Zinc
Zinc
Zinc
Research Papers
A R T I C L E I N F O A B S T R A C T
Keywords: Zn-ion batteries (ZIBs) continue to attract attention for commercial grid storage systems and as alternatives to
Zinc-ion batteries lithium-ion batteries owing to their safety, environmental friendliness, relatively high volumetric energy density,
Cathode dissolution material availability, and lower production cost. Unfortunately, issues such as dendrite formation at the anode,
Zinc anodes
cathode dissolution, and parasitic side reactions (such as hydrogen evolution and corrosion reactions) continue
Cathode materials
to plague this battery technology, thus hindering its practical application. In this review, we provide an in-depth
Electrolytes
understanding of the current issues that affect zinc-ion batteries and comprehensively discuss the issues affecting
zinc anodes, cathodes, and electrolytes. Further, the current research focusing on mitigating these issues has been
scrutinized. This review article presents recent perspectives on zinc-ion batteries regarding factors such as
environmental friendliness, cost of development, and enhancing the cycle life of zinc-ion batteries to guide the
future development of high-performance zinc-ion batteries.
1. Introduction friendliness. Currently, Li-ion batteries are the most extensively used
energy storage devices due to their excellent energy density, cyclic
Energy devices play a critical role in humanity’s technological as stability, and high discharge voltages [1]. Supercapacitors have also
well as socio-economic development. The day-to-day functioning of found extensive use in electric vehicles and other high-power devices
many sectors in the world today, such as electric vehicles, aerospace due to their significantly high power discharge capacities, cyclability
vehicles, smart devices, and other electronic devices, is energized by (>10,000 cycles), and short charging times [2–4].
energy storage devices. The overall energy framework consists of two
main components: (i) energy production, such as solar power, 1.1. Motivation for zinc-ion batteries
geothermal, and wind energy, and (ii) energy storage, such as batteries
and supercapacitors. Due to inconsistency in the source of the energy As mentioned in the previous section, Li-ion batteries (LIBs) are the
generation system, an energy storage system is a crucial part of any dominant battery technology being utilized commercially today owing
electronic device, and as a result, the development of an energy storage to their high energy densities and long cycle life [5]. The overall market
system has been the subject of extensive research in recent years. The scenario suggests that the Li-ion market will expand from $30 billion to
main energy storage devices on the market today are batteries and $100 billion by 2025 [6]. However, despite their inherent benefits, Li-
supercapacitors. Batteries have found widespread use in portable elec ion batteries face significant drawbacks. Dwindling lithium metal
tronic devices, electric vehicles, and large-scale grid energy storage due sources, the high cost of production, the decline in discharge capacity as
to their high efficiency, high specific energies, and environmental a result of corrosion and dendrite growth, and serious safety concerns
* Corresponding author.
** Correspondence to: R.K. Gupta, National Institute for Materials Advancement, Pittsburg State University, Pittsburg, KS 66762, United States.
E-mail addresses: anuj.kumar@gla.ac.in (A. Kumar), ramguptamsu@gmail.com (R.K. Gupta).
https://doi.org/10.1016/j.est.2023.108081
Received 1 April 2023; Received in revised form 26 May 2023; Accepted 13 June 2023
Available online 20 June 2023
2352-152X/© 2023 Elsevier Ltd. All rights reserved.
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
brought by the use of flammable organic electrolytes and explosions on ion battery—the cathode, anode, and electrolyte presenting a practical
overcharging are some of the challenges faced by Li-ion technology design perspective for more efficient batteries. Although there has been
[6–8]. As a result, there is a need to develop an alternative battery many emerging research on different types of Zinc-ion batteries such as
technology to replace Li-ion batteries. Several potential replacement Zn‑sulfur, Zn‑iodine, Zn‑nickel and other redox type Zn-ion batteries,
candidates for lithium have already been identified (including Na, K, our work mostly scrutinizes Zn-MnO2, Zn-V2O5 and Zn-air type Zn-ion
Mg, Ca, Al, and Zn), as shown in Fig. 1(a-b). Although next-generation batteries due to their favorability in real-time application. To this end,
Zn-ion batteries are promising candidates to act as a suitable replace we discuss the major issues that affect the performance of the Zn-ion
ment for traditional Li-ion batteries owing to their high volumetric ca from a cathodic, anodic, and electrolyte perspective, detailing the
pacity of 5854 mAh/cm3 for Zn anode vs Li anode (2061 mAh/cm3), in causative mechanisms involved in the occurrence of these issues.
practical scenario, ZIBs have shown limited circumvention over Additionally, we take a similar approach in discussing the mitigation
achievable energy density of LIBs [9–14]. Despite this fact, energy strategies for these challenges that have been studied in recent years,
density achieved by full-cell ZIBs in the field and abundance of Zn re providing the processes and mechanisms involved in the improvement
sources, have facilitated lower production costs for the fabrication of Zn- in the overall electrochemical performance of the Zn-ion batteries.
ion batteries with promising replacement opportunity over traditional Finally, we provide some future perspectives into the further develop
lead-acid, Ni–Cd and Ni-metal hydride (MH) type batteries [15,16]. In ment of high-performance Zn-ion batteries, highlighting potential areas
addition, Zn-ion batteries incorporate the use of relatively safer and less for further enhancement of electrochemical performance and also giving
complex electrolytes in their fabrication and are thus more advanta insights on the development of environmentally sustainable, low-cost
geous than Li-ion batteries in terms of electrolyte composition [6]. Zn-ion batteries.
Furthermore, Zn-ion batteries possess a longer service life, superior
environmental friendliness, and exhibit good stability in aqueous elec 2. Zinc-based batteries
trolytes [6,17]. As a result, current research efforts are focused on the
development of Zn-ion battery technology [18]. Zn-ion batteries can be broadly classified into two main groups: (i)
Zn-metal oxide batteries commonly termed Zn-ion batteries (ZIB) and
(ii) Zn-air batteries (ZAB). The working principles of these ZIBs are
1.2. Scope of this review
outlined in Section 2 of this review, and as such, this section focuses on
providing examples of each of these battery types. ZIBs have been
This review seeks to provide the readership with a comprehensive
extensively studied over a long period of time and have generated
view of the recent research into the development of high-performance
exceptional interest due to their low redox potential and high theoretical
Zn-ion batteries. Many reviews of this nature tend to focus on a spe
capacity [18]. ZIB with varying cathode materials has been studied, with
cific component of the battery exclusively, particularly on the Zn anode.
manganese-based cathodes and vanadium-based cathodes being the
In this review, however, we focus on all the major components of the Zn-
Fig. 1. (a) Comparison of reduction potentials for candidate metal anodes (b) Comparison of theoretical specific capacities for candidate metal anodes. Adapted with
permission [21]. Copyright (2021), American Chemical Society. Schematic diagram of a typical (c) Zn-ion battery and (d) Zn-air battery. Adapted with permission
[7]. Copyright (2021), American Chemical Society.
2
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
most heavily investigated cathode materials owing to their high safety, are inserted into the cathode material, which typically has a layered or
environmental friendliness, and abundant resources [19]. Zn-MnO2 and tunnel structure that facilitates the transport of these ions (Fig. 2a).
Zn-V2O5 are examples of ZIBs that have been extensively investigated in During charging, this process is reversed, whereby Zn2+ ions are dein
recent years. Fig. 1c shows a schematic diagram of a typical ZIB. Due to serted from the cathode and zinc is plated onto it [7,18]. The cathode
their high theoretical energy density, low fabrication cost, wide theo reactions for ZIBs are explained in later sections while discussing various
retical working voltage, and inherent safety, ZABs have garnered sig metal oxide cathodes.
nificant research focus in recent years. This is reinforced by the fact that Anode reactions:
current renewable energy sources such as wind and solar are largely The pH of the chosen electrolyte has a significant effect on the anodic
reliant on geographical and environmental conditions for their perfor reactions in Zn-ion batteries, as shown in Eqs. (1)–(3) [7].
mance, and their power output is often intermittent as a result of this In neutral or acidic electrolytes:
reliance [20]. ZABs are viewed as a promising potential technology to
Zn(s) ↔ Zn2+ + 2e− (1)
overcome these challenges and provide a continuous power supply.
Fig. 1d shows a schematic diagram of a typical ZAB. Other examples of In alkaline electrolytes:
Zn-ion-based batteries are Zn‑carbon battery, Zn-CoOx battery, Zn‑io
dine, Zn‑sulfur, Zn‑nickel and Zn-polymer batteries. Zn(s) + 4OH − ↔ Zn(OH)4 2− + 2e− (2)
In this review, we discuss the current issues that hinder the further
development of Zn-ion batteries, taking an in-depth look into issues such Zn(OH)4 2− ↔ ZnO(s) + H2 O + 2OH − (3)
as dendrite formation, parasitic reactions, and dissolution of cathode As shown in Fig. 2b, the reaction in the acidic or basic electrolyte has
materials. We then present several strategies to resolve these issues, thermodynamic force, resulting in the formation of either Zn2+ or ZnO
focusing on the current research in the development of these strategies. species on the anode surface. In the case of ZIBs, ZnO is not favorable for
In addition, perspectives on the development of high-performance Zn- the long cycle life of the Zn-ion battery and results in anode passivation.
ion batteries are provided. Previous reviews typically have a singular Hence, typical electrolytes used in Zn-ion batteries such as ZnSO4 and
focus on either the anode for Zn-ion batteries or the cathode for Zn-ion ZnCl2 have an acidic pH, resulting in dominant Zn2+ species favorable
batteries. This review thus takes a comprehensive approach, discussing for longer charging and discharging of ZIBs [22]. On the contrary, ZnO is
the issues facing both anode and cathode materials in ZIBs, as well as the desired species for Zn-air batteries, where strong alkaline electro
mitigation strategies and perspectives for both anode and cathode lytes such as KOH with a basic pH help in the formation of a reaction
materials. environment and are widely used for fabricating ZABs [23,24].
Cathode reactions:
In the case of the MnO2 cathode, the reaction occurs as a 1 or 2 e−
2.1. Working principle of Zn-ion batteries process, resulting in a specific capacity of 308 or 616 mAh/g [22]. The
overall reaction mechanism of MnO2 cathode in a Zn-MnO2 battery is
Zn-ion batteries are made up of three main components: (i) a Zn slightly complex and can be summarized as [25,26]:
metal anode, (ii) a Zn-containing aqueous electrolyte, and (iii) a cathode H+ insertion:
material for storing Zn ions, typically manganese-oxide or vanadium-
oxide [6,18]. When it comes to charging and discharging mechanisms Mn4+ + e − →Mn3+ (4)
of Zn-ion batteries, there are two known processes, including 1e− and
2e− based on Zn2+ insertion and deinsertion reactions occurring at the MnO2 (s) + H + (aq) + e− ↔ MnOOH (s) (5)
cathode, where Zn ions are correspondingly electro-stripped/electro- During discharging, the MnO2 cathode is more likely to produce
plated near the anode surface [7]. During discharge, the Zn anode is unstable Mn3+ species due to insertion of H+ ion resulting in MnOOH
dissolved, and through, oxidation releases Zn2+ ions. These Zn2+ ions
Fig. 2. (a) Schematic illustration of the zinc anode reaction mechanism. Adapted with permission [8]. Copyright (2020), American Chemical Society. (b) Pourbaix
diagram for zinc in different pH in water. Adapted with permission [30]. Copyright (2016), Elsevier. This is an open-access article distributed under the terms of the
Creative Commons CC-BY license.
3
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
which then undergoes disproportionation reaction leading to dissolution the optimum anode thickness for ZIBs. The dissolution of cathode
of manganese in aqueous solution. materials—mainly metal oxides—in the electrolyte is detailed, along
with a brief discussion on issues facing ZIB electrolytes.
2Mn3+ →Mn4+ (s) + Mn2+ (aq) (6)
The disproportionation of MnOOH via dissolution of Mn2+ species 3.1. Dendrite growth
occurs either as:
An electrochemical reduction reaction: One of the most significant issues in the development of battery
MnOOH (s) + H2 O + e − →Mn2+ (l) + 3OH − (7) technology is the formation of dendrites on the anode surface. This is
especially the case for ZIBs, where this phenomenon is of paramount
Or, chemical disproportionation reaction: concern. As such, considerable research efforts have been dedicated to
2MnOOH→Mn2+ + MnO2 + 2OH − (8) resolving this issue. Dendrite growth in ZIB is caused by non-ideal sur
face properties, such as uneven ion distribution, an uneven electric field,
The reaction in Eq. (8) continues until there is significant change and the free movement of zinc ions that stick to the surface in the same
observed in pH value of electrolyte in ZIBs and precipitation of zinc plane [31]. The dendrite growth process occurs as follows: (i) Small zinc
hydroxide sulfate (ZHS) occur at the cathode interface. The ZHS reaction protrusions are formed on the anode surface as Zn ions are reduced at
at the cathode interface can be detailed as [27]: energetically favorable charge transfer sites during initial battery
cycling (Fig. 3a), (ii) due to the lower surface energy of these pro
3MnO2 + 8 Zn2+ + 2 SO2−4 + 16 H2 O + 6e − →3 Mn2+ + 2 Zn4 (OH)6 (SO4 )
trusions, zinc ions preferentially aggregate on the protrusions, thus
• 5H 2 O↓ forming the initial dendrites (Fig. 3b), (iii) further dendrite growth is
(9) facilitated by the “tip effect” which enhances the local electric field in
In previous literature, this reaction is referred to as a Dissolution- tensity due to the large curvature of these protrusions that provides a
deposition reaction. [27,28] The formation of ZHS can take away higher surface charge density (Fig. 3c) [31–34]. If left undeterred, zinc
large amount of active H2O around MnO2 cathode and prevent subse dendrites continue growing until either the battery separator is punc
quent dissolution of additional MnO2 species, thereby limiting any tured (Fig. 3d) or the zinc dendrites fracture and fall off the anode, thus
further cathode reactions to achieve higher capacity for ZIBs. forming what is known as “dead zinc” as shown in Fig. 3e [32].
Stripping reaction at Zn anode Dendrite formation can degrade battery performance in several
ways. Due to the loose structure of zinc dendrites, the area of contact at
3Zn→6Zn2+ + 6e− (10) the anode-electrolyte interface is significantly lowered, leading to a
decrease in electron transfer at the interface and thereby facilitating
From reaction 9 and 10, the overall reaction can be detailed as:
poor electrochemical performance [33]. In addition, the puncturing of
ZIB reaction via Zn2+ insertion is often simplified as:
the battery separator by zinc dendrites and the subsequent contact be
Zn2+ + Mn2+ + MnO2 + 4OH − ↔ 2Zn0.5 MnO2 + 2H 2 O (12) tween the dendrite and the cathode leads to a short circuit and is
therefore a direct cause of battery failure [33]. The formation of dead
The complete reaction results in the formation of ZnMn2O4 species
zinc is known to greatly reduce the coulombic efficiency and capacity
with high specific capacity. In the case of the Zn-V2O5 battery, the re
delivered by the zinc anode while also increasing the impedance of the
action proceeds by reduction of Zn to Zn2+ and intercalation of multiple
ZIB through the generation of by-products by the reaction between dead
Zn2+ species in the V2O5 structure [29]:
zinc and the electrolyte [31]. In addition to dendrite growth, adverse
xZn2+ + V2 O5 + 2 xe − + nH 2 O ↔ Znx V2 O5 .nH 2 O (13) side reactions occurring in the ZIB are a major issue for the performance
of these batteries. The hydrogen evolution reaction (HER) and corrosion
Unlike MnO2, which has an oxidation state of Mn , V-coordination
+4
reactions are the main reactions that cause for the degradation of elec
can exhibit several polyhedral structures to accommodate multiple Zn trochemical performance and are discussed in the following subsection.
ions without breaking the structure of vanadium oxide [12,29]. With
this firm understanding of the working principle of ZIBs, the challenges
faced in the development of this battery technology can be examined in 3.2. Parasitic hydrogen evolution and corrosion
detail. Growth of zinc dendrites during charge and discharge, parasitic
hydrogen evolution and corrosion reactions, and dissolution of cathode The parasitic hydrogen evolution reaction (HER) and corrosion re
materials in the battery electrolyte are some of the major challenges actions are the two main reactions that negatively impact Zn-ion bat
faced in the development of ZIBs, hindering their large-scale applica teries. A schematic of these processes and their effects is presented in
tions. These challenges, among others, are discussed extensively in Fig. 3(h-i). These reactions are inseparable from each other, especially in
Section 3. systems with mild electrolytes, and often occur simultaneously [32].
