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Fundamentals and perspectives of electrolyte additives for aqueous

zinc-ion batteries

Shan Guo , Liping Qin , Tengsheng Zhang , Miao Zhou ,

Jiang Zhou , Guozhao Fang , Shuquan Liang

PII: S2405-8297(20)30396-2
DOI: https://doi.org/10.1016/j.ensm.2020.10.019
Reference: ENSM 1385

To appear in: Energy Storage Materials

Received date: 23 September 2020

Revised date: 16 October 2020
Accepted date: 20 October 2020

Please cite this article as: Shan Guo , Liping Qin , Tengsheng Zhang , Miao Zhou ,
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 Fundamentals and perspectives of electrolyte additives for

aqueous zinc-ion batteries

Shan Guo,a Liping Qin,b Tengsheng Zhang,a Miao Zhou,a Jiang Zhou,a,c Guozhao Fang*,a,c and

Shuquan Liang*,a,c

a
School of Materials Science and Engineering, Central South University, Changsha 410083, Hunan,

P. R. China.

b
College of Biological and Chemical Engineering, Guangxi University of Science and Technology,

Liuzhou 545006, Guangxi, P.R. China

c
Key Laboratory of Electronic Packaging and Advanced Functional Materials of Hunan Province,

Central South University, Changsha 410083, Hunan, P.R. China

Email: fg_zhao@csu.edu.cn, lsq@csu.edu.cn.

Abstract:

Electrolyte additive as an innovative energy storage technology has been widely applied in

battery field. It is significant that electrolyte additive can address many of critical issues such as

electrolyte decomposition, anode dendrites, and cathode dissolution for the low-cost and high-safety

aqueous zinc-ion batteries. However, there is a lack of systematic discussion on the features and

functional mechanisms of electrolyte additives, which highlights the importance of a timely review

with the academic perspective in this aspect. In this review, a comprehensive introduction of

commonly used zinc-ion electrolyte additives is covered. Particularly, an in-depth and fundamental

understanding on the disciplines and effects of electrolyte additives on electrolyte aspect, anode side,

1
and cathode side has been expounded and evaluated. Due to the lack of systematic research in

various electrolyte, anode and cathode issues, we have also highlighted the issues and pointed out

the promising strategies for each aspect. The final section presents the potential directions and

perspectives for further improvements and guidance of electrolytes and additives in aqueous

zinc-ion batteries.

Keywords: electrolyte additives, electrolyte, zinc anode, cathode chemistry, aqueous zinc-ion

batteries

2
 Outlines
Abstract: ............................................................................................................................................... 1
1 Introduction ....................................................................................................................................... 4
2 Electrolyte Additives for Zinc-Ion Batteries ..................................................................................... 9
3 Functional Additives Modifying Electrolyte Properties ................................................................. 12
3.1 Enhancing Ion Transport Properties ..................................................................................... 13
3.2 Modulation of Electrochemical Window ............................................................................. 15
3.3 Change of Other Electrolyte Features .................................................................................. 19
4 Toward Highly Reversible Zn Anode with Electrolyte Additives .................................................. 21
4.1 Regulation of Zinc Deposition Process ................................................................................ 21
4.2 Side Reaction Inhibition and Coulombic Efficiency Improvement ..................................... 31
5 Cathode Chemistry Associated with Electrolyte Additives ............................................................ 36
5.1 Protection and Stabilization of the Cathode ......................................................................... 36
5.2 Improvement of Capacity and Voltage ................................................................................. 41
5.3 Modification of Interface Compatibility .............................................................................. 45
6 Summary and Outlooks ................................................................................................................... 48
6.1 Structural Insight of Electrolyte ........................................................................................... 51
6.2 Promotion of Electrolyte Stability ....................................................................................... 52
6.3 Compound Additive Effects ................................................................................................. 52
6.4 Design of Novel Electrolyte ................................................................................................. 52
6.5 Application in Other Electrolyte System ............................................................................. 53
Conflict of Interest ............................................................................................................................. 53
Acknowledgments .............................................................................................................................. 54
References .......................................................................................................................................... 54
TOC Entry ........................................................................................................................................ 61

3
1 Introduction

The large-scale deployment of renewable energy sources is considered as an inevitable trend to

cope with the increasing fossil energy consumption, climate and environmental issues. The aqueous

zinc-ion batteries (ZIBs) are highly promising in this aspect due to their inherent advantages of low

cost, high safety, easy accessibility [1-3]. The research interests and achievements in aqueous ZIBs

have surged in the last past 5 years [4-6]. Unfortunately, the detrimental issues existing in aqueous

ZIBs greatly impede their large-scale deployment. These major challenges include: (1) The

dissolution of transition-metal (TM) ions and structural instability of cathode materials. The

dissolution of TM ions mainly occurs in manganese-based materials with Jahn-Teller effect or

vanadium-based materials in weakly acidic aqueous electrolyte [7]. What’s more, due to the

relatively high activity of water solvent, the serious capacity degradation problem will be generated

[8, 9]. Structural instability such as the collapse of the popular tunneled manganese oxides and

layered vanadates due to the continuous deformation (expansion and contraction) of the fragile

structure, can also make battery performance hastily decline [10, 11]; (2) The severe side reactions

in Zn anode surface. Common side reactions include the zinc dendrite growth that will cause battery

failure once piercing the diaphragm, the corrosion that will impair the coulombic efficiency, the

passivation that is the main reason for limiting the capacity of zinc anode, and the hydrogen

evolution reactions that will cause battery swelling and the formation of by-products; (3) The low

chemical stability and electrochemical stability of the electrolyte. These are mainly reflected in the

restricted voltage windows, capacity and stability which are the main factor limiting the energy

density and battery recyclability, and the decomposition of electrolyte which can cause hidden

danger of battery deformation and swelling. In short, these above-mentioned complications could

4
ultimately result in lower coulombic/energy efficiency and shorter life span for rechargeable

aqueous ZIBs.

Although the most research works focus on the construction and optimization of electrode

materials to improve the performance of aqueous ZIBs [12-17], the current key challenges of

aqueous ZIBs are closely related to the regulation of electrolyte [18, 19]. Many excellent works in

this aspect have been done, such as the widening of the electrochemical window of electrolyte [20],

electrostatic shell protection of the electrolyte on the anode side [21], and cathode/electrolyte ion

balance control [2]. It is obviously that the use of electrolyte additives is considered as the most

viable, economical, and effective approach to settle the major issues of aqueous ZIBs [2, 19]. In fact,

the electrolyte additive as an innovative energy storage technology has been widely applied in

battery field [22-24], especially in lithium-ion batteries (LIBs) or sodium-ion batteries (SIBs), to

enhance the energy density of battery [25], inhibit the growth of metal anode dendrites [26],

stabilize the electrode/electrolyte interface [27], increase the flame retardancy of the electrolyte [28],

and improve extreme environmental adaptability [29], etc. The role of electrolyte additives in

aqueous ZIBs is also very prominent. The comprehensive Table 1 summarizes the main electrolyte

additives and their effects in aqueous ZIBs for readers to understand the effectiveness of the

additives at a glance. It can be seen from the Table 1 that the research of electrolyte additives is

very necessary and valuable due to the extensive function of electrolyte additives. In terms of

electrolyte, electrolyte additives can improve ionic conductivity by augmenting the type and

number of conductive ions (e.g. Mn2+ additive [30], Na+ additive [31], etc.), and broaden the

electrochemical window by suppressing the oxygen evolution reaction (OER) and hydrogen

evolution reaction (HER), such as sodium dodecyl sulfate (SDS) additive [20], citric acid additive

