower than that of
111
[Zn(H2O)n]2+ counterparts. The polyacrylamide-based hydro-
gel exhibited superior electrochemical performance with a 10
M ZnCl2 WiS electrolyte. The polar end of polyacrylamide
contained abundant layers and interconnected pores which are
capable of storing several electrolytes and allowing dendrite-
free Zn deposition. The hydrogel-based fabricated device
exhibited 100000 GCD cycles with ∼95.1% capacity
retention.100 The K0.486V2O5 cathode with 0.95 nm interlayer
spacing exhibited a 419 mAh g−1 specific capacity using
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ACS Applied Electronic Materials
Figure 10. Schematic illustration of conclusion and outlook for the development of high performance ZiB.
sodium carboxymethyl cellulose based on a 15 M ZnCl2 WiS
electrolyte with a 10.08 mS cm−1 ionic conductivity.101 The
Zn//K0.486V2O5 ZiB delivered an ∼268.2 Wh kg−1 energy
density, 97.35% after 2800 cycles low self-discharge rate, and
good environmental suitability. Such a polymer gel electrolyte
based on a moderate WiS electrolyte significantly reduced
cathode dissolution.101 The extremely safe, flexible, robust, and
environmentally friendly aqueous ZiB based on a hydrophilic
polymer gel electrolyte had special advantages for flexible
electronics and electric vehicles transportation.102 The revolu-
tionary WiS electrolyte suppressed parasitic side reactions on
electrode materials by forming hydrated cation solvation
spheres in the bulk electrolyte, thereby extending the ESW.
In addition, molecular crowding is a common phenomenon in
our living cells where the water activity is considerably
suppressed by molecular crowding agents through altering the
hydrogen bonding structure.102 The WiS-based hydrophilic
molecular crowded polymer gel electrolyte and binder-free
V2O5@MnO2 cathode are used to augment the durability,
flexibility, safety, and electrochemical performance of ZiBs.
The “free water trapping” capability of the WiS-based cross-
linked molecular crowded polymer electrolyte provides an
extended ESW of the device. The hydrophilic poly(ethylene
glycol) methyl ether methacrylate (PEGMA) served as the
molecular crowding agent that can stabilize the free water
molecules and reduced the unwanted anode side reaction. The
bisphenol A ethoxylate dimethacrylate (BEMA) cross-linking
monomer significantly improved the mechanical strength of
the electrolyte.92 The quasi-solid-state ZiB delivered an ∼422
mAh g−1 discharge capacity and showed excellent cycling
112
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stability, as high as ∼79.83% retention in initial capacity after
5000 cycles. The durable, flexible, and ultrastable ZiB with
polymer gel electrolyte performed well under various severe
conditions, such as bending, hitting, overloading, cutting, and
subjection to water and fire, where both the battery safety and
energy density are of high priority (Figure 9).102 The
electrochemical performance of the recently reported ZiB
electrolyte engineering are summarized in Table 1.
5. SUMMARY AND FUTURE PERSPECTIVES
The advancements in rechargeable ZiBs are strongly related to
the electrolyte salt and solvent innovation. They start from
basic characteristics, fundamental insights of the electrode/
electrolyte interface, cathode dissolution, dendrite formation,
etc. Considering the recent scenario of ZiB research, future
prospects and potential directions of electrolytes are proposed
in the following aspects (Figure 10). The electrolyte
formulation is the key factor that affects the electrochemical
performance of the ZiB. The structural properties of the
primary and secondary solvation sheaths and their compati-
bility with the electrode material in the electrode interface
including the Mayer bond level, bond length, desolvation
energy, etc. play a vital role. Therefore, in-situ investigation of
the electrolyte state is needed during the GCD process.
Revealing the electrolyte in-situ structure is beneficial for better
electrolyte design. It is important to investigate the
morphology and phase change of the generated byproduct
caused by the electrolyte state change from liquid to solid state
during the GCD process. Furthermore, it is important to
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ACS Appl. Electron. Mater. 2023, 5, 100−116
ACS Applied Electronic Materials
monitor the electrolyte pH at the interface by an in-situ pH
meter which will directly influence the electrochemical
performance of ZiBs. The electrolyte structures influenced by
the functional groups of polymer gel electrolytes are taken into
consideration through in-situ FT-IR, NMR, Raman, etc.
studies. Density functional theory calculations and molecular
dynamic simulations are other important theoretical techni-
ques to understand the electrolyte environment more deeply
and analyze the corresponding reasonable mechanism.
The electrode/electrolyte interface tailors the ZiB perform-
ance as multistep electron transfer takes place at the electrode/
electrolyte interface. The interfacial properties of the ZiB are
closely related to the formation of new materials on the
electrode surface which will tailor the ionic conductivity, ESW,
ion transference number, interfacial compatibility, etc.