HER occurs easily in aqueous electrolytes during zinc plating, which is
3. Issues in zinc-ion batteries because the standard electrode potential of H+/H2 (0V vs SHE) is greater
than that of Zn2+/Zn (− 0.76 V vs SHE) (Fig. 3f) [7,32]. As is shown in
Despite the major interest that ZIBs have generated owing to their Fig. 3 g hydrogen evolution occurs in the space of a few minutes, indi
high theoretical capacity, excellent safety, and low cost, several major cating the rapid nature of this process. HER in ZIBs for different elec
challenges hinder their development and application. Factors such as trolyte types can be described in the following chemical equations [7]:
dendrite growth and parasitic side reactions plague the zinc anode, In neutral or alkaline electrolytes:
while the cathode materials face their own challenges such as dissolu Zn(s) + 2H 2 O ↔ Zn(OH)2 (s) + H2 (g)↑ (14)
tion in the electrolyte and passivation. Additionally, the electrolyte
utilized in ZIBs can also be susceptible to drying and decomposition. In acidic electrolytes:
This section details the major issues currently faced in ZIBs from an
2H + 2e− ↔ H2 (g)↑
+
(15)
anodic, cathodic, and electrolyte perspective. We begin by discussing
dendrite growth, detailing the process by which dendrites form in ZIBs. The corrosion process can be described as follows: during HER, H+
We also discuss the effect of the parasitic side reactions (hydrogen ions are consumed, therefore facilitating the increase in OH− ion con
evolution and corrosion reactions) as well as the challenge of developing centration at the surface of the zinc anode. Zinc reacts with OH− to form
Zn(OH)2−4 , which upon supersaturation precipitates to form Zn(OH)2.
4
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
Fig. 3. (a-d) Zinc Dendrite growth mechanism. Adapted with permission [35]. Copyright (2018), John Wiley and Sons. (e) Top-view SEM image of Zn anode after
short circuit. Inset: flake-like “dead zinc” dendrites. Adapted with permission [36]. Copyright (2021), Royal Society of Chemistry. (f) Pourbaix diagram of ZnSO4-H2O
system at 25 ◦ C. Adapted with permission [37]. Copyright (2021), American Chemical Society. (g) In-situ microscopy picture of the electrolyte‑zinc interface showing
bubble formation due to parasitic HER. Schematic diagrams showing (h) HER and corrosion reactions at the zinc anode surface and (i) their unfavorable effects.
Adapted with permission [38]. Copyright (2019), Elsevier.
5
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
used in fabricating ZIBs owing to its 2 × 2 tunnel structure. As explained an important parameter to consider in the development of ZIBs is the
in Section 2.1, the discharging of ZIB results in Zn2+ from the anode thickness of the anode utilized. The following subsection details the
diffusing in the MnO2 cathode via intercalation reaction and forming challenges faced and considerations made when determining the opti
ZnMn2O4 [22]. In terms of structure, the MnO6 octahedra are distorted mum thickness of anode materials depending on the final application of
during this intercalation in the presence of Mn3+ intermediate species the assembled ZIB.
following a conversion reaction of 2Mn3+ → Mn2+ + Mn4+ to stabilize
the defected MnO2 structure, commonly known as Jahn-Teller distortion
[12,39–43]. The formation of Mn2+ species further results in the 3.4. Optimum anode thickness
dissolution of cathode material in the electrolyte. During cycling, the
dissolution of transition metal ions from the cathode material frame The Zn anode delivers a high volumetric capacity of 5854 mAh/cm3
work into the electrolyte becomes worst, especially in aqueous electro resulting in a high volumetric energy density for ZIBs [47]. For grid
lytes consisting of Zn2+ and H+ species, eventually causing failure in energy storage applications, high volumetric density can significantly
ZIBs [44]. reduce the storage space required for ZIBs. In typical ZIBs, any access to
In manganese oxide cathodes, for example, the occurrence of intense the Zn anode results in dead weight, especially considering the high
Mn2+ dissolution during initial discharge and subsequent aggravation of density (7.13 g/cm3) of Zn metal, which affects the final energy density
this dissolution during further cycling results in inferior reversibility and of packaged ZIBs. This issue has been surprisingly neglected in many of
cycling performance compared to that which is expected in theory the previous studies [12,39,48–50]. Thicker Zn anodes (>100um) are
(Fig. 4a) [44]. A similar situation is found in vanadium-based cathode mostly studied in the literature corresponding to areal capacitor of 58.5
materials, where vanadium dissolution is intrinsic due to the use of mAh/cm2 to compensate for the anode passivation in ZIBs and low DOD
aqueous electrolytes. As shown in the schematic in Fig. 4b, water mol condition (<1 %), thereby enabling longer cycling life. However, for
ecules in aqueous electrolytes attack the crystal structure of the practical application of ZIBs, the Zn anode needs to have effective uti
vanadium-based cathode material due to their strong polarities [45], lization, lower negative to positive electrode capacity ratio (N/P ratio), a
directly leading to a decline in capacity and, subsequently, inferior higher depth of discharge (DOD), and stability against surface reactions.
electrochemical performance. Shifting attention back to the ZIB anode, Researchers proposed to have atleast 40 % DODZn to match the energy
density of Zn-air battery with conventional Li-ion batteries [51]. In
Fig. 4. (a) Battery reaction mechanism schematic diagram of α-MnO2 and CMO. Adapted with permission [46]. Copyright (2019), American Chemical Society. (b)
Schematic diagram showing the dissolution of vanadium in an aqueous electrolyte of V2O5 and NH-V. Adapted with permission [45]. Copyright (2021), Royal Society
of Chemistry.
6
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
concurrence to this, several strategies regarding efficient electrodepo coordinated with TFSI− ion pairs in case of Zn-(TFSI)2 electrolyte and
sition of Zn either via anode protection or using a 3D substrate have been CF3SO−3 ion pair in Zn(CF3SO3)2 electrolytes during electrodeposition
studied to enable higher DOD conditions [52–54]. process rather than interacting with H2O, which prevents the formation
A study presented by Ying et al. showed that the dendrite growth of zincate complexes on Zn anode surface and potential dendrite growth
increases with current density and limits the life cycle for higher depth [58–61]. Although these electrolyte present promising results, they are
of discharge in ZIBs [52]. To overcome this issue, multicapsular carbon significantly costlier than conventional ZnSO4 or KOH electrolyte
fibers (MCFs) interlayer was introduced near the interface of Zn metal limiting their practical application. Hence, a study has been focused on
anode to present homogenous Zn2+ flux and controlled DOD condition. using electrolyte additives to improve the properties of conventional
The cyclic test was conducted by fabricating a 2 × 3 cm2 pouch cell electrolytes that allow uniform Zn electrodeposition during the cycling
battery using 10 μm Zn foil (6.95 mg/cm2, 5.7 mAh/cm2) and MCFs as of ZIBs [58]. A high ion concentration of the electrolyte is one of the
interfacial layer, and the ZIB was cycled at DOD of 33 % to achieve a desired factors to obtain high ion conductivity in electrolytes. Unfortu
high specific capacity of 165.7 mAh/g over 250 cycles. The obtained nately, this results in electrolyte saturation issues and early drying of
energy density was 150.3 Wh/kg considering total weight of anode and electrolytes while improving the cathode dissolution problem and sta
cathode. bilizing the performance of ZIBs [62].
Li et al. proposed that the cycle life of Zn metal anodes with carbon Electrolyte decomposition is another issue realized in ZIBs. Side re
fiber backbone is affected by depth of discharge and current density in actions such as the hydrogen evolution reaction, Zn hydride formation,
ZIBs [55]. It was found that 3D porous Zn metal anode with a large dissolution of the cathode, and H+ interaction in the cathode can
surface area presents reduced local current density on electrode surface, significantly change the H2O concentration within the electrolyte and
and facilitates uniform stripping and plating of Zn against the traditional affect the long-term stability of ZIBs [62]. Especially in Zn-air batteries,
Zn metal anodes. The study evaluates PAN fibers as backbone for Zn the exposure to air also results in the evaporation of electrolyte and the
metal electrode under different DOD conditions as 10, 20, 40, and 60 %, drying of ZABs. Hence, special attention is necessary to counter these
and current density conditions as 0.5–4 mA/cm2 to present an in-depth anomalies and stabilize the functioning of ZIBs. To overcome this issue,
understanding for Zn electrodeposition. The study shows an increased researchers have focused on developing solid-state electrolytes and
overpotential value and decreased life cycle for symmetric cells as they reviewed them in previous reports [63–66]. ZIBs face significant chal
applied higher current density and DOD conditions. For Zn@CNF at 40 lenges in their development, involving issues such as cathode dissolu
% DOD and 4 mA/cm2, the cells showed high cycling stability and tion, dendrite growth, parasitic side reactions, and electrolyte
maintained low overpotential value for symmetrical cell voltage profile decomposition. This section detailed the major challenges faced by ZIBs,
as compared to that of reference cells using Zn@Ti. Although study discussing the causative mechanisms of these challenges as well as their
presents an increase in DOD upto 60 %, the practical applicability is still adverse effects on battery performance. The practical application of ZIBs
limited to 15.5 % based on their full cell analysis. can thus only be achieved through the mitigation of the issues put forth
Considering a detailed mechanistic understanding of Zn dendrite in this section. To this end, researchers have studied different strategies
growth, Zhao et al. proposed a multifunctional brightener-inspired to resolve these issues extensively in recent years. These strategies are
interphase for aqueous Zn anodes to enable 85 % DOD resulting in an detailed in the following section.
ultrahigh areal capacity of 10 mAh/cm2 and stable cyclic performance
over 150 h [56]. The low O2 permeability of polyamide polymer pre 4. Strategies to resolve issues facing Zn-ion batteries
vents water/O2 induced corrosion and passivation of Zn anode. Addi
tionally, the reduced Zn hydroxides and zincates species on coated Zn As has been brought forth in the previous section, there are
anode surface elevates the nucleation barrier and restricts 2D diffusion numerous challenges facing the development and application of Zn-ion
of Zn2+ ions, therefore inhibiting the dendrite growth. By fabricating a batteries currently. As such, current research is focused on developing
high mass loading MnO2 (15 mg/cm2, 4.5 mAh/cm2) cathode and Zn solutions to mitigate these challenges in order to facilitate the practical
foils (14.28 mg/cm2, 11.7 mAh/cm2) with resulting N/P ratio of 1.6, and large-scale application of ZIBs. The major focus of these mitigation
study presents a real prototype for ZIBs with high DOD condition, while strategies is the inhibition of the growth of zinc dendrites, which is the
also achieving a high capacity retention of 84 % after 600 cycles [56]. most prevalent issue facing the development of ZIBs. The majority of the
Achieving higher DOD condition can thus enable practical applica strategies employed achieve this either via the provision of additional
tions of high energy density ZIBs. More details on enhancing the anode mechanical strength or reduction of local current density. Other stra
protection and improving the cyclic performance for ZIB are discussed in tegies are employed to enhance corrosion resistance and inhibit the
later sections. Having discussed challenges faced from an anodic and prevalence of HER at the anode. [67] Furthermore, several strategies are
cathodic perspective in the previous sections, it is important to consider aimed specifically at mitigating cathode dissolution and passivation,
the major issue brought about by the electrolyte utilized in ZIBs. Elec with electrolyte optimization strategies also receiving research atten
trolyte drying and decomposition are major concerns in the develop tion. This section examines several major mitigation strategies in detail
ment of ZIBs and are directly affected by the type of electrolyte selected and provides an understanding of why the given strategy was chosen
as well as the quantity and consumption rate. These factors and chal and how it has been applied by researchers in recent years.
lenges are put forth and discussed in the following subsection.
4.1. Electrodeposition of Zn on carbon substrates
3.5. Issues with electrolyte type, quantity, consumption, and drying
Severe zinc dendrite growth is one of the most notorious challenges
An aqueous or non-aqueous ionic electrolyte serves as an electrically facing the operation of Zn-ion batteries, as it causes cell failure via short-
insulating and ionically conductive medium between the anode and circuit as well as poor cycling life, thereby hindering Zn-ion battery
cathode of ZIB. Several ionic compounds such as ZnCl2, ZnSO4, Zn- application. One of the potential strategies to mitigate this issue that has
(TFSI)2, Zn(CF3SO3)2, Zn(NO3)2, Zn(CH2COO)2, ZnF2, Zn(ClO4)2 and been extensively studied in recent years is the electrodeposition of zinc
KOH have been studied in the literature for the fabrication of ZIBs onto carbon substrates. The electrodeposition of Zn on carbon substrates
[12,57,58]. The type of ionic salt, its concentration, ion conductivity, has a significant effect on the inhibition of zinc dendrites during and
and electrolyte medium play a major role in affecting the performance of after cycling. The main purpose of incorporating carbon substrates is the
ZIBs. Recently, it has been realized that Zn stripping and plating in alleviation and inhibition of dendrites, however, these materials also
presence of Zn-(TFSI)2 and Zn(CF3SO3)2 electrolytes results in dense and display excellent electrical conductivity. This is advantageous for the
dendrite-free structures [58,59]. The Zn2+ ions in ZIBs stay closely stabilization of the Zn plating and stripping process. In addition, carbon
7
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
materials provide additional mechanical strength to the Zn anode can be seen from Fig. 5(e-f), there is no agglomeration present for the
thereby further inhibiting the growth of Zn dendrites. Li et al. carried out carbon and nitrogen elements and such these elements are evenly
a study in which an amine-functionalized carbon cloth (CC) was con distributed on the CC. Galvanostatic charge-discharge tests revealed that
structed to act as a guide for the nucleation and subsequent orderly the cycling life of the synthesized Zn/PANI@CC anode is 250 h at a
growth of the overall zinc anode [68]. A schematic of the Zn deposition current density of 0.05 mAh/cm2 and an areal capacitance of 0.25 mA/
process is shown in Fig. 5(a-b). Through the in situ polymerization of cm2 [68]. This value is about 5 times as long as that of a bare Zn foil
aniline, the researchers were able to incorporate abundant amine- anode (47 h) and about 3 times as long as that of a Zn/CC anode (75 h).
functional groups onto the surface of CC [68]. SEM images of the CC In addition, SEM images taken after cycling show that severe corrosion
before and after polymerization (Fig. 5(c-d)) show a negligible differ occurs on the Zn foil anode (Fig. 5(i-l)), with the Zn/CC anode producing
ence in morphology, with FTIR spectra indicating the successful growth large amounts of dead zinc (Fig. 5(j-m)). However, the morphology of
of PANI on the CC surface with the formation of three new absorption the Zn/PANI@CC anode remains largely unchanged (Fig. 5(k-n)) as a
peaks at 3500, 1598, and 795 cm− 1 (Fig. 5g) [68]. The DFT calculations result of the vast improvement in the zinc plating/striping process
on most stable configuration of basal plane and cross-section of Zn on brought about by the NH2 groups.
pure and amine decorated graphene revealed that the amine groups on In another study carried out by Wu et al., Zn was electrodeposited
CC surface significantly improves the binding energy between zinc onto carbon paper (CP) to form a Zn@CP anode for use in a Zn-ion
atoms and the CC surface. Moreover, resulting conductivity of amine battery [69]. The effect of electrodeposition conditions (current den
group functionalized graphene upon absorption of Zn-ion was much sity and time duration) on the underlying electrode morphology and
higher as compared to pure graphene resulting in an improved stripping subsequent electrochemical performance was extensively studied. Fig. 6
and plating behavior for Zn on NH2-functionalized CC surface [68]. As (a-h) shows SEM images of these varying morphologies. As can be
Fig. 5. Schematic illustration of Zn deposition on (a) raw CC and (b) amine-functionalized CC. SEM images of (c) CC and (d) PANI@CC. I Carbon and (f) nitrogen
element distribution in PANI@CC. (g) FTIR spectra of CC and PANI@CC. (h) GCD curves of cells assembled with Zn foil, Zn/CC, and Zn/PANI@ CC electrodes at a
current density of 0.25 mA/cm2, inset showing the local magnification. SEM images of the anodes after cycling: (i,l) Zn foil (j,m) Zn/CC and (k,n) Zn/PANI@CC.