5
[32], etc. As for the anodes, electrolyte additives can inhibit the growth of dendrites through some

ions or polar molecules additives (such as sodium ions [31], ether [21], etc.) to form the protective

layer on the surface of the anode by electrostatic action, through the method for increasing the

deposition overpotential of zinc (such as Pb [33] or imidazole ionic liquid additives [34]), as well as

through limiting the Zn2+ 2D diffusion on the anode surface (such as PEG200 additive[35]). In the

cathode side, the electrolyte additives can stabilize the cathode and prevent its dissolution by

adjusting the equilibrium reaction between the cathode and the electrolyte, forming the protection

film on the surface of cathode, and adjust the solvation structure [2, 8, 36]. More importantly,

additives such as Al3+ [37], Na+ [31], Mg2+ [38], and so on can increase the voltage and capacity

performance of the cathode through the mechanism of hybrid ions insertion. It is indicated that the

electrolyte additive is an important parameter for optimizing the battery performance.

At present, there are many excellent reviews in the field of ZIBs; these include the general

overview of ZIBs [5-7, 39-43], the design and energy storage mechanism of cathode materials [17,

44], and the issues and perspective of Zn anode [45, 46], the progress and strategy of zinc-ion

electrolyte [47, 48], etc. However, there have been few perspective reviews of electrolyte additives

in aqueous ZIBs. Considering that the cathode, anode, and electrolyte performance improvement is

inseparable from the help of electrolyte additives, a timely review with an academic perspective in

this aspect is urgent, which will help to improve our more comprehensive understanding of zinc-ion

electrolyte and have a significant assistance for further development of ZIBs. Herein, a systematic

and comprehensive summary of the types and functions of electrolyte additives for aqueous ZIBs

was introduced. We particularly highlighted the fundamental scientific understanding of the effects

of electrolyte additives on the electrolyte, anode side and cathode side based on the Zn chemistry.

6
Moreover, the outlook on the development of zinc-ion electrolyte additives regarding structural

insight of electrolyte, promotion of electrolyte stability, compound additives effect, design of novel

electrolyte, and application in other electrolyte system was proposed.

Table 1 Electrolyte additives and their effects in zinc-ion batteries

Type Additives Effects Ref.

Inhibit NaV3O8·1.5H2O dissolution
[31]
Form anode electrostatic shield
Na2SO4
Restrain Na5V12O32 dissolution [49]
Enhance stability of the Na0.56V2O5 [50]
Impede MgxV2O5·nH2O dissolution
MgSO4 [38]
Improve capacity
Enhance ion transport [30]
2+
Adjust the Mn dissolution balance [2]
Modulate electrochemical stability window [4]
Form the cathodic protection film
Enhance interface compatibility [8]
Improve capacity
Improve capacity
[51]
Improve stability
MnSO4
Improve the utilization of Mn2O3
[52]
Improve cycle stability
Form ε-MnO2
Ionic
Cause activation [53]
Stabilize the MnO2 cathode
Mn2+ ion deposition [54]
Enhance the reversibility
[55]
Improve capacity retention
CoSO4 Suppress Co dissolution of Co(III) rich-Co3O4 [56]
Modulate electrochemical stability window
Al2(SO4)3 [37]
Improve operating voltage
Ni(TfO)2 Increase zinc anodes stability [57]
Suppress dendrites
PbSO4
Pb2+ co-deposition
Suppress dendrites
NiSO4 [58]
Ni2+ co-deposition
Generate bubbles
CuSO4
Loose zinc dendrites adhere
ZnBr2 Improve the utilization of reactants [59]
Indium sulfate Affect zinc texture growth [60]
7
 Modulate electrochemical stability window [20]
SDS Adjust Zn crystallographic properties [61]
Have high dendritic growth [62]
Inhibit passivation [63]
SDBS Enhance interface compatibility [19]
Have high dendritic growth [62]
Diethyl ether Form anode electrostatic shield [21]
Increase the zinc nucleation overpotential [64]
CTAB Adjust Zn crystallographic properties [61]
Increase corrosion rate [62]
EMI-Cl Increase the zinc nucleation overpotential
EMI-PF6 Increase the zinc nucleation overpotential
[34]
EMI-TFSA Increase the zinc nucleation overpotential
EMI-DCA Increase the zinc nucleation overpotential
PEI Suppress zinc dendrite formation [65]
Change zinc morphology
BPEI [66]
Change deposition kinetics
Reduce zinc corrosion [67]
Adjust Zn crystallographic properties [61]
(NH4)2CS
Affect zinc morphology
[68]
Improve efficiency
organic Reduce zinc corrosion
Ethanol [69]
Reduce passivation
Decrease corrosion rate
Naphthalene
Decrease needle growth
Chloro [62]
Impede dendritic growth
benzene
Increase electrical capacity
Triton X-100
Inhibit zinc-dendrite growth [70]
Glue Maintain a high current efficiency [71]
Imidazole Reduce zinc corrosion
[72]
Reduce zinc corrosion
PEG Adjust Zn crystallographic properties [61]
Suppress dendrites [73]
2+
Limit Zn 2D diffusion
PEG200 [35]
Inhibit dendrite growth
Tartaric acid Increase the hydrogen overpotential
Succinic acid Increase the hydrogen overpotential [32]
Citric acid Increase the hydrogen overpotential
Limit Zn2+ 2D diffusion
TBA2SO4 [74]
Promote the uniform deposition
Urea Adjust the solvation structure [36]
PAM Regulate zinc uniform deposition [75]
8
 V2O5 Stimulate zinc corrosion
[67]
ZnO Reduce zinc corrosion
Suppress Zn dendritic growth [76]
SnO Suppress dendrite formation
Enhance cycle reversibility
[58]
Inorganic Suppress dendrite formation
Bi2O3
Enhance cycle reversibility
Boric acid Affect zinc texture growth
[60]
Tin oxide Affect zinc texture growth
Phosphoric
Increase the hydrogen overpotential [32]
acid
Increase the zinc nucleation overpotential
Pb
Metal Affect zinc texture growth [33]
Sn Affect zinc texture growth

2 Electrolyte Additives for Zinc-Ion Batteries

There are still many urgent problems in aqueous ZIBs, such as the dissolution of cathodes, the

low electrochemical stability of the electrolyte, and the growth of anode dendrites, which limits

their further application [16, 77, 78]. The electrolyte additives play an important role in addressing

these issues [26, 61]. Currently, there are mainly four types of electrolyte additives for aqueous

ZIBs, including ionic additives, organic additives, inorganic additives and metal additives, as shown

in Figure 1.