Depending on the interfacial interaction between different
electrodes and electrolytes, the Zn2+-ion desolvation dynamics
and ion transportation at the interface are closely related to the
electrochemical stability and rate performance of the ZiB. In
order to establish the electrolyte/electrode interface correla-
tion with the electrolyte, some important parameters such as
interface structure evolution, solid−liquid interface contact
compatibility, ionic conductivity, solvated ion and interface
interaction, etc. should be considered. In-situ experiments such
as online mass spectroscopy, optical microscopy, EXAFS, and
XANES modern techniques should be employed to investigate
the correlation between the electrolyte/electrode interface and
electrolyte.
In order to develop a ZiB with superior energy density, high
ESW, and long-term cycling stability at a large-scale, invention
of an economically affordable and environmentally friendly
electrolyte is urgently required to meet the recent scenario of
energy research. Some novel electrolyte approaches which
additionally contribute capacity to the device, such as
employing redox additives (hydroquinone/quinone, Fe3+/
Fe2+, I−/I2, Br−/Br2, etc.) in conventional electrolytes, should
be employed. Some functional additives in electrolytes, such as
organic solvents, organic polymers, asymmetric inorganic salt
additives, etc., are useful for enhancing the ESW, ionic
conductivity, and compatibility with the electrode and for
monitoring the electrolyte pH of the device. In addition,
selection of suitable electrode materials is more important
because different electrochemical performances are observed
for different electrode materials in aqueous electrolyte.
Moreover, detailed studies on different types of binders,
current collectors, and separators are very important. It is
believed that the electrolyte formulation maintains the merits
of solvent and salt for developing advanced ZiBs.
■ AUTHOR INFORMATION
Corresponding Author
Tapas Kuila − Surface Engineering & Tribology Division,
Council of Scientific and Industrial Research-Central
Mechanical Engineering Research Institute, Durgapur
713209 West Bengal, India; Academy of Scientific and
Innovative Research (AcSIR), CSIR - Human Resource
Development Centre, Ghaziabad 201002 Uttar Pradesh,
India; orcid.org/0000-0003-0976-3285; Email: tkuila@
gmail.com, t_kuila@cmeri.res.in
Authors
Prakas Samanta − Surface Engineering & Tribology Division,
Council of Scientific and Industrial Research-Central
113
pubs.acs.org/acsaelm Review
Mechanical Engineering Research Institute, Durgapur
713209 West Bengal, India; Academy of Scientific and
Innovative Research (AcSIR), CSIR - Human Resource
Development Centre, Ghaziabad 201002 Uttar Pradesh,
India; orcid.org/0000-0003-1508-7025
Souvik Ghosh − Surface Engineering & Tribology Division,
Council of Scientific and Industrial Research-Central
Mechanical Engineering Research Institute, Durgapur
713209 West Bengal, India; Academy of Scientific and
Innovative Research (AcSIR), CSIR - Human Resource
Development Centre, Ghaziabad 201002 Uttar Pradesh,
India; orcid.org/0000-0002-2577-3443
Aniruddha Kundu − Surface Engineering & Tribology
Division, Council of Scientific and Industrial Research-
Central Mechanical Engineering Research Institute, Durgapur
713209 West Bengal, India; orcid.org/0000-0002-6508-
6728
Pranab Samanta − Surface Engineering & Tribology Division,
Council of Scientific and Industrial Research-Central
Mechanical Engineering Research Institute, Durgapur
713209 West Bengal, India; Academy of Scientific and
Innovative Research (AcSIR), CSIR - Human Resource
Development Centre, Ghaziabad 201002 Uttar Pradesh,
India; orcid.org/0000-0003-3934-8648
Naresh Chandra Murmu − Surface Engineering & Tribology
Division, Council of Scientific and Industrial Research-
Central Mechanical Engineering Research Institute, Durgapur
713209 West Bengal, India; Academy of Scientific and
Innovative Research (AcSIR), CSIR - Human Resource
Development Centre, Ghaziabad 201002 Uttar Pradesh,
India; orcid.org/0000-0002-4644-3523
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsaelm.2c01355
Author Contributions
The manuscript is written through contributions of all authors.
All authors have given approval to the final version of the
manuscript.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors are thankful to the Council of Scientific &
Industrial Research (CSIR) for financial support through the
HCP-44/02/1 project. A. Kundu would like to acknowledge
the DST-INSPIRE Faculty Scheme, Department of Science
and Technology, New Delhi, Govt. of India (IFA20-MS-168)
for financial support. The authors are also thankful to the
Director of CSIR-CMERI, Durgapur.
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