Adapted with permission [68]. Copyright (2021), American Chemical Society.
8
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
observed, an increase in deposition time increases the Zn grain size, thus nucleation sites as there is great difficulty in overcoming nucleation
leading to a denser electrode overall. The morphologies range from activation energy, leading to the formation of nanowire and nanoflake
nanowires to flower-like nanoflakes to large Zn grains [69]. This morphology [69]. The Zn@CP electrode electrodeposited under 50 mA/
morphology variation is also a result of the deposition current density, as cm2 (Zn@CP-50) was found to possess a homogeneous structure and was
a lower current density leads to the formation of a small number of thus used as an anode in a Zn-ion battery. Fig. 6(i-l) shows the
Fig. 7. SEM images of (a) pristine carbon fiber substrate and (b) Zn@CFs anode, inset (b) is a cross-view of Zn@CFs anode (c) Mapping image of the as-prepared
Zn@CFs anode, Zn element was marked in red (d) XRD patterns of Zn@CFs and pristine carbon fiber substrate. (e) CV scanning profile at 0.5 mV/s, (f) galvanostatic
discharging/charging profiles at 1/3, 1, 2, 5C rate, respectively. (g) Cycling performances of Zn@CFs|α-MnO2 full cell at 1C rate. Adapted with permission [70].
Copyright (2018), Royal Society of Chemistry. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of
this article.)
9
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
Fig. 8. (a) Zn nucleation overpotentials of different collectors (b) Schematic diagram of the Zn plating and stripping process on Cu foam. Coulombic efficiencies of Zn
vs metal collector asymmetric cells under different current densities with an areal capacity of 1 mAh/cm2: (c) 1 mA/cm2; (d) 2 mA/cm2; and (e) 5 mA/cm2. (f) Long
cycle performance at 1 A/g. Adapted with permission [71]. Copyright (2019), American Chemical Society.
10
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
copper foam is shown in Fig. 8b. As can be observed from Fig. 8(c-e), the 4.3. Zn metal alloying
copper foam holds a stable coulombic efficiency of 98 % at 1.0, 2.0, and
5.0 mA/cm2 which is a stark contrast to nickel foam, which exhibits Zn metal alloying has emerged as a promising method to alleviate
severe volatility. This confirms the effect of a lower zinc nucleation severe dendrite growth and the subsequent limited cycle life of the
overpotential, as nickel foam possesses a relatively higher zinc nucle overall battery. Specifically, the alloying of zinc with other metals leads
ation overpotential of 101.4 mV, which leads to its inferior performance to the improvement of anode stability—through the reduction of local
in terms of coulombic efficiency and plating/stripping stability current density, thereby inhibiting dendrite growth—and corrosion
compared to that of copper foam. The Zn@Cu foam was then used as an resistance. Zinc alloys can also act as nucleation centers, thereby causing
anode in a full cell, and as shown in Fig. 8f, the Zn@Cu foam exhibits a uniform deposition of zinc [73]. Additionally, zinc metal alloying is
capacity of 173.8 mAh/g after 600 cycles at 1 A/g which is much higher utilized to inhibit adverse side reactions such as the hydrogen evolution
than that delivered by the Zn foil anode and the Zn@Cu foil anode. reaction. Zinc alloy materials also exhibit high damping and superior
Kang et al. developed a highly stable 3D Zn anode by electrodeposing bearing capacity [73]. Liu et al. fabricated a 3D nanoporous (NP)
Zn on a porous copper skeleton [72]. The 3D porous copper skeleton was Zn–Cu alloy to be utilized as a long-life anode in high-voltage double
prepared via a chemical etching method to prevent the introduction of electrolyte aqueous ZIBs [74]. The nanoporous structure is a direct
impurity phases like copper oxide, thereby ensuring excellent electrical result of the large electrochemical potential difference between zinc and
conductivity. A schematic of the resulting Zn deposition and stripping copper which thus facilitates the selective dissolution of zinc through the
process is shown in Fig. 9a. The coloumbic efficiency of the symmetric provision of a sufficient overpotential. Additionally, incorporating
cells with the 3D Zn anode is maintained at values close to 100 % after copper as an alloy material leads to a reduction of local current density
initial cycling (Fig. 9b) and as such, it can be concluded that excellent Zn and facilitates the homogeneous deposition of zinc, as the inherent rapid
deposition and stripping reversibility are achieved. Full-cell electro surface diffusivity of copper leads to the continuous opening up of the
chemical testing revealed that the 3D Zn|Mn02 full cell (Fig. 9c) delivers nanoporous structure. As a result, the fabricated 3D NP Zn–Cu alloy
a capacity of 364 mAh/g at 0.1 A/g with coulombic efficiency main anode exhibits excellent capacity retention of 95.2 % after 5000 cycles.
tained at 100 % over 300 cycles, as shown in Fig. 9d. The excellent Symmetric cell testing reveals a highly stable zinc deposition/stripping
electrochemical performance can be attributed to the excellent electrical behavior as the cell can be charged and discharged for up to 300 h at 2
conductivity and open structure of the 3D porous copper skeleton that mA/cm2.
was used as a deposition substrate. To alleviate irreversibility problems caused by zinc dendrite growth,
Electrodeposition of zinc on metal substrates has been proven to be Wang et al. proposed a eutectic-composition alloying strategy that is
an effective method to inhibit dendrite growth in ZIBs. However, this based on a Zn/Al alloy system [75]. The underlying eutectic structure of
strategy does not address the other major issue facing ZIBs: adverse side this alloy system is composed of alternating zinc and aluminium
reactions such as HER and corrosion reactions. Left unaccounted for, lamellae. An Al2O3 shell forms on the aluminium lamellae which
these side reactions can severely limit the performance and life cycle of effectively prevents the dissolution of Al, thereby facilitating selective
the ZIB. The following section discusses Zn metal alloying as a method of stripping or plating of zinc and, in turn, guiding the growth of zinc. As a
improving corrosion resistance and inhibiting HER at the anode. result, the fabricated Zn/Al exhibited dendrite-free Zn stripping/plating
with high coulombic efficiency for >2000 h. Furthermore, when used in
a full cell, an energy density of 230 Wh/kg is delivered with a capacity
retention of almost 100 % after long-term charge/discharge cycling. The
Fig. 9. (a) Schematic diagrams of Zn deposition/stripping processes on 3D Zn electrodes and planar Zn foil electrodes (b) CE values vs cycle number (c) Schematic of
3D Zn anode-MnO2 nanosheet cathode full cell (d) Cycling performance of full cells with 3D Zn anodes or planar Zn foil anodes at 0.4 A/g in an electrolyte containing
2 M ZnSO4 and 0.5 M MnSO4. Adapted with permission [72]. Copyright (2019), American Chemical Society.
11
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
inherent low cycle life exhibited by zinc anodes can be made worse with better tolerance to the dendrite formation as observed in sym
under operating conditions of high current densities and high depth of metrical cell test. Based on the overall research, the controlled In doping
discharge (DOD) [76]. Fayette et al. sought to mitigate this issue by facilitates the formation of a unique porous structure during dealloying,
fabricating high-performance InZn alloy anodes for zinc battery appli resulting in improved dendrite suppression and, subsequently, improved
cations [76]. This approach takes advantage of well-dispersed zinc do electrochemical performance.
mains that surround indium domains. This amplifies the tolerance to In another study, Qi et al. fabricated a dendrite-free composite anode
zinc dendrites through the formation of porosity during discharge. The made up of a eutectic ZnAl alloy and copper mesh (ZnAl@Cu-mesh)
fabricated InZn alloy anode exhibits a polarization of ~5 mV, a value [77]. Similar to the aforementioned study by Wang et al. [75], the ZnAl
that is much lower than that of the Zn foil anode (~30–40 mV) and AlZn alloy structure is comprised of alternating Al nanoflakes and Zn blocks.
alloy (~20 mV). In addition, the InZn alloy also exhibits the longest The copper mesh was incorporated as a scaffold to facilitate the provi
cycle life of 1000 h, compared to 130 and 225 h exhibited by Zn foil and sion of a uniform electric field distribution. The Al nanoflakes form an
AlZn alloy anodes, respectively (Fig. 10(a-c)). The asymmetric spikes in Al2O3/Al shell-core structure by consuming the oxygen present in the
polarization were possibly caused either due to difference in loading of electrolyte, which restrains the lateral diffusion of zinc ions during the
electrodeposited samples as compared to target loading amount and/or zinc deposition process. This leads to a reduction in zinc dendrite for
some additional possibilities of In accumulation on anode surface for mation. This also allows the zinc region of the anode to remain active
InZn anode that causes change in potential of anode vs pure Zn and/or during Zn stripping or plating, which reduces the possibility of Zn
uneven dissolution of Zn over the electrode surface [76]. Even at a passivation. The resulting symmetric cell using this composite exhibits a
higher current density of 10 mA/cm2, the InZn alloy still displays the low polarization of 30 mV at 0.5 mA/cm2 and cycling stability of 240 h
longest cycle life of over 700 h compared to 90 h and 310 h for Zn foil at 0.5 mA/cm2. When the ZnAl@Cu-mesh was used as an anode in a full
and AlZn alloy anodes, respectively (Fig. 10(d-f)). Comparing the cell, the cell achieved capacity retention of 95 % after 2000 cycles at 2
cycling stability of the alloyed Zn anodes in full cells to that of com A/g, a vast improvement compared to a similar full cell using a Zn metal
mercial zinc foil, it was found that both the InZn and AlZn alloy anodes anode, which failed after 750 cycles due to short-circuiting. Through
exhibit similar performance to the commercial zinc (Fig. 10g), however zinc metal alloying, the challenge of parasitic side reactions can be
12
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
mitigated by the selection of metal alloys that improve corrosion resis free energy [78]. Such epitaxial deposition of Zn yields high reversibility
tance while simultaneously inhibiting the prevalence of HER at the in Zn stripping and plating study at 4 mA/cm2 current and capacity of
anode. An alternative method of inhibiting corrosion of the anode that 0.8 mAh/cm2 with coulombic efficiency >99 % for over 1000 cycles.
has been found to be effective is the application of coatings on the anode. Even at higher current densities of 40 mA/cm2 and current density of 1.6
The application of coatings has the advantage of even further tuning the mAh/cm2 the symmetrical cell retained CE = 99.9 % over 10,000 cycles.
anode properties, such as its electronic conductivity, to enhance per In a study by Hao et al., a nitrogen (N)-doped graphene (NGO)
formance for a given electrochemical application. The following section protective layer was fabricated on Zn foil via a facile squeegee coating
examines the utilization of protective coatings in the design and syn process [79]. The incorporation of graphene reduces the release of
thesis of zinc anodes. hydrogen during cycling and prevents the hydrolysis of Zn. Further
more, the deposition morphology of Zn metal is regulated by the ample
4.4. Coatings on Zn anode N-doped functional groups, which result in the inhibition of porous
dendrite growth. Symmetric cell testing shows that stable cycling per
The design and incorporation of protective coating layers on Zn formance over 500 h is achieved, as well as a low overpotential of 19
metal anodes have received increasing interest as a strategy to prevent mV. Incorporating the NGO@Zn anode in a full cell results in the battery
dendrite formation as well as inhibit the accumulation of reaction delivering a capacity of 89.1 mAh/g and a coulombic efficiency of ≈99
byproducts. The utilization of coatings on Zn anodes restricts the direct % at 1C after 600 cycles.
contact between the battery electrolyte and anode, which inhibits the Fan et al. sought to mitigate uncontrollable dendrite growth and
corrosion of the anode material. Additionally, coatings can also facilitate anode corrosion by coating natural halloysite nanotubes (HNTs) on Zn
the provision of ample zinc deposition sites and provide a uniform foil to make an HNTs@Zn electrode material [80]. As can be observed in
electric field distribution. Zinc coatings can either be electronically Fig. 11(a-c), HNTs@Zn//HNTs@Zn symmetric cells exhibit a longer
conductive or insulative, with the former facilitating uniform electric lifespan than that of Zn//Zn cells across all the tested current densities,
field distributions while the latter inhibiting side reactions and the with a maximum lifespan of 2000 h being realized at 0.2 mA/cm2. This
growth of zinc dendrites by blocking the charge transfer from metallic is brought about by the negative charge present on the surface of the
zinc to water molecules [7]. Furthermore, the close contact between the HNTs which facilitates the inhibition of dendrite growth under the
coatings and the Zn anode can lead to a decrease in interface resistance protective layer by enabling uniform charge distribution on the surface
and anode polarization [7]. of Zn foil. HNTs@Zn reversibility during Zn plating and stripping was
Recent scientific study by Zheng et al. presented epitaxial electro also enhanced, with an average coulombic efficiency of 97.9 % for 500
deposition of Zn with a locked crystallographic orientation at (0002)Zn cycles realized, as shown in Fig. 11d. This is in stark contrast to the
place on graphene coated substrate [78]. It was proposed that textured behavior of a Zn foil anode, in which pronounced fluctuations appeared
interphases with low-lattice mismatch and electrochemically inactive after just 70 cycles, implying unstable Zn stripping and plating
nature with selected crystal symmetry would facilitate heteroepitaxial (Fig. 11e). A schematic of the Zn stripping/plating behavior of bare Zn
nucleation and growth of metal anode in a strain free state to create foil and HNTs@Zn is presented in Fig. 11f, which visually shows the
uniform deposition behavior. Zn exhibits strong tendency to deposit as a random deposition and accumulation of zinc dendrite present in the Zn
platelet with exposed closed pack (0002) plane and low thermodynamic foil.
Fig. 11. Symmetric plating/stripping tests on HNTs@Zn and bare Zn electrodes: (a) 0.2 mA/cm2 up to 0.2 mAh/cm2; (b) 1 mA/cm2 up to 1 mAh/cm2; (c) 5 mA/cm2
up to 5 mAh/cm2. (d) Coulombic efficiency of HNTs@Zn//Cu of 500 cycles (e) Coulombic efficiency of Zn//Cu of 100 cycles (f) Schematic of the Zn stripping/plating
behavior on the surface of bare Zn and HNTs@Zn. Adapted with permission [80]. Copyright (2022), American Chemical Society.