9
Figure 1. Overview of classification of electrolyte additives for zinc-ion batteries.

Ionic additives include Na+, Mg2+, Co2+, Mn2+, Al3+, Pb2+, Ni2+, Cu2+, In3+, Bi3+, In3+, Br- [31,

37, 55, 56, 59, 60, 79], etc. This type of additive with simple preparation but high performance

possesses the widest range of functions. Not only can they change the reaction mechanism and

optimize the electrochemical performance of the cathode, but also can increase the ionic

conductivity of the electrolyte and inhibit the dendrite growth of the Zn anode [30, 38]. For example,

Co2+ [56], Mn2+ [2], additives can protect the cathode by adjusting the dissolution equilibrium

reaction on the cathode side. Na+ [31], Mg2+ [38], Al3+ [37], additives hybrid intercalation can

change the cathode capacity, voltage properties. Pb2+ [33], Bi3+ [79], Ni2+, Cu2+ [58], In3+ [60],

additives can be used to regulate the zinc anode dissolution/deposition process. Br- additives can

increase the capacity of zinc flow batteries by increasing the utilization ratio of reactants [59]. In

conclusion, the versatility of ionic additives can be adjusted by changing the ion type, the size of the

ion charge, the solvation structure of the ion and the water solvent, the bond energy between the ion

and the electrolyte or the electrode, the electrochemical stability of the ion, and interface electric
10
double layer structure, etc. More importantly, their versatility, combined with the high ionic

conductivity, abundant production and easy preparation make them extremely practical.

In addition to ionic additives, organic additives are also popular subjects in additive research.

Organic additives possess the most abundant diversification, which can be divided into five

categories, namely small molecules, polymers, ionic, organic acids, and surfactant [8, 21, 61, 65].

Small molecule types such as ether, thiourea (TU), benzalacetone (BA), ethanol, imidazole,

naphthalene, chlorobenzyl, chlorobenzene, aniline, urea [21, 62, 69, 72, 80], etc., whose role is

mainly to change the surface morphology and reaction kinetics of zinc anode. The main types of

polymers are polyethylene glycol (PEG), polyacrylamide (PAM), and branched polyethyleneimine

(BPEI), polyethyleneimine (PEI), glue [7, 73]. Their main role is to change the overpotential of zinc

anode deposition, inhibit dendritic growth, and inhibit corrosion [7, 73]. Ionic type mainly refers to

imidazole ionic liquids, such as 1-ethyl-3-methylimidazolium hexafluorophosphate (EMI-PF6),

EMI-Cl, EMI-TFSA, and EMI-DCA which mainly affect the nucleation overpotential of the zinc

anode, and the degree of polarization can be controlled by adjusting the type of anions [34]. Organic

acids mainly include tartaric acid, succinic acid, citric acid, etc., which can increase hydrogen

overpotential and prevent dendrite growth [32]. Surfactants can be subdivided into three categories:

cationic surfactants, such as cetyltrimethylammonium ammonium bromide (CTAB),

tetrabutylammonium sulfate (TBA2SO4), which can make zinc deposition more dense and inhibit

dendrite growth, anionic surfactants, such as sodium dodecyl sulfate (SDS), and sodium dodecyl

benzene sulfonate (SDBS), which can increase the discharge capacity of the zinc anode and inhibit

surface passivation, and non-ionic surfactants, such as Triton X-100, which can inhibit dendrite

growth [62, 64, 70]. In short, organic additives could affect the properties of anode, cathode and

11
electrolyte, especially anode. Organic additives, especially surfactant types, are easily adsorbed on

the interface between the electrode and the electrolyte due to the influence of surface tension, which

affects the contact energy barrier between the water solvent and the electrode, the desolvation

process of the solute, and the deposition process of zinc ions. However, this is not clear about

whether organic additives on the cathode side will affect the size of the contact potential, the

insertion/extraction of ions and the cathode reaction mechanism.

As for inorganic additives and metal additives, in general, little research has been done in this

regard due to their own solubility limitations, and their soluble concentration is generally at the

level of mmol/L. Although it has extremely low solubility compared to ionic additives and organic

additives, a huge impact on the performance of the anode has been proved [33, 60]. Inorganic

additives are mainly divided into two types: oxide and inorganic acid. Oxides principally include

vanadium oxide, zinc oxide, lead oxide, tin oxide, bismuth oxide, etc. [60, 67, 76] Inorganic acid

chiefly refers to boric acid and phosphoric acid [32, 60]. They can adjust the crystal orientation or

morphology of zinc anode, thus affecting the dendrite growth, anode passivation and discharge

capacity [60]. Metal electrolyte additives primarily refer to lead and tin, whose principal function is

to change the deposition behavior of zinc and affect the texture growth [33]. Therefore, these two

types of additives are only used for the deposition control of zinc anodes mainly by affecting the

surface texture of zinc. Moreover, the limited low solubility can make an excellent effect of

inhibiting dendrite growth. However, the effect of these additives on the electrolyte and cathode is

still unknown.

3 Functional Additives Modifying Electrolyte Properties

As we known, the electrolyte, as the main components of battery, is of great importance.

12
However, the research of electrolyte is a complicated and tough task. At present, the electrolyte

systems for ZIBs are mainly divided into three major aspects including solid state electrolyte, gel

state electrolyte, and fluid state electrolyte. Among the fluid state electrolyte, it is subdivided into

aqueous system and organic system. All the discussion of electrolyte additives in this review are

based on the aqueous electrolyte unless noted otherwise. The electrolyte ion transport,

electrochemical window, and chemical stability of aqueous electrolyte are the crucial limiting

factors for rate performance, high voltage property, and high/low temperature performance [12, 18].

As demonstrated above, the breakthroughs in these aspects are inseparable from the electrolyte

additives. Therefore, it is of great significance to discuss the effects of electrolyte additives on the

electrolyte properties.

3.1 Enhancing Ion Transport Properties

Ion transport properties are one of the most basic properties of electrolytes. The conductivity

of the electrolyte characterizes the ability of ions to transport in the electrolyte, which directly

affects the rate performance of the battery. In the electrolytes system of zinc-ion batteries, poor

ionic conductivity is still an urgent problem for organic, gel and solid electrolyte systems [81-83].

Therefore, the rate capability of these electrolytes is generally not as good as that of aqueous

electrolytes [31]. In addition, the low ionic conductivity also hinders the application of batteries in

the field of low temperature and fast charge/discharge.

The magnitude of ionic conductivity is generally related to the type of solution, the species and

quantity of solute ions. The introduction of electrolyte additives plays a crucial role in improving

the ionic conductivity because it changes the type and quantity of conductive ions. Taking strong

electrolyte system as an example, the conductivity of the low concentration strong electrolyte

13
solution complies with Kohlrausch’s Law, as shown Equation 1.

𝛬𝑚 = 𝛬0𝑚 − 𝐾 √𝑐 (1)

where 𝛬𝑚 is the molar conductivity, which is the ratio (𝜅/𝑐) of conductivity (κ) to concentration (𝑐),

𝛬0𝑚 is limiting molar conductivity, 𝐾 is an empirical constant, 𝑐 is the electrolyte concentration.

Therefore, the conductivity κ can be expressed as Equation 2.

𝜅 = 𝑐(𝛬0𝑚 − 𝐾 √𝑐) (2)

It should be noted that when the solubility of the electrolyte is relatively low, 𝐾 √𝑐 can be

ignored. So for strong electrolytes, the ionic conductivity 𝜅 is proportional to the concentration 𝑐. In

addition, according to the additivity of the anion and cation limiting molar conductivity of

Kohlrausch’s Law (Equation 3), the conductivity κ can be further expressed as Equation 4.

𝛬0𝑚 = 𝜈+ 𝜆0+ + 𝜈− 𝜆0− (3)

𝜅 = 𝑐(𝜈+ 𝜆0+ + 𝜈− 𝜆0− ) (4)

where 𝜈+ and 𝜈− are the number of moles of cation and anion dissociated by dissolving 1

mole of electrolyte respectively, 𝜆0+ and 𝜆0− are the limiting molar conductivity of cations and

anions. Based on the Equation 4, the ionic conductivity of the electrolyte is not only related to the

solubility 𝑐, but also to the types of anions and cations. Therefore, operating the ion solubility and

adjusting the ion type can change the electrolyte ion conductivity. For example, adding ionic

additives such as manganese ions to the electrolyte can improve the electrolyte ionic conductivity due

to the increase of conductive ions. A typical example reported by Chen et al [30]. shows that by

adding Mn(CF3SO3)2 additive to 3M Zn(CF3SO3)2 electrolyte, the content of Mn2+ increased from 0

to 0.1M, and the conductivity increased from 4 S·m-1 to 6 S·m-1 (Figure 2a), which indicates that the

increase of additive ion solubility can obviously improve the conductivity of electrolyte. In addition,

14
it also demonstrates that the conductivity of CF3SO3-based aqueous electrolyte is higher than that of

SO4-based aqueous electrolyte (Figure 2b), which confirms that the type of additive ions will also

affect the ionic conductivity of the electrolyte.

Therefore, according to the above analysis, in general, any additives that help to increase the ion

richness and ion solubility such as Na+, Mg2+, Cl-, ClO4- etc. are conducive to the improvement of the

ionic conductivity of the electrolyte [31, 38]. In addition, considering the low ionic conductivity of

organic electrolytes, this introduction of ionic additives may be a practicable strategy to improve its

diffusion ability. What’s more, as for solid electrolyte, Doping additives can increase the defect and

vacancy concentration of the solid electrolyte, thereby increasing the ion conductivity. However, it

is worth noting that there may be a synergistic or antagonistic effect between different ionic

electrolytes. That is to say, not all ion mixing can enhance ion conductivity. For example, the

co-deposition of Ca2+ and SO42- will reduce the conductivity, so the interaction criterion between

the electrolytes should be considered when preparing new electrolytes.

3.2 Modulation of Electrochemical Window

Aqueous ZIBs are presently far from reaching large-scale, high-energy-density energy storage

requirements due to their limitations of the electrochemical stability window (ESW). The low ESW

of aqueous electrolyte would suppress the operating voltage and lead to insufficient energy density

for aqueous ZIBs [12]. In general, the ESW is influenced by two aspects: the lowest unoccupied

molecular orbital (LUMO) (or conduction band (CB)) and highest occupied molecular orbital

(HOMO) (or valence band (VB)) of electrolyte, the chemical potential 𝜇𝐶 of the cathode and 𝜇𝐴

of the anode, as shown in Figure 2c [84]. The band gap 𝐸𝑔 between the electrolyte LUMO and

HOMO energy levels is the electrochemical stable window of the electrolyte. And the 𝑉𝑜𝑐 between

15
the 𝜇𝐴 of the anode and the 𝜇𝐶 of the cathode is called the electromotive force of the battery. In

order to form the thermodynamically stable battery system, the conditions of 𝜇𝐴 <LUMO and

𝜇𝐶 >HOMO must be met, and the corresponding relational expression can be expressed as Equation

5 [85].

𝑒𝑉𝑜𝑐 = 𝜇𝐴 − 𝜇𝐶 ≤ 𝐸𝑔 (5)

To sum up, upgrading the voltage window of the aqueous zinc-ion battery can be improved in

two ways, including reducing the HOMO level of water, namely, increasing OER potential, and

increasing the LUMO level of water, namely, reducing HER potential. A typical example that

elevate voltage window is that adding SDS additive to the 1M Na2SO4/1M ZnSO4 aqueous

electrolyte by using Na2MnFe(CN)6 as the cathode and zinc as the anode can make the

electrochemical stability window of aqueous ZIBs reach 2.5V [20]. SDS additive can form a

hydrophobic layer at the electrode/electrolyte interface. When water passes through this

hydrophobic layer, there will be a high energy barrier, so water is not easily splitted to produce

oxygen, thereby expanding electrochemical stability window, as shown in Figure 2d. Furthermore,

this dewatering mechanism, on the one hand, hinders the contact between water and the electrode,

thereby improving the electrochemical stability of the water. On the other hand, it is conducive to

the desolvation of zinc ions, thereby preventing dendrite growth and by-product generation and

improving Coulombic efficiency [86-88].

In addition, ionic additives also help to increase the electrochemical stability window of water

solvent. Mn2+ additives can help to suppress the oxygen evolution reaction to broaden the reaction

window through the competition mechanism of the deposition reaction of Mn2+ and the oxygen

evolution reaction of the solvent [89]. Figure 2e exhibits that ionic additives such as Al3+ also can

16
increase the electrochemical window of the battery. The electrolyte containing Al3+ additives

compared to the ordinary Zn(CF3SO3)2 electrolyte can reduce the hydrogen evolution potential from

0.8V to 0.61V, and increase the oxygen evolution potential from 2.31V to 2.51V, thus increasing the

electrochemical window by nearly 0.4 V [37]. One possible reason for this enhancement is the

change in the interface electric double layer and solvation structure of the electrolyte. On the one

hand, Al3+ preferentially Zn2+ adsorbs on the interface to change the interface structure. On the other

hand, according to molecular dynamics calculations, the peak in Al-O Radial Distribution Function

(RDF, 1.86 Å) [90] is smaller than that in Zn-O RDF (1.97 Å) [91], which proves that Al3+ has a

stronger constraint effect on water, so that the water solvent can be more stable. However, more

in-depth works in the future will need to confirm this guess. Anyhow, ionic additives that broaden

the electrochemical window can be divided into decomposable ionic additives that compete for

electrons through their own redox reaction, and stable ionic additives that mainly affect the

electrolyte or interface structure.

In short, in aqueous ZIBs, the electrolyte issues are the most vulnerable problem. Especially

near the electrode/electrolyte interface, the decomposition of water and other related side reactions,

such as the formation of (Zn(OH)2)3(ZnSO4)(H2O)3 by-product, are particularly serious. Adding

additives in the electrolyte can change the interface structure and properties of the electrolyte and

the electrode. We would like to highlight that electrolyte additives can improve the performance of

electrolyte mainly in three ways: One is to isolate the contact between water and electrode, such as

introducing interface hydrophobic substances to make it difficult for water to contact the electrode,

whose function is similar to that of the MOF coating or the in-situ formed interface film on the zinc

anode[87, 88]; The second is to change the solvation structure of water, for example, from

17
Zn(H2O)6 to Al(H2O)6, which is similar to the high concentration electrolyte effect; The last is

introducing competing reactions to reduce the side reactions of water, for example, introducing

Mn2+ deposition reactions.