13
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
Li et al. developed a low-cost multifunctional Zeolite-membrane as a for zinc deposition dissolution, facilitates the provision of a small zinc
separator using a slurry casting method consisting a mixture of Zeolite, deposition overpotential, and enhances electrolyte wettability [84]. As
ZnSO4 and PTFE to obtain a conductive Zn-ion membrane for sup such, the Ag-coated Zn anode (Ag–Zn) sustains up to 1450 h of repeated
pressing the dendrite growth and I−3 shuttling [81]. As compared to the plating/stripping at 0.2 mA/cm2 compared to a bare Zn anode that
traditional glass-fiber separator, Zeolite-membrane showed significant sustains Zn plating/stripping up to 110 h (Fig. 12a). The Ag–Zn anode
reduction in dendrite growth. The uniform electric field distribution and continues to outperform the bare Zn anode as the current density is
ion-conductive pathways within the Zeolite membrane allowed the increased to 1 mA/cm2 and 2 mA/cm2, as shown in Fig. 12 (b-c).
Zn–I2 battery to retain 91 % capacity for over 30,000 cycles at current Following in-situ optical visualizations, it was confirmed that for the
density of 4 A/g. In a similar study, the first principle calculation using bare zinc anode, small protrusions begin to appear and evolve into
FAU and ETR type zeolite structures showed high migration barrier for dendrites gradually (Fig. 12d) whereas the Ag–Zn anode exhibits a
hydrate Zn2+ as compared to bare Zn2+, responsible for preventing the smooth surface during zinc deposition (Fig. 12e). Post-mortem SEM
corrosive side-reactions and dendrite formation on Zn anode surface images show that porous dendrites are formed on the surface of the bare
[82]. The resulting battery showed high cyclic performance of over Zn anode due to uneven Zn deposition (Fig. 12f) whereas dense and
5600 cycles with 91.92 % capacity retention at current density of 2 A/g. uniform Zn deposition is observed for the Ag–Zn anode (Fig. 12g). This
In another study, Cao et al. sought to promote uniform Zn nucleation confirms that incorporating Ag leads to the formation of nucleation sites
by coating the surface of Zn foil with a Ni2Zn21 alloy (ZnNi) via elec that guide the uniform deposition of zinc. Full cell performance
trodeposition [83]. Density functional theory (DFT) was utilized for confirmed that the Ag–Zn anode delivers excellent electrochemical
further analysis of the nucleation mechanism. DFT results showed that performance compared to that of a bare Zn anode as is shown in
due to the stronger binding ability of ZnNi to Zn compared to bare Zn, Zn Fig. 12h, where the difference in specific capacity delivered by the
nuclei will preferentially form around ZnNi instead of forming dendrites respective anodes becomes more pronounced with an increase in current
by the continual growth of protrusions on the surface of initial Zn nuclei. density. Fig. 12i shows that after 1500 cycles, the full cell with an
As a result, the as-synthesized anode (Zn@ZnNi) exhibits excellent sta Ag–Zn anode retains a capacity of 171 mAh/g which is greater than that
bility for over 2200 h at 2 mA/cm2 in the symmetric cell. A full cell retained by the full cell with a bare Zn anode (143 mAh/g) for the same
utilizing the Zn@ZnNi anode delivers a cycling performance of 500 number of cycles, thus confirming that the incorporation of an Ag
cycles with a capacity of 207 mAh/g at 0.5 A/g and 1100 cycles with a coating on Zn leads to an overall improvement in electrochemical per
capacity of 148.5 mAh/g at 1 A/g. formance for a Zn-ion battery.
Lu et al. coated Zn with Ag to guide uniform zinc deposition for The mitigation strategies discussed up to this point have focused
improved aqueous Zn-ion batteries [84]. By incorporating Ag with a exclusively on challenges affecting the Zn anode. In order to have a
strong Zn affinity into the anode material, the energy barrier of Zn comprehensive and holistic mitigation of the issues facing zinc ion
nucleation can be reduced. Furthermore, Ag coating improves kinetics batteries, electrolyte issues must also be addressed and mitigated. The
Fig. 12. Cycling performance of symmetric cells at a current density of (a) 0.2, (b) 1, and (c) 2 mA/cm2. In situ digital microscopy images of the surface cross-section
of (d) Zn and (e) Ag- Zn, recorded at different deposition times. SEM images of (f) Zn and (g) Ag–Zn in symmetric cells after plating at 1 mA/cm2 for 2 mAh/cm2. (h)
Rate performance of Zn//V2O5-PEDOT and Ag-Zn//V2O5-PEDOT cells. (i) Long-term cycling performance of Zn//V2O5-PEDOT and Ag-Zn//V2O5-PEDOT cells at 5
A/g. Adapted with permission [84]. Copyright (2021), American Chemical Society.
14
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
following section examines the incorporation of additives in the elec (PEG), and polyethylenimine (PEI)) or inorganic (such as Bi2O2, Pb3O4,
trolyte as a strategy to resolve issues in ZIBs brought about by the use of and Na2SO4). Organic additives can reduce the local current density via
a particular electrolyte type and/or quantity. direct adsorption on the tips of zinc protuberances and as such Zn that
has been reduced from Zn2+ ions will not deposit on these pro
4.5. Electrolyte additives tuberances, effectively alleviating the growth of zinc dendrites [7].
Additionally, some organic electrolytes can decrease the energy barrier
Electrolyte engineering plays vital role in alleviating the issues of the Zn2+ desolvation process, which leads to improvements in reac
including cathode dissolution, dendrite formation, corrosion, hydrogen tion kinetics and zinc plating/stripping reversability [7]. Inorganic ad
evolution and so on. There have been several approaches including ditives decrease the ionic conductivity, which in turn increases
electrolyte types, organic or aqueous systems, salt-in-water, water-in- polarization, thereby inhibiting the rate of zinc deposition. Additionally,
salt, semi-solid or gel-type electrolytes and solid-state electrolytes dis inorganic additives can alter the crystallographic orientation of depos
cussed in previous reports [85–88]. Since majority of research is focused ited zinc from the reactive (100) plane to the less reactive (002) plane,
on aqueous systems considering safety and cost efficiency, scope of this which leads to a lower probability of zinc dendrites being formed [7].
section is focused more towards aqueous ZIBs and electrolyte optimi Liu et al. sought to study two typical additives, namely PVA and vanillin,
zation using additive materials. to understand their modifying effects on (i) charge/discharge of the zinc
The incorporation of additive materials in electrolytes is a facile anode, and (ii) zinc electrodeposition [89]. Both additives were found to
strategy for improving zinc anode stability and hence improving cycling be capable of guiding the uniform deposition of zinc during the plating
performance. The additives incorporated into the electrolyte can either process. However, their effects on zinc anode dissolution are different.
be organic (such as poly(vinyl alcohol) (PVA), polyethylene glycol PVA promotes zinc corrosion which causes a shape change of the anode,
Fig. 13. Schematic illustrations of Zn deposition on Cu foam (a) without or (b) with TBA2SO4 as an electrolyte additive. Cycling performance comparisons of Zn//Zn
and 3D- Zn//3D-Zn symmetric cells in different electrolytes at current densities of (c) 2 mA/cm2 with a fixed capacity of 2 mAh/cm2, (d) 5 mA/cm2 with a fixed
capacity of 2 mAh/cm2, (e) 10 mA/cm2 with a fixed capacity of 2 mAh/cm2, and (f) 5 mA/cm2 with a fixed capacity of 5 mAh/cm2. SEM images of (g) Zn plate in
normal electrolyte after 20 cycles, (h) 3D–Zn in normal electrolyte after 20 cycles, (i) 3D–Zn in the TBA electrolyte after 20 cycles, and (j) 3D–Zn in the TBA
electrolyte after 150 cycles, all at 2 mA/cm2 for 2 mAh/cm2. Adapted with permission [90]. Copyright (2020), American Chemical Society.
15
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
leading to adverse effects on the electrochemical performance of the exhibited an average coulombic efficiency of 99.16 % for 100 cycles, as
resulting battery. PVA does, however, improve the utilization of active shown in Fig. 14e. Additionally, adding GO into the electrolyte leads to a
materials. Vanillin, on the other hand, inhibits anode dissolution, with lower nucleation overpotential of 116 mV, compared to 155 mV
the adverse side-effect of its use being a decrease in rate performance of exhibited by cells utilizing a pure ZnSO4 electrolyte, which confirms
the anode. To this end, it was found that the electrochemical perfor faster reaction kinetics due to the additional Zn2+ nucleation sites
mance of the battery can be improved by the simultaneous addition of (Fig. 14 (f,g)). The impact of various electrolyte additions in ZIBs is
PVA and vanillin to the electrolyte. The additives work synergistically to summarized in Table 2.
realize improvements in cycle life, rate performance, and discharge Having discussed mitigation strategies for issues facing Zn anodes
energy retention. and now having discussed the electrolyte, it is imperative to direct focus
Bayaguud et al. incorporated tetrabutylammonium sulfate to the cathode materials utilized in ZIBs. Cathode materials are a major
(TBA2SO4) as a cationic surfactant-type electrolyte for Zn-ion battery bottleneck in the development of ZIBs owing to issues such as cathode
applications [90]. During the process of plating TBA+ cations adsorb and passivation and cathode dissolution. The following section examines a
aggregate at protuberances, thereby forming a protective layer on the strategy to prevent cathode passivation via the stabilization of anodes,
anode that inhibits the lateral diffusion and aggregation of Zn2+ along which takes advantage of the counter-dependent nature of anode and
the anode surface, as well as inhibiting the tip effect as Zn2+ ions are cathode stability inherent to ZIBs.
forced to deposit on flat regions of the anode, thereby inhibiting
dendrite formation. A schematic of this process is presented in Fig. 13 (a- 4.6. Stabilizing anodes to prevent cathode passivation and vice versa
b). As a result, symmetric cells using an electrolyte with the (TBA2SO4)
additive greatly outperformed cells utilizing normal electrolytes. As can Even though the Zn anode presents a high specific capacity of 820
be observed in Fig. 13 (c-f), cells in the TBA electrolyte exhibit superior mAh/g and 5854 mAh/cm3, the final capacity of ZIB depends on the
cycling stability across varying current densities and specific capacities. specific capacity of the cathode [10]. The access to anode material will
Post-mortem morphological changes of the Zn anodes were character be a dead weight for ZIBs if the Zn ions from the anode are not effectively
ized by SEM as shown in Fig. 13 (g-j), where it can be observed that utilized. Since the Zn ion consumption is controlled by the gravimetric
anodes cycled in the normal electrolyte form large dendrites that lead to capacity of the cathode, the electric field distribution in the cathode can
the failure of the corresponding cells (Fig. 13g). However, the zinc anode be affected by the passivation of the Zn anode and needs further
cycled in the TBA electrolyte exhibited a dense, smooth, dendrite-free investigation [22]. It has been found that anode and cathode stabiliza
surface after 150 cycles (Fig. 13j). tion are counter-dependent phenomena that significantly affect the
Abdulla et al. developed a hybrid electrolyte utilizing graphene oxide performance of ZIBs. [22] At neutral pH, the reactions at the anode
(GO) as an additive to eliminate zinc dendrites for Zn-ion battery ap follow [22]:
plications [91]. Symmetric cell testing was utilized to study the effect of
GO additives on long-term Zn plating/stripping processes. As can be Zn ↔ Zn2+ + 2e− (20)
observed from Fig. 14 (a-c), Zn//Zn batteries in an electrolyte with no
GO suffered short circuits and had relatively short lifespans across Zn2+ + 2H2 O ↔ Zn (OH)2 + 2H+ (21)
varying current densities. This is in stark contrast to Zn//Zn batteries
which consistently supply long lifespans of up to 650, 400, and 140 h at Zn(OH)2 ↔ HZnO−2 + H+ (22)
1, 5, and 10 mA/cm2 respectively. EIS measurements showed that the
internal impedance of the battery with GO additive was lower than that HZnO−2 ↔ ZnO2+
2 +H
+
(23)
of the battery without GO additive (Fig. 14d). Additionally, coulombic Fig. 15 shows the water immersion test for the Zn anode, presenting
efficiency measurements during zinc plating/stripping confirmed the the natural oxidation of Zn in presence of water over time. Eventual
excellent reversibility of the zinc anode in the TBA electrolyte, which dendrite growth can further worsen the Zn oxidation, resulting in dead
Fig. 14. Electrochemical investigation of Zn anodes employing GO electrolyte additive at current densities of (a) 1, (b) 5, and (c) 10 mA/cm2. (d) EIS measurements
of Zn//Zn batteries with various electrolytes (e) Coulombic efficiency of Zn//Ti batteries. GCD profiles of Zn//Ti batteries (f) without GO additive and (g) with GO
additive in the electrolyte. Adapted with permission [91]. Copyright (2021), American Chemical Society.
16
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
17
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
Fig. 15. (a) Partially MoS2 coated Zn foil before and after 7 days of water immersion test with an SEM image of MoS2 coated and non-coated interface showing the
oxidation of Zn in water. (b) SEM image of partially MoS2 coated Zn anode after 10 charge-discharge cycles. (c) Higher magnification SEM image of the interface. (d)
Stability test of Zn-MnO2 battery using MoS2 coated Zn anode at 1 A/g. (e) The galvanostatic charge-discharge curves for ZIBs using MoS2-coated Zn anode after 60
cycles. Adapted with permission [22]. Copyright (2020), American Chemical Society.
Table 3
The performance of batteries assembled with different Zn-anode.
Different Zn-anode Electrolyte Current density Capacity retention rate Life cycle Ref.
Zn@CDs ZnSO4 5.0 A/g 81.6 % afterwards 500 cycles 3000 h [106]
Zn@InF3 ZnSO4 + MnSO4 3.0C 80 % afterwards 1000 cycles 6000 h [107]
Zn@ZIF-8 ZnSO4 + MnSO4 0.5 A/g 76.0 % afterwards 250 cycles 5000 h [108]
Nb2O5@Zn Zn(OTf)2 2.0 A/g 78.6 % afterwards 500 cycles 1000 h [109]
Cu-Zn@Zn Zn(OTf)2 2.0 A/g 88.2 % afterwards 600 cycles 5496 h [110]
ZnLiMn ZnSO4 + MnSO4 1.0C 96.0 % afterwards 400 cycles 1000 h [111]
ZnxCuy@Zn Zn(OTf)2 + SDS + Mn(OTf)2 1.0 A/g 84.0 % afterwards 800 cycles 1900 h [112]
Zn@Cu-Sn@SSM Zn(OTf)2 2.0 A/g 84.0 % afterwards 1000 cycles 1050 h [113]
ZIF-8@Zn ZnSO4 5.0 A/g 96 % afterwards 13,000 cycles 800 h [114]
ZnAl Zn(OTf)2 5.0 A/g 95.0 % afterwards 1000 cycles 300 h [115]
CNF/MXene@Zn Zn(OTf)2 2.0 A/g 93.2 % afterwards 500 cycles 2800 h [116]
20F-Zn ZnSO4 + MnSO4 2.0 A/g 68.4 % afterwards 500 cycles 1275 h [117]
electrochemical performance is provided in Table 4. 5. Conclusion and perspectives for high-performance zinc ion
In this section, several mitigation strategies for the challenges facing batteries
ZIBs were detailed from anodic, cathodic, and electrolyte perspectives.