Figure 2. Functional regulation of additives on electrolyte bulk properties. (a) The conductivity

diagram of 3M Zn(CF3SO3)2 electrolyte with different concentrations of Mn(CF3SO3)2 additive. (b)

The pH and conductivity diagrams of adding 0.1M Mn2+ additive to 3M Zn(CF3SO3)2 and 3M

ZnSO4 electrolyte. Reprinted with permission from Zhang et al. [30] Copyright 2017 Springer

Nature. (c) Energy level schematic diagram of cathode, anode and electrolyte. Reprinted with

permission from Xu et al. [85] Copyright 2018 Elsevier Inc. (d) Energy barrier image of water

passing through the SDS hydrophobic layer. Reprinted with permission from Hou et al. [20]

Copyright 2017, The Royal Society of Chemistry. (e) Comparison of the electrochemical windows

of 2M Zn(CF3SO3)2 electrolyte and 1M Al(CF3SO3)3/1M Zn(CF3SO3)2 electrolyte. Reprinted with

permission from Li et al. [37] Copyright 2020 American Chemical Society.

18
3.3 Change of Other Electrolyte Features

The function of electrolyte additives is wonderful, electrolyte additives can enhance some

other peculiar characteristics of the electrolyte, for example, high/low temperature performance,

high voltage performance, electrolyte protection under overcharge conditions, etc. [28] which are of

significant meaning for battery applications. High and low temperature performance is conducive to

the use of the battery in harsh environments; the high voltage performance is favorable for

improving the energy density of the battery; the overcharge protection can increase the safety factor

of the battery. The indispensable reason why electrolyte additives cause this electrolyte features is

that the SEI film formed by electrolyte additive separate the electrode and electrolyte, therefore,

embellishing the interfacial circumstances. This fresh interface compared with the primary one

could be stabilized (the foundation of persistent cycle), electronically insulated (blocking electrolyte

getting electron from electrode), and highly ionic conductive (profitable for low temperature

conduction).

The formation of SEI film is mostly in connection with the basic properties of electrolyte

additives, the most important of which are the HOMO and LUMO energy level properties of the

additives. For example, under extreme acute conditions of high temperature and high voltage, it is

easy to cause electrolyte decomposition and side reactions at the electrode/electrolyte interface.

According to the molecular orbital theory, the oxidation potential of the molecule is related to the

HOMO orbit, and the molecule reduction potential is related to the LUMO orbit. Therefore, if the

selected LUMO orbital of the electrolyte additive is lower than the anode chemical potential 𝜇𝐴 ,

the electrolyte additive is easily reduced and decomposed on the anode surface to form the stable

SEI film to protect the anode to prevent the electrolyte from further decomposing. Similarly, if the

19
HOMO energy level of the selected additive is higher than the cathode chemical potential 𝜇𝐶 , then

the additive is likely to deposit the cathode electrolyte interface (CEI) on the cathode to prevent

further decomposition of the electrolyte, as shown in Figure 2c [85]. Hence, the formation of

interface film cuts off the interminable consumption of electrolyte and alleviates the stacking of

by-product. In addition, the cathode dissolution and anode corrosion, which is particularly severe

under hyperactive situation, could also be restrained due to the separation from electrolyte and

interface film protection.

The discussion above is primarily about extremely rigorous reaction condition, where

by-product is easily generated, nevertheless, low temperature condition is distinct, where ions

transport capacity is the preferential consideration. Therefore, the role of the SEI film with high

ionic connection decomposed by electrolyte additive is significantly important, which is one of

critical factor to improve the low temperature performance of the electrolyte. In addition to the

interface ionic transport properties, bulk ionic conduction at low temperature is another

considerable parameter. An effective method to promote bulk ion transmission is to bring down the

freezing point of electrolyte system. According to the freezing point drop formula of Blagden's Law

in the ideal solution, as shown in Equation 6.

∆𝑇𝐹 = 𝐾𝐹 ∙ 𝑏 (6)

Where ∆𝑇𝐹 is the freezing point depression, 𝐾𝐹 is the cryoscopic constant, and 𝑏 is the

molality. As can be seen from Equation 6, the increase in solute concentration (𝑏) can lower the

freezing point, so the addition of additives can also reduce the freezing point of the solution.

Furthermore, As discussed in Enhancing Ion Transport Properties section, electrolyte additives are

beneficial for increasing ion transport performance. Therefore, additives are favorable for increasing

20
the low temperature characteristics of the electrolyte [92].

In general, electrolyte features under extreme conditions as discussed in this section could be

roughly classified to two status, namely, severe reactivity condition (high temperature and high

voltage) and low reactivity condition (low temperature). High reactivity will be accompanied by

severe side reactions, such as cathode discussion, electrolyte split, and anode corrosion. In order to

alleviate the occurrence of this unfavorable situation, the introduction of electrolyte additive can

optimize this performance by interface film, such as CaSO4•2H2O film, relieving sophisticated

interface reaction at severe reactivity condition. Inspired by this, artificial cathode or anode

interface film will be a good choice to improve the extreme performance of the battery. Conversely,

under low temperature conditions, ion migration is the most head-scratching problem. Electrolyte

additives can improve its low temperature performance by facilitating the ionic conduction

(including interface conduction and bulk conduction).

4 Toward Highly Reversible Zn Anode with Electrolyte Additives

Many additives, such as ionic, organic, inorganic, and metallic additives, have been used in

zinc anodes to control the zinc surface morphology and inhibit side reaction, such as zinc dendrite

growth, hydrogen evolution reaction, and zinc surface corrosion and passivation. With the help of

these advanced additives, the significant results on the protection of the anode and the optimization

of the overall performance of the battery have been achieved [60, 61].

4.1 Regulation of Zinc Deposition Process

The deposition process of the metal anode is a major problem in the battery, whether it is

lithium ion battery or zinc ion battery, because the uneven deposition will not only cause low

coulombic efficiency, but also lead to the failure of battery. Regulation of zinc deposition process

21
mainly includes inhibiting the growth of zinc dendrites and affecting the texture growth. The

adjustment of the growth of dendrites in the zinc deposition process is the most intuitive. The

change in texture is not easy to see intuitively, which represents the crystal surface of zinc metal in

contact with the electrolyte, but indirectly affects zinc anode corrosion, dendrite growth and other

anode performance.

Among them, the inhibition of zinc dendrite growth is widely studied, whose main methods

are the electrostatic shield mechanism and improvement of nucleation rate [21, 33]. The

electrostatic shield mechanism has been extensively studied in LIBs and ZIBs. Taking deposition of

Li+ ions as a typical example, this mechanism can fundamentally change the Li+ deposition

morphology, as shown in Figure 3a-c, which depends on the electrolyte additive cation that has an

effective reduction potential lower than that of Li+ ion [26]. The sharp end of initial protuberant tips

that unavoidably occur during the Li+ deposition process could serve as a charge center in the

electric field for continuous accumulation of charges (Figure 3a). During the charging process, the

additive cation with a lower reduction potential are preferentially adsorbed on initial protuberant

tips to form an electrostatic shield. This positively charged shield will repel incoming Li + from the

protrusion forcing further Li+ deposition to adjacent regions of the anode (Figure 3b) until a smooth

deposition layer is formed (Figure 3c). Obviously, this mechanism has also been applied to aqueous

ZIBs with good results. According to the electrostatic shield mechanism, Niu et al added Na2SO4

additive into ZnSO4 electrolyte, which can effectively suppress the zinc dendrites (Figure 3d) [31].

The surface of the protruding zinc dendrite will be covered by sodium ions to form a thin layer of

sodium ion protection shell. The protective shell is positively charged and repels zinc-ions, which

hinders the further growth of zinc dendrites. The current theory also extends to not only metal

22
cation additives, but other non-metal ion additives with similar properties to metal cation, for

example, diethyl ether small molecules can also cause the same effect [69]. The reason why ether

molecules has a similar effect to metal cation is that they are relatively stable and do not participate

in the electron transfer process in the zinc deposition process. More importantly, they are polar

substances that can be attracted to the surface of the initial protuberant zinc tips under the action of

electrostatic field and further hinder zinc ion deposition. The diethyl ether used as an electrolyte

self-healing additive was a typical example in this aspect (Figure 3e). By adding 2 vol% diethyl

ether to the electrolyte, the highly polarized diethyl ether additive can be easily adsorbed on the

surface of zinc dendrites because of the high electric field strength at the tip of the zinc dendrites,

thereby, the growth of zinc dendrites is suppressed [21]. As we known, other organic molecules like

ethanol and acetone, are also stable and polar, which is worth to be tried as electrolyte additives. In

addition, interestingly, some oxides for example Al2O3 [93], can also serve as the electrostatic

protection shell, as exhibited in Figure 3f. Therefore, the additives that can be preferentially

deposited to generate dielectric oxide on zinc dendrite could also be potential to act as the dendrite

growth inhibitors.

23
Figure 3. Protective shell mechanism for inhibiting dendrite growth. (a-c) Evolution of lithium

dendrite growth inhibition by electrostatic shield mechanism. Reprinted with permission from Ding

et al. [26] Copyright 2013 American Chemical Society. (d) Schematic diagram of the inhibition

effect of growth of zinc dendrites and protection effect of cathode by sodium ion additives.

Reprinted with permission from Wan et al. [31] Copyright 2018 Springer Nature. (e) Protective

shell effect of diethyl ether additive on inhibiting zinc dendrite growth. Reprinted with permission

from Xu et al. [21] Copyright 2019 Elsevier Ltd. (f) Dendrite growth inhibition by Al2O3 protective

shell. Reprinted with permission from Wang et al. [93] Copyright 2020 Springer Nature.

24
 Inhibiting the growth of zinc dendrites can not only by using a electrostatic shield mechanism,

but also by using the method of increasing nucleation rate to make zinc grains more uniform [33],

including increasing zinc deposition overpotential and limits the Zn2+ 2D diffusion on the anode

surface. Generally speaking, the increase of overpotential is not conducive to the deposition of zinc

ions, but the appropriate overpotential, which has little effect on the deposition process, is on the

contrary conducive to inhibit the growth of dendrites. The overpotential mainly affects the

parameter of the number of nucleation, and its corresponding mechanism is shown in Figure 4a.

According to the classical deposition nucleation mechanism, the improvement of the overpotential

of the deposition will lead to the increase in the number of nucleation and the nucleation speed, thus

making not conducive to dendrite growth [94]. Conversely, a smaller number of nucleation may

lead to excessive deposition of zinc ions at a certain site, resulting in uneven growth of zinc and

therefore leading to the formation of dendrites. Many kinds of additives can increase the

overpotential of zinc deposition, including surfactant [64], metals [33], ionic liquids [34], etc. A

typical example reported by Zhu et al. is that the addition of CTAB to the zincate electrolyte can

make the initial potential of zinc deposition negative, reduce the rate of dendrite growth, and make

the zinc deposition denser and more uniform [64]. Otani et al. reported that the addition of 1.0

mmol dm−3 Pb to the electrolyte can significantly shift the deposition potential of zinc (Figure 4b)

and change the nucleation behavior of the initial stage of zinc electrodeposition, which is from

layered micro-step deposition to discrete uniform deposition [33]. In the absence of Pb additive, the

growth of zinc is coarse and irregular (Figure 4c), while under the condition of Pb additive, the zinc

deposition is more finer and uniform (Figure 4d). In addition, ionic liquid additives have similar

effects. The addition of imidazole ionic liquid additives to the zincate electrolyte is a typical

25
example in this aspect, in which imidazole ionic liquid additives can inhibit the growth of zinc

dendrites by increasing the nucleation overpotential and polarization degree, and the degree of

polarization is related to the type of anion (Cl- <PF6- <bis(trifluoromethanesulfonyl)imide(TFSA-)

<dicyanamide(DCA-)) [34]. As shown in Figure 4e and 4f, the addition of ionic liquid additives

significantly inhibited the growth of zinc dendrites compared to that without additives. These

additives above augmenting the overpotential of zinc deposition is due to the reduction of active site

for Zn2+ deposition on the anode surface, which is occupied by electrolyte additive. For example,

CTAB and imidazole ionic liquid additives can be absorbed on active site, therefore, hindering the

incipient nucleation of Zn2+. As for Pb additive, which can be deposited on zinc surface, this

deposited Pb compared with original Zn possess higher nucleation overpotential, so the procedure

of nucleation is consequently postponed.

In addition to increasing the nucleation overpotential, limiting the 2D diffusion of Zn2+ on the

anode surface is also an effective way to increase the nucleation rate. Typical additives that limit 2D

diffusion include PEG200 and TBA2SO4 [35, 74], etc. The growth of zinc dendrites undergoes the

following process. First, the zinc ions in the solution are adsorbed on the surface of the anode, and

then these ions can diffuse on the surface. In order to reduce the surface energy of the system, the

zinc ions will aggregate into large nucleation sites. Then the zinc ions in the solution continue to be

adsorbed, repeat the above process to form zinc dendrites. Therefore, limiting the 2D diffusion of

zinc ions on the anode surface by adding additives is of great significance to inhibit the growth of

zinc dendrites. The PEG200 and TBA2SO4 additive are adsorbed on the anode surface, thereby

hindering the process of zinc ion migration and aggregation on the anode surface, so that a large

number of tiny nucleation centers are formed on the anode surface, thereby controlling the uniform

26
deposition of zinc and inhibiting the growth of dendrites, as shown in Figure 5a and 5b. In addition

to PEG200 and TBA2SO4 additive, polyacrylamide (PAM) additives also have a similar effect [75],

which makes the zinc deposit uniformly without Zn2+ 2D diffusion and aggregation into dendrites

through the strong adsorption of acyl groups.

Figure 4. Anode dendrite regulation by overpotential effect. (a) Schematic diagram of

overpotential effect on zinc deposition and growth. (b) Zinc overpotential effect curve of Pb

additive with different content. The morphology comparison of zinc surface (c) without additives

and (d) under 1 mM Pb additive. Reprinted with permission from Otani et al. [33] Copyright 2017

Elsevier Ltd. The effect of blank, EMI-Cl, EMI-PF6, EMI-TFSA, EMI-DCA additives on the (f)

CV curve in ammoniacal electrolytes and (g) zinc surface morphology. Reprinted with permission

from Song et al. [34] Copyright 2016 American Chemical Society.

27
Figure 5. Anode dendrite regulation by limiting Zn2+ 2D diffusion. (a) Effect of PEG200

additive on zinc deposition process. Reprinted with permission from Mitha et al. [35] Copyright

2018 Wiley-VCH. (b) The process of zinc deposition regulated by TBA2SO4 additives. Reprinted

with permission from Bayaguud et al. [74] Copyright 2020 American Chemical Society.