The prevention of zinc dendrite growth and inhibition of parasitic side The success of practical ZIBs is strongly dependent on the anode,
reactions are the main issues addressed by the majority of the presented cathode, and electrolyte designs. As has been put forth in this review, a
mitigation strategies, however, methods to optimize cathode electro holistic approach is therefore required to achieve the design and large-
chemical performance and stability were also presented and discussed in scale application of high-performance ZIBs. Through the successful
detail. The mitigation of the challenges faced in ZIB development re mitigation of the cathode, anode, and electrolyte issues discussed in this
quires a holistic approach in which the anode, cathode and electrolyte review, high-performance ZIBs can be designed and assembled in a
are fully optimized. To this end, the following section provides some facile manner. However, while resolving the issues that plague ZIBs is an
perspectives for the development of high-performance ZIBs. important milestone to achieve, it is not sufficient on its own to realize
the large-scale production of ZIBs. There are other important factors to
consider in the design and production of ZIB technology. Parameters
such as energy density and cycle life are crucial to optimize in order to
realize high-performance ZIBs. Additionally, the cost of production must
18
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
Table 4
Summary of cathode modification strategies to improve the ZIB performance.
Strategy Structural engineering Cathode Capacity Cyclic stability Ref.
materials
Intercalation of pillars Enlarge layer spacing ZnxMnO2 1.746 F/cm2 at 2 83.1 % capacity [139]
mA/cm2 retention (5000
cycles at 15 mA/cm2)
Stabilize material structure Cu-V2O5 (CuVO) 359 mAh/g at 1 A/g 180 mAh/g (10,000 [140]
cycles at 10 A/g)
Reduce electrostatic interactions. LixV2O5⋅nH2O 407.6 mAh/g at 1 A/ 192 mAh/g (1,000 [141]
g cycles at 10 A/g)
Heteroatom doping Promote electronic re-arrangement Ni-doped Mn2O3 252 mAh/g at ≈85.6 % capacity [142]
0.1 A/g retention (2500
cycles at 1 A/g)
Enhance electrical conductivity Mn-doped ZnO 268.1 mAh/g at 147 mAh/g (10,000 cycles at [143]
1 A/g 5 A/g)
Defect engineering Modify the electronic properties Od-MnO2 345 mAh/g at 80 % capacity [144]
0.2 A/g retention (2000
cycles at 5 A/g)
Mn-defective 300 mAh/g at 116 mAh/g (1,500 [145]
MnO 0.1 A/g cycles at 1 A/g)
Micro/nanostructure Enlarge specific surface area H11Al2V6O23.2 288.4 mAh/g at 88.6 % capacity [146]
design hollow spheres 0.1 A/g retention (7000
cycles at 5 A/g)
Enhance accessibility to electrolyte VO2 hollow 408 mAh/g at 116 mAh/g (20,000 [147]
spheres 0.1 A/g cycles at 15 A/g)
Increase the number of active sites TiN@V2O5 636 mAh/g at 90.6 % retention [148]
core-shell 0.5 mA/cm2 (3500 cycles at
8 mA/cm2)
Composite construction Combine the advantages and synergistic effects between the V2O5⋅nH2O- 466 mAh/g at 100 % retention [149]
different components graphene 0.1 A/g (5000 cycle at 10
A/g)
be optimized in order to ensure the large-scale production of zinc ion centers is another way of improving the overall energy density of ZIBs
batteries. The environmental impact of ZIBs is an important parameter [150]. Through cathode engineering, this enhancement can be achieved
to consider, especially in light of the current climate crisis, therefore the in two main ways: (i) activation and stabilization of metal active centers
development of environmentally sustainable ZIBs is of paramount via regulation of the chemical environment, and (ii) incorporation of
importance. The following subsections highlight perspectives on extra metal active centers into the atomic matrix of cathode materials
improving energy density and cycle life, optimizing the cost of pro [150].
duction, and ensuring the environmental friendliness of ZIBs. A significant barrier to increased energy density is the overuse of the
Zn anode, which results from the incompatibility between the cathode’s
5.1. Improving energy density and the Zn anode’s unique capacities. The design of advanced Zn anodes
with low thickness and high reversibility through electrode structure
Energy density is an important parameter to consider when devel design is one way of mitigating this issue. Furthermore, increasing the
oping any battery technology, with a high energy density being the most loading mass of cathode materials through cathode engineering is
desirable. Therefore, improving the energy density that these technol another way to reduce the mismatch between anode and cathode,
ogies deliver is a key goal in the development of aqueous batteries, thereby improving the overall energy density of the ZIB.
particularly aqueous zinc-ion batteries. ZIBs have garnered major in
terest in recent years owing to their comparatively higher energy den 5.2. Cost
sities as a result of the direct utilization of zinc metal as an anode [150].
However, the energy density delivered by ZIBs is still not competitive The cost of ZIB presents a major advantage over current Li-ion
enough for industrial-scale applications, which are associated with high technology. The relative cost of ZIBs is targeted at <$100 kW− 1 h− 1
operating voltages and large discharge capacities [44]. This is a result of and potentially <$10 kW− 1 h− 1, whereas Li-ion technology is limited to
the failure of current cathode materials to achieve large specific ca ~$150 kW− 1 h− 1 or higher [14]. Owing to the low cost of Zn metal as an
pacities, large mass loading, and high discharge potentials [150]. As anode, and the natural abundance of MnO2 for the cathode, there is still
such, improving the specific capacity and discharging potential of room for cost improvement through effective design and utilization of
cathode materials is of primary focus to improve the energy density of anode and cathode materials. Cheap fabrication methodology, cost-
high-performance ZIBs. effective electrolytes, and additives, improved anode design by cost-
Replacing traditional ion intercalation cathodes with conversion- efficient passivation methods, and cell component design are a few
type cathodes possessing multi-electron transfer is one of the latest important points to be considered. The stability of the Zn anode in an
strategies to enhance the capacity and hence the energy density of ZIBs aqueous electrolyte presents a greater advantage of ZIBs over LIBs for
[44,150]. Chalcogen-based (S, Se, and Te) and halogen-based (I2 and Br) large-scale production and storage. Hence, cost-effective and scalable
multi-electron conversion reaction cathodes are the main types of con cell components can significantly improve the total weight of the ZIB cell
version type cathodes being investigated. Chalcogens possess high spe and its final energy density.
cific capacities as a result of their multi-electron conversion reaction,
whereas halogens provide a high specific capacity within the voltage 5.3. Long cycle life
window of aqueous electrolytes, thereby forming non-flow cells [150].
Taking advantage of the multi-electron transfer reactions present in The development of long-cycle zinc-ion batteries is critical for their
these two systems has the potential to greatly enhance the energy den practical application. The formation of zinc dendrites, passivation, and
sity of ZIBs. Additionally, enhancing the utilization ratio of metal active hydrogen evolution greatly undermine the cycle life and overall
19
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
electrochemical performance of ZIBs. To this end, mitigating these symmetric cell drops rapidly as DOD and current density increase, as the
challenges will lead to an extended cycle life for the ZIB. Several stra cells exhibited a cycle life of 843 h under 10 % DOD and 0.5 mA/cm2
tegies have been employed in this regard. Liu et al. recently developed a and a cycle life of 60.75 h under 60 % DOD and 4 mA/cm2. While full
novel MOF-based Zn anode (ZIF/Zn) through rational electrode- cells consisting of a Zn@CNF anode and V2O5 cathode exhibited excel
electrolyte design for long-life rechargeable aqueous ZIB applications lent capacity retention (92.1 % after 260 cycles at 0.5 A/g), Zn metal
[151]. This was achieved by the in-situ growth of the ZIF-MOF layer on electrodes must be tested at high current densities and DODs to facilitate
zinc particles through a hydrothermal method shown in the schematic in practical applications.
Fig. 16a. This direct growth, coupled with the utilization of an organic
zinc trifluoromethanesulfonate-based electrolyte, facilitates uniform
charge-discharge and ion distribution at the electrode-electrolyte 5.4. Environmental friendliness
interface. As can be observed in the galvanostatic cycling performance
plot in Fig. 16b, the ZIF/Zn electrode is stable for 110 h, a vast By developing electrochemical energy storage systems that are based
improvement from the bare Zn electrode, which experiences a short on renewable resources, a more environmentally sustainable electricity
circuit at just 20 h of cycling. Furthermore, cycling stability is confirmed generation and storage system can be put in place as an alternative to
by the almost unchanged polarization voltage for the ZIF/Zn electrode, those based on fossil fuels, thereby accelerating progress towards
shown in Fig. 16 (e-f). Testing of a coin cell utilizing a ZIF/Zn anode and achieving the objective of 30 % carbon emission reduction set by the
a MnO2 cathode shows that the coloumbic efficiency is at approximately Paris Agreement [153]. To this end, Iturrondobeitia et al. carried out a
100 % for over 300 cycles (Fig. 16c) indicating excellent charge- study of the cradle-to-gate environmental impacts of six AZIBs utilizing
discharge performance. The cell exhibited an initial specific capacity varying cathode materials [153]. As presented in Fig. 17a, the impact on
of 149 mAh/g, then reached 119.6 mAh/g after 330 cycles, which cor global warming of the 6 AZIBs ranges between 22.1 and 95.2 kg CO2
responds to a retention of 80.3 % (Fig. 16d). equiv. per 1 kWh with an average impact of 45.1 CO2 equiv. being
In another study by Chen et al., a dendrite-free dual porous 3D zinc realized. This value is competitive with that of Zn-air and Li–O2 bat
anode (Zn-3D@600) was developed by coating a Zn@C protective layer teries while also being much lower than those exhibited by sodium ion,
on a 3D zinc skeleton [152]. Through the incorporation of the Zn@C Li–S, and lithium-ion batteries. The high operating voltages of the
protective layer, the resulting Zn-3D@600 anode is endowed with a Na2MnFe(CN)6 and V2O5-bronze batteries facilitate the translation of
more uniformly distributed electric field, which facilitates the inhibition their active mass loading (5 and 10 mg/cm2) into large energy densities,
of dendrite growth. Dendrite growth is inhibited further by the 3D thereby reducing the overall environmental impact. Fig. 17b lays out the
porous structure of the anode provided by the 3D zinc skeleton, which cradle-to-gate environmental impacts of the 6 AZIBs in 18 of the in
accommodates any possible Zn protrusions forming on the anode sur dicators provided by ReCiPe 2016, whereby the Na2MnFe(CN)6 battery
face. As a result, the Zn-3D@600 cell exhibits a discharge capacity of exhibits the lowest impacts across the board.
198.8 mAh/g at 1 A/g after 1000 cycles, thereby exhibiting excellent To ensure improved environmental friendliness of AZIBs, several
cycling stability and extended cycle life. Depth of discharge (DOD) and promising strategies can be followed, such as (i) developing high-
current density are major factors that affect the cycle life of Zn metal voltage cathode materials, (ii) increasing cathode mass loadings to
anodes. Li et al. sought to investigate the effect of these two parameters reduce battery size, (iii) incorporating the use of electrostatic fillers to
on 3D Zn electrodes with carbon nanofiber (CNF) framework backbones prevent dissolution of cathode materials, (iv) utilizing of electrolytes
(Zn@CNF) [55]. It was determined that the cycle life of the Zn@CNF and separators based on renewable materials, and (v) improving the
recycling and recovery of raw materials from used AZIBs (Fig. 17c)
Fig. 16. (a) Schematic illustration of the fabrication of ZIF/Zn heterostructure. (b) Cycling performance at a constant current of 0.25 mA/cm2 with Zn deposition/
dissolution capacity of 0.05 mAh/cm2 (c) The Columbic efficiencies of ZIF/Zn-MnO2 and Zn-MnO2 battery at 1 A/g (d) The cycling performance of ZIF/Zn-MnO2 and
Zn-MnO2 battery at the discharge density of 1 A/g (e) The first-cycle voltage profiles of symmetrical cells with bare Zn and ZIF/Zn electrodes. (f) The 251-cycle
voltage profiles of symmetrical cells with ZIF/Zn electrodes. Adapted with permission [151]. Copyright (2022), American Chemical Society.
20
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
Fig. 17. (a) Global warming of six aqueous zinc ion batteries standardized to 1 kWh of storage capacity. (b) Environmental impacts of the selected six AZIBs
standardized to 1 kWh of storage capacity. (c)Schematic diagram showing possible future steps towards AZIBs with reduced environmental impacts. Adapted with
permission [153]. Copyright (2021) by the authors. Published by John Wiley and Sons. This is an open-access article distributed under the terms of the Creative
Commons CC BY license.
[153]. For example, Wu et al. recently developed a biodegradable gel propagation, which causes a decline in discharge capacity, (iii) high cost
electrolyte (GAE) based on gum arabic (GA) capable of inhibiting of production, and (iv) safety concerns because of the utilization of
corrosion and hydrogen evolution reactions within the cell [154]. As organic electrolytes as well as explosions caused by overcharging. To
shown in Fig. 18a, the Zn-symmetric cell based on this electrolyte ex this end, next-generation Zn-based batteries, specifically Zn-ion batte
hibits an extended cycle life of 1300 h at 0.2 mA/cm2 with 0.2 mAh/ ries, come into the picture as a promising candidate to replace Li-ion
cm2, a value 10 times longer than that in a normal aqueous electrolyte. batteries owing to their stable charge/discharge performance, high
The cycling stability of the GAE battery is also much higher than that of safety through the utilization of less complex electrolytes, low cost, and
the battery utilizing a normal aqueous electrolyte as shown in Fig. 18b. high theoretical energy densities. In this review, we summarized the
Recycling and recovery of raw materials from used ZIBs is an main challenges facing the development of high-performance zinc-ion
important approach to preventing the generation of waste streams and batteries from the perspective of anode and cathode materials as well as
the subsequent need for extraction of primary raw materials [153]. electrolytes, focusing on dendrite growth, parasitic side reactions,
Through recycling, the adverse effects of emissions resulting from the cathode dissolution, insufficient electrolyte, electrolyte decomposition,
manufacture of new cells can be prevented and the resources can be and Jahn-Teller distortions in metal oxide cathodes. In addition, we
optimally utilized. However, further research is required to realize this, reviewed the research progress in the development of strategies to
as the recycling technology for ZIBs is still in its infancy. Incorporating mitigate these challenges from the perspective of not only anode and
the use of renewable and biocompatible materials such as biopolymer cathode design, but also electrolyte composition and design. These
electrolytes can help in this regard as they facilitate environmentally strategies include (i) the electrodeposition of zinc on different substrates
friendly end-of-life approaches. such as carbon, (ii) developing zinc alloys as anode materials, (iii)
incorporating coatings on the zinc anode, (iv) utilization of additives in
the electrolyte to inhibit dendrite growth, and (v) stabilization of cath
5.5. Conclusion ode materials. We find that a large majority of the mitigation strategies
that have been devised and incorporated in recent years focus on (i) the
The dominance of Li-ion batteries as electrochemical energy storage inhibition of zinc dendrite growth, and (ii) the elimination of parasitic
devices in use today comes about because of their high energy densities side reactions. Indeed, this is a reflection of the fact that the growth of
and cycle life. However, their continued use is facing significant chal zinc dendrites and parasitic side reactions are the most prevalent issues
lenges such as (i) dwindling lithium metal sources, (ii) severe dendrite
21
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
Fig. 18. (a) Voltage-time profiles of the Zn//Zn symmetric cell with different electrolytes at 0.2 mA/cm2 with 0.2 mAh/cm2 at room temperature (b) Cycle per
formance at 2C of the Zn//LFP hybrid ion batteries with AE and GAE. Adapted with permission [154]. Copyright (2022), American Chemical Society.