The surface texture regulation of zinc deposition is another main content in zinc deposition

process. The zinc surface texture has an important influence on the surface morphology of zinc

anode. The texture represents the preferred orientation of the zinc anode at its interface with the

electrolyte, which determines the corrosion resistance and the direction of dendrite growth. In

general, the greater the angle between the direction of zinc dendrite growth and the surface of the

zinc anode, the more favorable the growth of dendrites. It was proved by Mackinnon et al. that

crystallographic orientation affects the surface morphology and dendrite growth state by affecting

the crystal growth direction (Figure 6a) [60, 71]. When the crystallographic orientation of the zinc

28
surface is (002), (103), (105) plane, the angle between the growth direction of the crystal and the

substrate shows 0-30°, which generally shows no dendrite growth; These directions can reduce zinc

corrosion, is favorable for smooth deposition and resistant to zinc dendrite growth [60]. When the

crystallographic orientation of the zinc surface is (114), (112), (102), (101), the angle between the

crystal growth direction and the substrate exhibits 30-70°, which dispalys the intermediate state;

When the crystallographic orientation of the zinc surface is (100) and (110), the angle between the

crystal growth direction and the substrate exhibits 70-90°, which is very conducive to the growth of

dendrites, as shown in Figure 6a. Some oxide and metal type additives are beneficial to the

formation of (002) basal plane. Typical oxide additives are indium sulfate, tin oxide, and boric acid

[60]. As the solubility of the boric acid additive increases, the orientation of the (002) basel crystal

plane increases (Figure 6b). Similarly, tin oxide and indium sulfate additives can also reduce the

growth of (101) crystal plane and promote the growth of (002) or (103) crystal planes. In addition,

metallic additives such as Pb can also regulate the growth of texture, and make zinc preferentially

grow in the (002) direction (Figure 6c) [33]. The probable cause why the crystallographic

orientation of the zinc surface affect the deposition morphology can be summarized as follows:

firstly, metal Zn is the hexagonal close-packed (HCP) structure, and the close packed face is (001)

plane, which is stable basal plane and is detrimental to dendrite formation. On these grounds, the

planes that are equivalent to or approximately parallel to the (001) plane are resistant to dendrite

growth, such (002), (103), (105) plane. Otherwise, the planes that are perpendicular to the (001)

plane are be inclined to dendrite production, such as (100), (110) plane. In other words, the

tendency of zinc anode dendrite emerging will enlarge with the increase of the angel between the

(001) basal plane and the crystallographic plane of anode surface texture.

29
 In short, the regulation of zinc deposition mainly includes dendrite growth and surface texture.

As for the regulation of dendrite growth, one method is to introduce polar ions or molecules to form

the electrostatic shielding effect to inhibit the growth of dendrites; The second method is to increase

the overpotential to increase the nucleation sites of zinc deposition, so that the zinc deposition is

uniform and thus dendrite growth can be inhibited. The third one is to limit Zn2+ 2D diffusion on the

anode surface to prevent the migration and accumulation of zinc ions on the anode surface to form

large nucleation sites. As for the regulation of surface texture, increasing the ratio of 002 crystal

planes can effectively inhibit the occurrence of dendrites and other side reactions, which is because

002 plane is the close-packed crystal planes owning the lowest energy.

Figure 6. Texture regulation mechanism for inhibiting zinc dendrite growth. (a) The discipline

of the zinc surface texture affecting the surface morphology. The effects of (b) boric acid additives

with different concentrations and other inorganic additives on zinc deposition texture. Reprinted

with permission from sun et al. [60] Copyright 2018 WILEY-VCH. (c) The effects of Pb additive on

zinc deposition texture. Reprinted with permission from Otani et al. [33] Copyright 2017 Elsevier

Ltd.

30
4.2 Side Reaction Inhibition and Coulombic Efficiency Improvement

The side reactions of zinc anode mainly include zinc corrosion, hydrogen evolution reaction

and anode passivation [69, 72]. Depending on the electrolyte additive's mechanism for inhibiting

side reactions, electrolyte additives can be roughly divided into two types: those that adjust the zinc

surface orientation, where different surface orientations of zinc anodes are corresponding to

different surface activity, and those that adjust the anode surface film structure. Here, the second

type is emphatically discussed. The influence mechanism that additives participate in the formation

of zinc surface film structure and regulate side reactions is shown in the Figure 7a. And this film

effects are often associated with the regional galvanic cell reaction on the metal surface which is the

result of metal corrosion. The regional galvanic cell reaction includes regional anode reaction and

regional cathode reaction [67, 72]. Additives that can inhibit anode reactions are called anodic type

inhibitor; additives that can inhibit cathode reactions are called cathodic type inhibitor; and

additives that can both inhibit anode reactions and cathode reactions are called mixed-type

inhibitors. Such additives that favor film formation are often beneficial to regulate this galvanic cell

reaction, thereby inhibiting corrosion, delaying zinc electrode passivation, and hindering the

reduction of hydrogen ions on the metal surface [63]. What’s more, side reaction can be adjusted by

the densify degree of this anode surface film. Generally speaking, the denser one is favorable for

restraining corrosion, and the looser one is in favour of suppressing passivation.

Corrosion is one of the most common side reactions of zinc anodes. Zinc corrosion can lead to

the gradual dissolution of zinc anodes, causing the reduction in coulombic efficiency and the

decrease in battery capacity, which is the major cause of zinc anode failure and battery lifespan

reduction. Crystallographic orientation can affect the corrosion rate of zinc metal. By adding

31
corresponding texture-prone additives, such as indium sulfate [60], it is pointed out that the

corrosion rate of (002) or (103) oriented electrogalvanized zinc is 11 times lower than that of

ordinary zinc foil [60]. In addition, the type and concentration of electrolyte additives will also

affect the corrosion rate by regulating the galvanic cell reaction process on the surface of the zinc

anode. For V2O5 additives, V2O5 can stimulate zinc corrosion by reducing oxygen overpotential and

increase the corrosion rate; while ZnO and thiurea additives can reduce corrosion, and increased

concentration will lead to enhanced corrosion inhibition [67]. For ethanol additives, 5% v/v ethanol

has the lowest corrosion potential, as shown in Figure 7b [69]. In addition, it was confirmed that

the zinc corrosion could be greatly inhibited by the synergistic effect of hybrid additives, such as

0.05% imidazole + 0.05% polyethylene glycol composite electrolyte additives [72]. In short, the

essence of corrosion is the tiny galvanic battery on the anode surface, including cathodic process

and anodic process. Texture could affect corrosion due to stability difference of different

crystallographic plane. The effective anode surface film (for example, the film formed by ZnO,

thiurea, ethanol, imidazole, and polyethylene glycol etc.) can also slow down the corrosion rate.

What’s more, it will be affected by the densify degree of anode surface film. For example, the

imidazole + polyethylene glycol composite electrolyte additives own higher surface coverage than

the individual one, therefore, higher corrosion resistance is exhibited.