facing ZIBs, as they are the major causes of battery failure and low cycle development of ZIBs. Promising combination strategies include
life. To this end, we believe that resolving these two issues in particular combining (i) structural design optimization and electrolyte optimiza
will be the major catalyst in the widespread production of ZIBs as a tion strategies, and (ii) zinc alloying and protective coatings. Another
suitable replacement to LIBs. Additionally, we find that there are few area with minimal investigation is the development of solid-state ZIBs.
studies on the incorporation of zinc alloying as an optimization strategy The development of solid-state batteries has the major advantage of
for the zinc anode, with most current works focusing on Zn–Ni, Zn–Cu, further enhancing the safety of the overall ZIBs, as solid-state electro
and Zn–Al alloys. These eutectic alloys presented in this review can lytes are much less flammable than their counterparts while also
inspire further research into alloying zinc with other metals, as they providing high voltage and high capacity. Solid-state ZIBs therefore
have proven to be effective in the prevention of anode deformation have the potential to be a safer, lower-cost, and more eco-friendly
during cycling as well as in inhibiting dendrite growth and corrosion alternative to the commercially available LIBs while also electrochem
reactions. Finally, we presented some perspectives for the development ically outperforming them. Through the mitigation strategies and per
of high-performance zinc-ion batteries, focusing on improving energy spectives presented in this work, it is possible to envision a future where
density, minimizing the cost of production, enhancing the cycle life of dendrite-free zinc-ion batteries can be designed and fabricated.
the battery, and ensuring the environmental friendliness of the battery
technology. Further research is required to this end, as there is still much CRediT authorship contribution statement
more progress and development required to realize the commercializa
tion of zinc-ion battery technology. For example, further investigation TM prepared the pre-draft of the manuscript. SDB and KMD reviewed
into the development of zinc anode coatings, specifically coatings that and edited the manuscript. AK and RKG provided the comments,
only conduct ions and not electrons, is required to alleviate anode- reviewed and edited the manuscript, and supervised this project.
electrolyte interface issues as well as facilitate the reduction of side re
actions such as HER and corrosion at the anode [8]. Additionally, Declaration of competing interest
developing consumable-resistant electrolytes by optimizing electrolyte
composition for long-term stability and cycling is another area of future The authors declare that they have no known competing financial
interest, as this can solve the issue of capacity fading brought about by interests or personal relationships that could have appeared to influence
insufficient electrolytes. Furthermore, research into the development of the work reported in this paper.
the Zn2+ intercalated anode is also required to solve issues of poor
conductivity and low energy density. This anode material is based on the Data availability
Zn2+ intercalation/deintercalation mechanism and does not incorporate
the direct use of zinc metal as an anode material, thereby effectively No data was used for the research described in the article.
avoiding the issues of dendrite growth and parasitic side reactions.
Possible strategies to improve the conductivity and energy density of References
this anode material include (i) incorporation of conductive agents such
as graphene and (ii) utilization of tunnel-structured anode material for [1] T. Mageto, S.D. Bhoyate, F.M. de Souza, K. Mensah-Darkwa, A. Kumar, R.
K. Gupta, Developing practical solid-state rechargeable Li-ion batteries: concepts,
optimal Zn2+ intercalation/extraction. The combination of different challenges, and improvement strategies, J. Energy Storage. 55 (2022), 105688.
optimization strategies, especially for zinc anodes, is not widely inves
tigated and could be a potential avenue for further study and
22
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
[2] S. Bhoyate, P.K. Kahol, R.K. Gupta, Nanostructured materials for supercapacitor [34] V. Jabbari, T. Foroozan, R. Shahbazian-Yassar, Dendritic Zn deposition in zinc-
applications, in: P.J. Thomas, N. Revaprasadu (Eds.), Nanosci 5, The Royal metal batteries and mitigation strategies, Adv. Energy Sustain. Res. 2 (2021)
Society of Chemistry, 2019, pp. 1–29. 2000082.
[3] S. Bhoyate, P.K. Kahol, R.K. Gupta, Broadening the horizon for supercapacitor [35] W. Lu, C. Xie, H. Zhang, X. Li, Inhibition of zinc dendrite growth in zinc-based
research via 2D material systems, in: N. Revaprasadu (Ed.), Nanosci 6, The Royal batteries, ChemSusChem. 11 (2018) 3996–4006.
Society of Chemistry, 2020, pp. 120–149. [36] Y. Zhang, M. Zhu, K. Wu, F. Yu, G. Wang, G. Xu, M. Wu, H.-K. Liu, S.-X. Dou,
[4] C. Zequine, S. Bhoyate, F. de Souza, R. Arukula, P.K. Kahol, R.K. Gupta, Recent C. Wu, An in-depth insight of a highly reversible and dendrite-free Zn metal
advancements and key challenges of graphene for flexible supercapacitors, in: anode in an hybrid electrolyte, J. Mater. Chem. A 9 (2021) 4253–4261.
ACS Symp. Ser., 2020: pp. 49–77. [37] X. Guo, Z. Zhang, J. Li, N. Luo, G.-L. Chai, T.S. Miller, F. Lai, P. Shearing, D.J.
[5] G. Fang, J. Zhou, A. Pan, S. Liang, Recent advances in aqueous zinc-ion batteries, L. Brett, D. Han, Z. Weng, G. He, I.P. Parkin, Alleviation of dendrite formation on
ACS Energy Lett. 3 (2018) 2480–2501. zinc anodes via electrolyte additives, ACS Energy Lett. 6 (2021) 395–403.
[6] S. Ponnada, M.S. Kiai, R. Krishnapriya, R. Singhal, R.K. Sharma, Lithium-free [38] J. Zhao, J. Zhang, W. Yang, B. Chen, Z. Zhao, H. Qiu, S. Dong, X. Zhou, G. Cui,
batteries: needs and challenges, Energy Fuel 36 (2022) 6013–6026. L. Chen, “Water-in-deep eutectic solvent” electrolytes enable zinc metal anodes
[7] W. Lu, C. Zhang, H. Zhang, X. Li, Anode for zinc-based batteries: challenges, for rechargeable aqueous batteries, Nano Energy 57 (2019) 625–634.
Strategies, and Prospects, ACS Energy Lett. 6 (2021) 2765–2785. [39] C.M. Julien, A. Mauger, Nanostructured MnO2 as electrode materials for energy
[8] T. Wang, C. Li, X. Xie, B. Lu, Z. He, S. Liang, J. Zhou, Anode materials for aqueous storage, Nanomaterials. 7 (2017) 396.
zinc ion batteries: mechanisms, properties, and perspectives, ACS Nano 14 (2020) [40] S. Randau, D.A. Weber, O. Kötz, R. Koerver, P. Braun, A. Weber, E. Ivers-Tiffée,
16321–16347. T. Adermann, J. Kulisch, W.G. Zeier, F.H. Richter, J. Janek, Benchmarking the
[9] R. Wang, W. Cui, F. Chu, F. Wu, Lithium metal anodes: present and future, performance of all-solid-state lithium batteries, Nat. Energy 5 (2020) 259–270.
J. Energy Chem. 48 (2020) 145–159. [41] N. Nitta, F. Wu, J.T. Lee, G. Yushin, Li-ion battery materials: present and future,
[10] N. Dong, F. Zhang, H. Pan, Towards the practical application of Zn metal anodes Mater. Today 18 (2015) 252–264.
for mild aqueous rechargeable Zn batteries, Chem. Sci. 13 (2022) 8243–8252. [42] I. Manke, J. Banhart, A. Haibel, A. Rack, S. Zabler, N. Kardjilov, A. Hilger,
[11] Y. Liu, Z. Qin, X. Yang, J. Liu, X.-X. Liu, X. Sun, High-voltage manganese oxide A. Melzer, H. Riesemeier, In situ investigation of the discharge of alkaline
cathode with two-electron transfer enabled by a phosphate proton reservoir for Zn–MnO2 batteries with synchrotron x-ray and neutron tomographies, Appl.
aqueous zinc batteries, ACS Energy Lett. 7 (2022) 1814–1819. Phys. Lett. 90 (2007), 214102.
[12] M. Song, H. Tan, D. Chao, H.J. Fan, Recent advances in Zn-ion batteries, Adv. [43] M. Freire, N. V. Kosova, C. Jordy, D. Chateigner, O.I. Lebedev, A. Maignan, V.
Funct. Mater. 28 (2018) 1802564. Pralong, A new active Li–Mn–O compound for high energy density Li-ion
[13] A. Konarov, N. Voronina, J.H. Jo, Z. Bakenov, Y.K. Sun, S.T. Myung, Present and batteries, Nat. Mater. 2015 152.15 (2015) 173–177.
future perspective on electrode materials for rechargeable zinc-ion batteries, ACS [44] X. Wang, Z. Zhang, B. Xi, W. Chen, Y. Jia, J. Feng, S. Xiong, Advances and
Energy Lett. 3 (2018) 2620–2640. perspectives of cathode storage chemistry in aqueous zinc-ion batteries, ACS
[14] J. Zhang, Q. Zhou, Y. Tang, L. Zhang, Y. Li, Zinc–air batteries: are they ready for Nano 15 (2021) 9244–9272.
prime time? Chem. Sci. 10 (2019) 8924–8929. [45] L. Zhang, J. Hu, B. Zhang, J. Liu, H. Wan, L. Miao, J. Jiang, Suppressing cathode
[15] D. Chao, W. Zhou, F. Xie, C. Ye, H. Li, M. Jaroniec, S.Z. Qiao, Roadmap for dissolution via guest engineering for durable aqueous zinc-ion batteries, J. Mater.
advanced aqueous batteries: from design of materials to applications, Sci. Adv. 6 Chem. A 9 (2021) 7631–7639.
(2020). [46] S. Guo, S. Liang, B. Zhang, G. Fang, D. Ma, J. Zhou, Cathode interfacial layer
[16] Y. Liang, C.-Z. Zhao, H. Yuan, Y. Chen, W. Zhang, J.-Q. Huang, D. Yu, Y. Liu, M.- formation via in situ electrochemically charging in aqueous zinc-ion battery, ACS
M. Titirici, Y.-L. Chueh, H. Yu, Q. Zhang, A review of rechargeable batteries for Nano 13 (2019) 13456–13464.
portable electronic devices, InfoMat. 1 (2019) 6–32. [47] D. Kundu, S. Hosseini Vajargah, L. Wan, B. Adams, D. Prendergast, L.F. Nazar,
[17] N. Wang, H. Wan, J. Duan, X. Wang, L. Tao, J. Zhang, H. Wang, A review of zinc- Aqueous vs. nonaqueous Zn-ion batteries: consequences of the desolvation
based battery from alkaline to acid, Mater. Today Adv. 11 (2021), 100149. penalty at the interface, Energy Environ. Sci. 11 (2018) 881–892.
[18] D. Yang, H. Tan, X. Rui, Y. Yu, Electrode materials for rechargeable zinc-ion and [48] H. Pan, Y. Shao, P. Yan, Y. Cheng, K.S. Han, Z. Nie, C. Wang, J. Yang, X. Li,
zinc-air batteries: current status and future perspectives, Electrochem. Energy P. Bhattacharya, K.T. Mueller, J. Liu, Reversible Aqueous Zinc/Manganese Oxide
Rev. 2 (2019) 395–427. Energy Storage From Conversion Reactions 1, 2016.
[19] S. Zuo, X. Xu, S. Ji, Z. Wang, Z. Liu, J. Liu, Cathodes for aqueous Zn-ion batteries: [49] Z. Yi, G. Chen, F. Hou, L. Wang, J. Liang, Strategies for the stabilization of Zn
materials, mechanisms, and kinetics, Chem. – A Eur. J. 27 (2021) 830–860. metal anodes for Zn-ion batteries, Adv. Energy Mater. 11 (2021) 1–31.
[20] A. Kundu, S. Mallick, S. Ghora, C.R. Raj, Advanced oxygen electrocatalyst for air- [50] H. Wang, R. Tan, Z. Yang, Y. Feng, X. Duan, J. Ma, Stabilization perspective on
breathing electrode in Zn-air batteries, ACS Appl. Mater. Interfaces 13 (2021) metal anodes for aqueous batteries, Adv. Energy Mater. 11 (2021) 1–18.
40172–40199. [51] B.J. Hopkins, C.N. Chervin, J.F. Parker, J.W. Long, D.R. Rolison, An areal-energy
[21] I.D. Hosein, The promise of calcium batteries: open perspectives and fair standard to validate air-breathing electrodes for rechargeable zinc–air batteries,
comparisons, ACS Energy Lett. 6 (2021) 1560–1565. Adv. Energy Mater. 10 (2020) 2001287.
[22] S. Bhoyate, S. Mhin, J. Jeon, K. Park, J. Kim, W. Choi, Stable and high-energy- [52] H. Ying, P. Huang, Z. Zhang, S. Zhang, Q. Han, Z. Zhang, J. Wang, W.-Q. Han,
density Zn-ion rechargeable batteries based on a MoS 2 -coated Zn anode, ACS Freestanding and flexible interfacial layer enables bottom-up Zn deposition
Appl. Mater. Interfaces 12 (2020) 27249. toward dendrite-free aqueous Zn-ion batteries, Nano-Micro Lett. 14 (2022) 180.
[23] J. Di, J. Guo, N. Wang, G. Ma, Multicomponent doped sugar-coated haws stick- [53] D.J. Arnot, M.B. Lim, N.S. Bell, N.B. Schorr, R.C. Hill, A. Meyer, Y. Cheng, T.
like nanofibers as efficient oxygen reduction reaction catalysts for the Zn-air N. Lambert, High depth-of-discharge zinc rechargeability enabled by a self-
battery, ACS Sustain. Chem. Eng. 7 (2019) 7716. assembled polymeric coating, Adv. Energy Mater. 11 (2021) 2101594.
[24] C. Lin, X. Li, S.S. Shinde, D.H. Kim, X. Song, H. Zhang, J.H. Lee, Long-life [54] D. Chao, C. (Rose) Zhu, M. Song, P. Liang, X. Zhang, N.H. Tiep, H. Zhao, J. Wang,
rechargeable Zn air battery based on binary metal carbide armored by nitrogen- R. Wang, H. Zhang, H.J. Fan, A high-rate and stable quasi-solid-state zinc-ion
doped carbon, ACS Appl. Energy Mater. 2 (2019) 1747. battery with novel 2D layered zinc orthovanadate array, Adv. Mater. 30 (2018)
[25] T.N.T. Tran, S. Jin, M. Cuisinier, B.D. Adams, D.G. Ivey, Reaction mechanisms for 1803181.
electrolytic manganese dioxide in rechargeable aqueous zinc-ion batteries, Sci. [55] J. Li, Q. Lin, Z. Zheng, L. Cao, W. Lv, Y. Chen, How is cycle life of three-
Report. 2021 111.11 (2021) 1–11. dimensional zinc metal anodes with carbon fiber backbones affected by depth of
[26] N. Zhang, F. Cheng, J. Liu, L. Wang, X. Long, X. Liu, F. Li, J. Chen, Rechargeable discharge and current density in zinc–ion batteries? ACS Appl. Mater. Interfaces
aqueous zinc-manganese dioxide batteries with high energy and power densities, 14 (2022) 12323–12330.
Nat. Commun. 2017 81.8 (2017) 1–9. [56] Z. Zhao, J. Zhao, Z. Hu, J. Li, J. Li, Y. Zhang, C. Wang, G. Cui, Long-life and
[27] B. Lee, H.R. Seo, H.R. Lee, C.S. Yoon, J.H. Kim, K.Y. Chung, B.W. Cho, S.H. Oh, deeply rechargeable aqueous Zn anodes enabled by a multifunctional brightener-
Critical role of pH evolution of electrolyte in the reaction mechanism for inspired interphase, Energy Environ. Sci. 12 (2019) 1938–1949.
rechargeable zinc batteries, ChemSusChem. 9 (2016) 2948–2956. [57] Y. Zhang, F. Wan, S. Huang, S. Wang, Z. Niu, J. Chen, A Chemically Self-charging
[28] X. Guo, J. Zhou, C. Bai, X. Li, G. Fang, S. Liang, Zn/MnO2 battery chemistry with Aqueous Zinc-Ion Battery 11 (2020) 1–10.
dissolution-deposition mechanism, Mater. Today Energy. 16 (2020), 100396. [58] Z. Song, L. Miao, L. Ruhlmann, Y. Lv, D. Zhu, L. Li, L. Gan, M. Liu, Lewis pair
[29] Y. Zhang, E.H. Ang, K.N. Dinh, K. Rui, H. Lin, J. Zhu, Q. Yan, Recent advances in interaction self-assembly of carbon superstructures harvesting high-energy and
vanadium-based cathode materials for rechargeable zinc ion batteries, Mater. ultralong-life zinc-ion storage, Adv. Funct. Mater. 2208049 (2022).
Chem. Front. 5 (2021) 744–762. [59] F. Wang, O. Borodin, T. Gao, X. Fan, W. Sun, F. Han, A. Faraone, J.A. Dura, K. Xu,
[30] A. Krężel, W. Maret, The biological inorganic chemistry of zinc ions, Arch. C. Wang, Highly reversible zinc metal anode for aqueous batteries, Nat. Mater. 17
Biochem. Biophys. 611 (2016) 3–19. (2018) 543–549.
[31] X. Zhang, J.-P. Hu, N. Fu, W.-B. Zhou, B. Liu, Q. Deng, X.-W. Wu, Comprehensive [60] L. Cao, D. Li, T. Deng, Q. Li, C. Wang, Hydrophobic organic-electrolyte-protected
review on zinc-ion battery anode: challenges and strategies, InfoMat. 4 (2022), zinc anodes for aqueous zinc batteries, Angew, Chemie. 132 (2020)
e12306. 19454–19458.
[32] J. Yang, B. Yin, Y. Sun, H. Pan, W. Sun, B. Jia, S. Zhang, T. Ma, Zinc anode for [61] Y. Huang, Q. Gu, Z. Guo, W. Liu, Z. Chang, Y. Liu, F. Kang, L. Dong, C. Xu,
mild aqueous zinc-ion batteries: challenges, Strategies, and Perspectives, Nano- Unraveling dynamical behaviors of zinc metal electrodes in aqueous electrolytes
Micro Lett. 14 (2022) 42. through an operando study, Energy Storage Mater. 46 (2022) 243–251.
[33] W. Du, E.H. Ang, Y. Yang, Y. Zhang, M. Ye, C.C. Li, Challenges in the material and [62] Y. Du, Y. Li, B. Bin Xu, T.X. Liu, X. Liu, F. Ma, X. Gu, C. Lai, Electrolyte salts and
structural design of zinc anode towards high-performance aqueous zinc-ion additives regulation enables high performance aqueous zinc ion batteries: a mini
batteries, Energy Environ. Sci. 13 (2020) 3330–3360. review, Small. 18 (2022) 2104640.
23
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
[63] M. Wu, G. Zhang, L. Du, D. Yang, H. Yang, S. Sun, Defect electrocatalysts and [92] B.W. Olbasa, F.W. Fenta, S.-F. Chiu, M.-C. Tsai, C.-J. Huang, B.A. Jote, T.
alkaline electrolyte membranes in solid-state zinc–air batteries: recent advances, T. Beyene, Y.-F. Liao, C.-H. Wang, W.-N. Su, H. Dai, B.J. Hwang, High-rate and
challenges, and future perspectives, Small Methods. 5 (2021) 2000868. long-cycle stability with a dendrite-free zinc anode in an aqueous Zn-ion battery
[64] E.J. Hansen, J. Liu, Materials and structure design for solid-state zinc-ion using concentrated electrolytes, ACS Appl. Energy Mater. 3 (2020) 4499–4508.
batteries: a mini-review, Front. Energy Res. 8 (2021) 368. [93] P. Wang, X. Xie, Z. Xing, X. Chen, G. Fang, B. Lu, J. Zhou, S. Liang, H.J. Fan,
[65] Y. Lv, Y. Xiao, L. Ma, C. Zhi, S. Chen, Recent advances in electrolytes for “beyond Mechanistic insights of mg 2+ − electrolyte additive for high-energy and long-life
aqueous” zinc-ion batteries, Adv. Mater. 34 (2022) 2106409. zinc-ion hybrid capacitors, Adv. Energy Mater. 11 (2021) 2101158.
[66] S. Zhao, K. Wang, S. Tang, X. Liu, K. Peng, Y. Xiao, Y. Chen, A new solid-state [94] F. Wan, L. Zhang, X. Dai, X. Wang, Z. Niu, J. Chen, Aqueous rechargeable zinc/
zinc–air battery for fast charge, Energ. Technol. 8 (2020) 1901229. sodium vanadate batteries with enhanced performance from simultaneous
[67] Y. Lin, Z. Mai, H. Liang, Y. Li, G. Yang, C. Wang, Dendrite-free Zn anode enabled insertion of dual carriers, Nat. Commun. 9 (2018) 1656.
by anionic surfactant-induced horizontal growth for highly-stable aqueous Zn-ion [95] C. Sun, C. Wu, X. Gu, C. Wang, Q. Wang, Interface engineering via Ti(3)C(2)T(x)
pouch cells, Energy Environ. Sci. 16 (2023) 687–697. MXene electrolyte additive toward dendrite-free zinc deposition, Nano-Micro
[68] Y. Li, Z. Tan, Y. Liang, Y. Xiao, D. Cen, Y. Liu, Y. Liang, Amine-functionalized Lett. 13 (2021) 89.
carbon cloth host for dendrite-free Zn metal anodes, ACS Appl. Energy Mater. 4 [96] X. Zeng, J. Mao, J. Hao, J. Liu, S. Liu, Z. Wang, Y. Wang, S. Zhang, T. Zheng,
(2021) 4482–4488. J. Liu, P. Rao, Z. Guo, Electrolyte design for in situ construction of highly Zn 2+
[69] Z. Wu, X. Yuan, M. Jiang, L. Wang, Q. Huang, L. Fu, Y. Wu, Zinc–carbon paper -conductive solid electrolyte interphase to enable high-performance aqueous Zn-
composites as anodes for zn-ion batteries: key impacts on their electrochemical ion batteries under practical conditions, Adv. Mater. 33 (2021) 2007416.
behaviors, Energy Fuel 34 (2020) 13118–13125. [97] Turning the Byproduct Zn4(OH)6SO4xH2O into a Uniform Solid Electrolyte
[70] W. Dong, J.-L. Shi, T.-S. Wang, Y.-X. Yin, C.-R. Wang, Y.-G. Guo, 3D zinc@carbon Interphase to Stabilize Aqueous Zn Anode, (n.d.).
fiber composite framework anode for aqueous Zn–MnO2 batteries, RSC Adv. 8 [98] R. Zhao, H. Wang, H. Du, Y. Yang, Z. Gao, L. Qie, Y. Huang, Lanthanum nitrate as
(2018) 19157–19163. aqueous electrolyte additive for favourable zinc metal electrodeposition, Nat.
[71] X. Shi, G. Xu, S. Liang, C. Li, S. Guo, X. Xie, X. Ma, J. Zhou, Homogeneous Commun. 13 (2022) 3252.
deposition of zinc on three-dimensional porous copper foam as a superior zinc [99] C. Huang, X. Zhao, Y. Hao, Y. Yang, Y. Qian, G. Chang, Y. Zhang, Q. Tang, A. Hu,
metal anode, ACS Sustain. Chem. Eng. 7 (2019) 17737–17746. X. Chen, Self-healing SeO 2 additives enable zinc metal reversibility in aqueous
[72] Z. Kang, C. Wu, L. Dong, W. Liu, J. Mou, J. Zhang, Z. Chang, B. Jiang, G. Wang, ZnSO 4 electrolytes, Adv. Funct. Mater. 32 (2022) 2112091.
F. Kang, C. Xu, 3D porous copper skeleton supported zinc anode toward high [100] P. Sun, L. Ma, W. Zhou, M. Qiu, Z. Wang, D. Chao, W. Mai, Simultaneous
capacity and Long cycle life zinc ion batteries, ACS Sustain. Chem. Eng. 7 (2019) regulation on solvation shell and electrode interface for dendrite-free Zn ion
3364–3371. batteries achieved by a low-cost glucose additive, Angew, Chemie. 133 (2021)
[73] R. Li, Y. Du, Y. Li, Z. He, L. Dai, L. Wang, X. Wu, jiujun Zhang, J. Yi, Alloying 18395–18403.
strategy for high-performance zinc metal anodes, ACS Energy Lett. 8 (2023) [101] S. Gao, J. Han, Z. Liu, K. Wang, K. Jiang, C. Guo, Y. Tan, D. Zhou, W. Shi,
457–476. Polyvinyl pyrrolidone as electrolyte additive for aqueous zinc batteries with
[74] B. Liu, S. Wang, Z. Wang, H. Lei, Z. Chen, W. Mai, Novel 3D nanoporous Zn–cu MnO2 cathode, J. Electrochem. Soc. 168 (2021) 80514.
alloy as Long-life anode toward high-voltage double electrolyte aqueous zinc-ion [102] Z. Hou, X. Zhang, X. Li, Y. Zhu, J. Liang, Y. Qian, Surfactant widens the
batteries, Small. 16 (2020) 2001323. electrochemical window of an aqueous electrolyte for better rechargeable
[75] S.-B. Wang, Q. Ran, R.-Q. Yao, H. Shi, Z. Wen, M. Zhao, X.-Y. Lang, Q. Jiang, aqueous sodium/zinc battery, J. Mater. Chem. A 5 (2017) 730–738.
Lamella-nanostructured eutectic zinc–aluminum alloys as reversible and [103] J. Shi, K. Xia, L. Liu, C. Liu, Q. Zhang, L. Li, X. Zhou, J. Liang, Z. Tao, Ultrahigh
dendrite-free anodes for aqueous rechargeable batteries, Nat. Commun. 11 (2020) coulombic efficiency and long-life aqueous Zn anodes enabled by electrolyte
1634. additive of acetonitrile, Electrochim. Acta 358 (2020), 136937.
[76] M. Fayette, H.J. Chang, X. Li, D. Reed, High-performance in Zn alloy anodes [104] K. Zhao, F. Liu, G. Fan, J. Liu, M. Yu, Z. Yan, N. Zhang, F. Cheng, Stabilizing zinc
toward practical aqueous zinc batteries, ACS Energy Lett. 7 (2022) 1888–1895. electrodes with a vanillin additive in mild aqueous electrolytes, ACS Appl. Mater.
[77] Z. Qi, T. Xiong, T. Chen, C. Yu, M. Zhang, Y. Yang, Z. Deng, H. Xiao, W.S.V. Lee, & Interfaces. 13 (2021) 47650–47658.
J. Xue, Dendrite-free anodes enabled by a composite of a ZnAl alloy with a copper [105] K. Guan, L. Tao, R. Yang, H. Zhang, N. Wang, H. Wan, J. Cui, J. Zhang, H. Wang,
mesh for high-performing aqueous zinc-ion batteries, ACS Appl. Mater. Interfaces H. Wang, Anti-corrosion for reversible zinc anode via a hydrophobic Interface in
13 (2021) 28129–28139. aqueous zinc batteries, Adv. Energy Mater. 12 (2022) 2103557.
[78] J. Zheng, Q. Zhao, T. Tang, J. Yin, C.D. Quilty, G.D. Renderos, X. Liu, Y. Deng, L. [106] H. Zhang, S. Li, L. Xu, R. Momen, W. Deng, J. Hu, G. Zou, H. Hou, X. Ji, High-yield
Wang, D.C. Bock, C. Jaye, D. Zhang, E.S. Takeuchi, K.J. Takeuchi, A.C. carbon dots interlayer for ultra-stable zinc batteries, Adv. Energy Mater. 12
Marschilok, L.A. Archer, Reversible epitaxial electrodeposition of metals in (2022) 2200665.
battery anodes, Science (80-.). 366 (2019) 645–648. [107] S. Zhang, J. Ye, H. Ao, M. Zhang, X. Li, Z. Xu, Z. Hou, Y. Qian, In-situ formation of
[79] Y. Hao, J. Zhou, G. Wei, A. liu, Y. Zhang, Y. Mei, B. Lu, M. Luo, M. Xie, Artificial hierarchical solid-electrolyte interphase for ultra-long cycling of aqueous zinc-ion
N-doped graphene protective layer enables stable Zn anode for aqueous Zn-ion batteries, Nano Res. 16 (2022) 449–457.
batteries, ACS Appl. Energy Mater. 4 (2021) 6364–6373. [108] X. Zeng, J. Zhao, Z. Wan, W. Jiang, M. Ling, L. Yan, C. Liang, Controllably
[80] L. Fan, A. Lin, L. Cao, F. Gu, S. Xiong, Z. Li, Enabled uniform Zn stripping/plating electrodepositing ZIF-8 protective layer for highly reversible zinc anode with
by natural halloysite nanotube coating with opposite charge for aqueous Zn-ion ultralong lifespan, J. Phys. Chem. Lett. 12 (2021) 9055–9059.
batteries, ACS Sustain. Chem. Eng. 10 (2022) 5838–5846. [109] S. So, Y.N. Ahn, J. Ko, I.T. Kim, J. Hur, Uniform and oriented zinc deposition
[81] Z. Li, X. Wu, X. Yu, S. Zhou, Y. Qiao, H. Zhou, S.G. Sun, Long-life aqueous Zn- induced by artificial Nb2O5 layer for highly reversible Zn anode in aqueous zinc
I2Battery enabled by a low-cost multifunctional zeolite membrane separator, ion batteries, Energy Storage Mater. 52 (2022) 40–51.
Nano Lett. 22 (2022) 2538–2546. [110] B. Li, K. Yang, J. Ma, P. Shi, L. Chen, C. Chen, X. Hong, X. Cheng, M. Tang, Y. He,
[82] W. Shang, Q. Li, F. Jiang, B. Huang, J. Song, S. Yun, X. Liu, H. Kimura, J. Liu, F. Kang, Multicomponent copper-zinc alloy layer enabling ultra-stable zinc metal
L. Kang, Boosting Zn, I2 Battery’s performance by coating a zeolite-based cation- anode of aqueous Zn-ion battery, Angew. Chem. Int. Ed. 61 (2022).
exchange protecting layer, Nano-Micro Lett. 14 (2022) 1–13. [111] Y. Zhang, X. Yang, Y. Hu, K. Hu, X. Lin, X. Liu, K.M. Reddy, G. Xie, H. Qiu, Highly
[83] P. Cao, J. Tang, A. Wei, Q. Bai, Q. Meng, S. Fan, H. Ye, Y. Zhou, X. Zhou, J. Yang, strengthened and toughened Zn–Li–Mn alloys as long-cycling life and dendrite-
Manipulating uniform nucleation to achieve dendrite-free Zn anodes for aqueous free Zn anode for aqueous zinc-ion batteries, Small. 18 (2022) 2200787.
Zn-ion batteries, ACS Appl. Mater. Interfaces 13 (2021) 48855–48864. [112] H. Meng, Q. Ran, T.-Y. Dai, H. Shi, S.-P. Zeng, Y.-F. Zhu, Z. Wen, W. Zhang, X.-
[84] Q. Lu, C. Liu, Y. Du, X. Wang, L. Ding, A. Omar, D. Mikhailova, Uniform Zn Y. Lang, W.-T. Zheng, Q. Jiang, Surface-alloyed nanoporous zinc as reversible and
deposition achieved by ag coating for improved aqueous zinc-ion batteries, ACS stable anodes for high-performance aqueous zinc-ion battery, Nano-Micro Lett. 14
Appl. Mater. Interfaces 13 (2021) 16869–16875. (2022) 128.
[85] S. Liu, R. Zhang, J. Mao, Y. Zhao, Q. Cai, Z. Guo, From room temperature to harsh [113] Y. Long, X. Huang, Y. Li, M. Yi, J. Hou, X. Zhou, Q. Hu, Q. Zheng, D. Lin, In-situ
temperature applications: fundamentals and perspectives on electrolytes in zinc regulation of zinc metal surface for dendrite-free zinc-ion hybrid supercapacitors,
metal batteries, Sci. Adv. 8 (2022) 1–25. J. Colloid Interface Sci. 614 (2022) 205–213.
[86] C. Liu, X. Xie, B. Lu, J. Zhou, S. Liang, Electrolyte strategies toward better zinc-ion [114] Q. Zhao, W. Liu, Y. Chen, L. Chen, Ultra-stable Zn metal batteries with dendrite-
batteries, ACS Energy Lett. 6 (2021) 1015–1033. free Cu-Sn alloy induced high-quality composite Zn mesh, Chem. Eng. J. 450
[87] Q. Yang, Q. Li, Z. Liu, D. Wang, Y. Guo, X. Li, Y. Tang, H. Li, B. Dong, C. Zhi, (2022), 137979.
Dendrites in Zn-based batteries, Adv. Mater. 32 (2020) 1–32. [115] Z. Qi, T. Xiong, Z.G. Yu, F. Meng, B. Chen, H. Xiao, J. Xue, Suppressing zinc
[88] T. Zhang, Y. Tang, S. Guo, X. Cao, A. Pan, G. Fang, J. Zhou, S. Liang, dendrite growth in aqueous battery via Zn–Al alloying with spatially confined
Fundamentals and perspectives in developing zinc-ion battery electrolytes: a zinc reservoirs, J. Power Sources 558 (2023), 232628.
comprehensive review, Energy Environ. Sci. 13 (2020) 4625–4665. [116] W. Xu, X. Liao, W. Xu, K. Zhao, G. Yao, Q. Wu, Ion selective and water resistant
[89] B. Liu, T. Wu, F. Ma, C. Zhong, W. Hu, Long-life and highly utilized zinc anode for cellulose nanofiber/MXene membrane enabled cycling Zn anode at high currents,
aqueous batteries enabled by electrolyte additives with synergistic effects, ACS Adv. Energy Mater. 13 (2023).
Appl. Mater. Interfaces 14 (2022) 18431–18438. [117] X. Wang, X. Wang, Y. Zhou, H. Qi, X. Li, C. Wei, T. Zou, W. Wang, Z. Yang, In-situ
[90] A. Bayaguud, X. Luo, Y. Fu, C. Zhu, Cationic surfactant-type electrolyte additive construction of multifunctional protection interface for ultra-stable zinc anodes,
enables three-dimensional dendrite-free zinc anode for stable zinc-ion batteries, J. Alloys Compd. 947 (2023), 169510.
ACS Energy Lett. 5 (2020) 3012–3020. [118] P. He, S. Chen, Cathode strategies to improve the performance of zinc-ion
[91] J. Abdulla, J. Cao, D. Zhang, X. Zhang, C. Sriprachuabwong, S. Kheawhom, batteries, Electrochem. Sci. Adv. 2 (2022), e2100090.
P. Wangyao, J. Qin, Elimination of zinc dendrites by graphene oxide electrolyte [119] G. Su, S. Chen, H. Dong, Y. Cheng, Q. Liu, H. Wei, E.H. Ang, H. Geng, C.C. Li,
additive for zinc-ion batteries, ACS Appl. Energy Mater. 4 (2021) 4602–4609. Tuning the electronic structure of layered vanadium pentoxide by pre-
24
T. Mageto et al. Journal of Energy Storage 70 (2023) 108081
intercalation of potassium ions for superior room/low-temperature aqueous zinc- [138] Z. Pan, J. Yang, J. Yang, Q. Zhang, H. Zhang, X. Li, Z. Kou, Y. Zhang, H. Chen,
ion batteries, Nanoscale. 13 (2021) 2399–2407. C. Yan, J. Wang, Stitching of Zn3(OH)2V2O7⋅2H2O 2D nanosheets by 1D carbon
[120] S. Chen, Y. Zhang, H. Geng, Y. Yang, X. Rui, C.C. Li, Zinc ions pillared vanadate nanotubes boosts ultrahigh rate for wearable quasi-solid-state zinc-ion batteries,
cathodes by chemical pre-intercalation towards long cycling life and low- ACS Nano 14 (2020) 842–853.
temperature zinc ion batteries, J. Power Sources 441 (2019), 227192. [139] Q. Chen, J. Jin, Z. Kou, C. Liao, Z. Liu, L. Zhou, J. Wang, L. Mai, Zn 2+ pre-
[121] J. Shin, D.S. Choi, H.J. Lee, Y. Jung, J.W. Choi, Hydrated intercalation for high- intercalation stabilizes the tunnel structure of MnO 2 nanowires and enables zinc-
performance aqueous zinc ion batteries, Adv. Energy Mater. 9 (2019) 1900083. ion hybrid supercapacitor of battery-level energy density, Small. 16 (2020)
[122] J. Zeng, Z. Zhang, X. Guo, G. Li, A conjugated polyaniline and water co- 2000091.
intercalation strategy boosting zinc-ion storage performances for rose-like [140] Y. Yang, Y. Tang, S. Liang, Z. Wu, G. Fang, X. Cao, C. Wang, T. Lin, A. Pan,
vanadium oxide architectures, J. Mater. Chem. A 7 (2019) 21079–21084. J. Zhou, Transition metal ion-preintercalated V2O5 as high-performance aqueous
[123] G. Liu, H. Huang, R. Bi, X. Xiao, T. Ma, L. Zhang, K+ pre-intercalated manganese zinc-ion battery cathode with broad temperature adaptability, Nano Energy 61
dioxide with enhanced Zn2+ diffusion for high rate and durable aqueous zinc-ion (2019) 617–625.
batteries, J. Mater. Chem. A 7 (2019) 20806–20812. [141] Y. Yang, Y. Tang, G. Fang, L. Shan, J. Guo, W. Zhang, C. Wang, L. Wang, J. Zhou,
[124] Q. Chen, J. Jin, Z. Kou, C. Liao, Z. Liu, L. Zhou, J. Wang, L. Mai, Zn2+ pre- S. Liang, Li+ intercalated V2O5⋅nH2O with enlarged layer spacing and fast ion
intercalation stabilizes the tunnel structure of MnO2 nanowires and enables zinc- diffusion as an aqueous zinc-ion battery cathode, Energy & Environ. Sci. 11
ion hybrid supercapacitor of battery-level energy density, Small. 16 (2020) (2018) 3157–3162.
2000091. [142] D. Zhang, J. Cao, X. Zhang, N. Insin, S. Wang, J. Han, Y. Zhao, J. Qin, Y. Huang,
[125] Z. Li, Y. Ren, L. Mo, C. Liu, K. Hsu, Y. Ding, X. Zhang, X. Li, L. Hu, D. Ji, G. Cao, Inhibition of manganese dissolution in Mn2O3 cathode with controllable Ni2
Impacts of oxygen vacancies on zinc ion intercalation in VO2, ACS Nano 14 +
incorporation for high-performance zinc ion battery, Adv. Funct. Mater. 31
(2020) 5581–5589. (2021) 2009412.
[126] X. Pu, X. Li, L. Wang, H. Maleki Kheimeh Sari, J. Li, Y. Xi, H. Shan, J. Wang, W. Li, [143] J. Zhou, A. Dong, L. Du, C. Yang, L. Ye, X. Wang, L. Zhao, Q. Jiang, Mn-doped ZnO
X. Liu, S. Wang, J. Zhang, Y. Wu, Enriching oxygen vacancy defects via ag–O–Mn microspheres as cathode materials for aqueous zinc ion batteries with
bonds for enhanced diffusion kinetics of δ-MnO2 in zinc-ion batteries, ACS Appl. ultrastability up to 10 000 cycles at a large current density, Chem. Eng. J. 421
Mater. Interfaces 14 (2022) 21159–21172. (2021), 127770.
[127] H. Luo, B. Wang, C. Wang, F. Wu, F. Jin, B. Cong, Y. Ning, Y. Zhou, D. Wang, [144] T. Xiong, Z.G. Yu, H. Wu, Y. Du, Q. Xie, J. Chen, Y. Zhang, S.J. Pennycook, W.S.
H. Liu, S. Dou, Synergistic deficiency and heterojunction engineering boosted V. Lee, J. Xue, Defect engineering of oxygen-deficient manganese oxide to achieve
VO2 redox kinetics for aqueous zinc-ion batteries with superior comprehensive high-performing aqueous zinc ion battery, Adv. Energy Mater. 9 (2019) 1803815.
performance, Energy Storage Mater. 33 (2020) 390–398. [145] C. Zhu, G. Fang, S. Liang, Z. Chen, Z. Wang, J. Ma, H. Wang, B. Tang, X. Zheng,
[128] J. Wang, J.-G. Wang, X. Qin, Y. Wang, Z. You, H. Liu, M. Shao, Superfine MnO2 J. Zhou, Electrochemically induced cationic defect in MnO intercalation cathode
nanowires with rich defects toward boosted zinc ion storage performance, ACS for aqueous zinc-ion battery, Energy Storage Mater. 24 (2020) 394–401.
Appl. Mater. Interfaces 12 (2020) 34949–34958. [146] F. Yan, K. Huang, T. Jiang, X. Zhou, Y. Shi, G. Ge, B. Shen, J. Zhai, Significantly
[129] Q. Tan, X. Li, B. Zhang, X. Chen, Y. Tian, H. Wan, L. Zhang, L. Miao, C. Wang, enhanced energy storage density and efficiency of BNT-based perovskite ceramics
Y. Gan, J. Jiang, Y. Wang, H. Wang, Valence engineering via in situ carbon via A-site defect engineering, Energy Storage Mater. 30 (2020) 392–400.
reduction on octahedron sites Mn3O4 for ultra-Long cycle life aqueous Zn-ion [147] L. Chen, Z. Yang, Y. Huang, Monoclinic VO2(D) hollow nanospheres with super-
battery, Adv. Energy Mater. 10 (2020) 2001050. long cycle life for aqueous zinc ion batteries, Nanoscale. 11 (2019) 13032–13039.
[130] Y. Gan, C. Wang, J. Li, J. Zheng, Z. Wu, L. Lv, P. Liang, H. Wan, J. Zhang, [148] Q. Li, Q. Zhang, C. Liu, Z. Zhou, C. Li, B. He, P. Man, X. Wang, Y. Yao, Anchoring
H. Wang, Stability optimization strategies of cathode materials for aqueous zinc V2O5 nanosheets on hierarchical titanium nitride nanowire arrays to form
ion batteries: a mini review, Front. Chem. 9 (2022). core–shell heterostructures as a superior cathode for high-performance wearable
[131] Q. Zong, Q. Wang, C. Liu, D. Tao, J. Wang, J. Zhang, H. Du, J. Chen, Q. Zhang, aqueous rechargeable zinc-ion batteries, J. Mater. Chem. A 7 (2019)
G. Cao, Potassium ammonium vanadate with rich oxygen vacancies for fast and 12997–13006.
highly stable Zn-ion storage, ACS Nano 16 (2022) 4588–4598. [149] H. Luo, B. Wang, F. Wu, J. Jian, K. Yang, F. Jin, B. Cong, Y. Ning, Y. Zhou,
[132] N. Liu, X. Wu, Y. Yin, A. Chen, C. Zhao, Z. Guo, L. Fan, N. Zhang, Constructing the D. Wang, H. Liu, S. Dou, Synergistic nanostructure and heterointerface design
efficient ion diffusion pathway by introducing oxygen defects in Mn2O3 for high- propelled ultra-efficient in-situ self-transformation of zinc-ion battery cathodes
performance aqueous zinc-ion batteries, ACS Appl. Mater. Interfaces 12 (2020) with favorable kinetics, Nano Energy 81 (2021), 105601.
28199–28205. [150] Q. Yang, X. Li, Z. Chen, Z. Huang, C. Zhi, Cathode engineering for high energy
[133] X. Ge, S. Liu, M. Qiao, Y. Du, Y. Li, J. Bao, X. Zhou, Enabling superior density aqueous Zn batteries, accounts, Mater. Res. 3 (2022) 78–88.
electrochemical properties for highly efficient potassium storage by impregnating [151] W. Liu, P. Guo, T. Zhang, X. Ying, F. Zhou, X. Zhang, Rational
ultrafine Sb nanocrystals within nanochannel-containing carbon nanofibers, electrode–electrolyte design for long-life rechargeable aqueous zinc-ion batteries,
Angew. Chem. Int. Ed. 58 (2019) 14578–14583. J. Phys. Chem. C 126 (2022) 1264–1270.
[134] J. Chen, J. Liang, Y. Zhou, Z. Sha, S. Lim, F. Huang, Z. Han, S.A. Brown, L. Cao, D.- [152] K. Chen, H. Guo, W. Li, Y. Wang, Dual porous 3D zinc anodes toward dendrite-
W. Wang, C.H. Wang, A vertical graphene enhanced Zn–MnO2 flexible battery free and long cycle life zinc-ion batteries, ACS Appl. Mater. Interfaces 13 (2021)
towards wearable electronic devices, J. Mater. Chem. A 9 (2021) 575–584. 54990–54996.
[135] Y. Huang, J. Liu, Q. Huang, Z. Zheng, P. Hiralal, F. Zheng, D. Ozgit, S. Su, S. Chen, [153] M. Iturrondobeitia, O. Akizu-Gardoki, O. Amondarain, R. Minguez, E. Lizundia,
P.-H. Tan, S. Zhang, H. Zhou, Flexible high energy density zinc-ion batteries Environmental impacts of aqueous zinc ion batteries based on life cycle
enabled by binder-free MnO2/reduced graphene oxide electrode, Npj Flex. assessment, Adv. Sustain. Syst. 6 (2022) 2100308.
Electron. 2 (2018) 21. [154] K. Wu, J. Cui, J. Yi, X. Liu, F. Ning, Y. Liu, J. Zhang, Biodegradable gel electrolyte
[136] B. Wu, W. Luo, M. Li, L. Zeng, L. Mai, Achieving better aqueous rechargeable zinc suppressing water-induced issues for long-life zinc metal anodes, ACS Appl.
ion batteries with heterostructure electrodes, Nano Res. 14 (2021) 3174–3187. Mater. Interfaces 14 (2022) 34612–34619.
[137] J. Kumankuma-Sarpong, W. Guo, Y. Fu, Advances of metal oxide composite
cathodes for aqueous zinc-ion batteries, Adv. Energy Sustain. Res. 3 (2022)
2100220.
25