Hydrogen evolution reaction is another serious side reaction of zinc anode, which is often

accompanied by severe zinc corrosion. Furthermore, due to the generation of gas, the battery will

swell which will lead to electrolyte leakage and even battery failure. The hydrogen evolution

reaction can be suppressed by increasing the hydrogen overpotential. Acid additives such as tartaric

acid, succinic acid, phosphoric acid, citric acid, etc. can put off the hydrogen reaction process, and

32
tartaric acid possesses the strongest ability among these acids, as shown in Figure 7c [32]. In

addition, quaternary mixed additives (PEG, CTAB, BA, and TU) also can effectively inhibit this

side reaction [80]. The reason why these additives can behave above capability is that these additive

molecules can be adsorbed on the surface of the zinc anode to block the active sites on the zinc

surface [32].

The passivation of zinc metal is also a serious side reaction, which suppresses the Zn2+

stripping from the zinc anode, thereby limiting the discharge capacity. It is usually accompanied by

by-product deposition on the surface of the zinc metal. Typical additives such as ethanol molecule

and sodium dodecyl benzene sulfonate (SDBS) can make a big change in this respect. Ethanol

additives can enhance the dissolution of zinc and hinder the passivation of zinc anodes, thereby

improving the discharge capacity [69], while SDBS additives can make the zinc surface appear

porous structure, thereby inhibiting the passivation process (Figure 7d) and promoting the

discharge capacity (Figure 7e) [63]. In short, passivation process will produce dense passive films,

which sever the pathway Zn deposition and dissolution. Though regulating this dense structure to

porous one by adding electrolyte additive, anode passivation will consequently be delayed.

It is worth noting that the side reactions in aqueous ZIBs including corrosion, passivation,

hydrogen evolution reactions, and other by-product formation, are closely interconnected.

Combination with the zinc dendrites, these symptoms will eventually affect coulombic efficiency

[21]. In general, the smooth zinc surface has higher coulombic efficiency than the uneven zinc

surface which easily lead to the shedding of protruding zinc dendrites [33, 61, 95]. Inhibiting the

generation of side reactions can strengthen the utilization of zinc and reduce irreversible

consumption of zinc and electrolytes [60, 69]. Therefore, any electrolyte additives which could

33
inhibit the growth of zinc dendrites and the generation of side reactions can improve the coulombic

efficiency of Zn2+/Zn plating/stripping.

As discussed above, the electrolyte additives can affect the corrosion, passivation, and

hydrogen evolution processes by participating in the composition of the anode interface film.

Generally speaking, side reactions can be accompanied with regional galvanic reactions on zinc

anode surface, including regional cathode processes and regional anode processes. The dense

interface film form by additives can effectively isolate the direct contact between water solvent and

zinc anode which cuts off the possibility of regional battery reactions, thereby reducing the

corrosion of zinc and the process of hydrogen evolution. In addition, additives can also reduce the

density of the passivation film on zinc anode surface to ease the passivation process. Furthermore,

reducing side reactions can cut down the excess consumption of zinc anode, thereby increasing the

coulombic efficiency of the Zn2+/Zn plating/stripping.

34
Figure 7. Side reaction regulation of electrolyte additive. (a) Mechanism of additives to inhibit

side reactions of zinc anode. (b) The effects of different concentrations of ethanol additives on zinc

corrosion potential. Reprinted with permission from Hosseini et al. [69] Copyright 2018 Springer

Nature. (c) The effect of phosphoric (ZnOPA), succinic (ZnOSA), tartaric acids (ZnOTA) and citric

additives (ZnOCA) on hydrogen evolution curve. Reprinted with permission from Lee et al. [32]

Copyright 2005 Elsevier B.V.. Effect of SDBS additives on (d) zinc anode passivation and (e)

capacity. Reprinted with permission from Yang et al. [63] Copyright 2003 Elsevier B.V..

35
5 Cathode Chemistry Associated with Electrolyte Additives

The cathode material has many serious problems such as active material dissolution, structural

collapse, fast capacity decay, low capacity, low operating voltage, and sluggish reaction kinetic [44,

96, 97]. The functional limitation of the cathode is another main reason why the aqueous ZIBs

cannot be practically used. Adding additives into electrolyte can efficiently help protect the cathode,

improve cycle stability, and increase capacity and operating voltage, etc [8, 37].

5.1 Protection and Stabilization of the Cathode

In aqueous ZIBs, the stability of the cathode material is vital important to the battery longevity

[40]. There are many reasons that can lead to instability of cathode materials. Firstly, the material

dissolution is common in the aqueous electrolyte, mainly including V and Mn dissolution [2, 38]. A

typical example is Mn dissolution resulted by the classic Jahn teller effect. The manganese oxygen

octahedron deforms, and the trivalent manganese is prone to disproportionation reaction to generate

divalent manganese ions, which will cause interface dissolution, and gradually cause the internal

structure of the material to collapse [98]; Secondly, Cathode crystal structure collapse will result in

the instability. On the one hand, material dissolution may cause structural collapse; on the other

band, divalent zinc ions have a strong binding force with the host structure, which is easy to cause

structural damage and material shedding [99]; Thirdly, stress can also cause cathode instability

[100]. the continuous insertion and extraction of ions causes the expansion and contraction of the

cathode material, which eventually leads to the presence of the electrode material stress, which

leads to capacity decay. These factors will cause a series of serious problems, such as the decrease

in specific capacity and reduced service life. Therefore, this aspect is of great concern to researchers,

and many efforts have been made. On the one hand, some good results have been achieved from the

36
perspective of the cathode, such as the stabilization of the crystal structure with K ions embedded in

the cathode [96], but the ideal effect has not been achieved; another important aspect is from the

perspective of electrolyte regulation, such as adjusting the state of the electrolyte and changing the

composition of the electrolyte. Among them, additives are the most commonly used and effective

means, whose main principle is to adjust the equilibrium reaction between the cathode and the

electrolyte and the mechanism of film formation (Figure 8a-c).

Cathode protection mainly include Mn-based material protection and V-based material

protection in aqueous ZIBs. Firstly, with regard to Mn-based cathodes, adjusting the equilibrium

reaction between the electrolyte and the cathode can effectively protect the cathode [101]. A typical

example is that Mn2+ additives were originally used to suppress the dissolution of manganese in

manganese-based material. Pan et al. deem that there is a dissolution/oxidation balance between the

Mn2+ dissolved in the electrolyte and the MnO2 in the cathode material [2]. The 0.1M Mn2+ additive

can maintain this balance, resulting that the active substance not easily dissolved in the electrolyte

to protect the cathode and reduce capacity loss (Figure 8d and 8e), and the corresponding

dissolution/oxidation reaction equation is shown in Equation 7.

1 1 1 2 1
𝑀𝑛𝑂2 + 6 ZnSO4 + 𝐻 + + 2 𝑍𝑛 + 3 𝐻2 𝑂 ↔ 2 𝑀𝑛2+
2

1
+ 6 ZnSO4 [𝑍𝑛(𝑂𝐻)2 ]3 ∙ 4𝐻2 O (7)
1 −2∆𝐺0
[𝑀𝑛2+ ]=[ZnSO4 ]3 ∙ [𝐻 + ]2 ∙ 𝑒 𝑅𝑇 (8)

Furthermore, according to the Equation 7, the solubility of Mn2+ at equilibrium state was

calculated according to Equation 8. In addition, the content of Mn2+ additives will also affect the

level of stability. For instance, in the 2M ZnSO4 electrolyte, as the concentration of the Mn2+

additive increases, the battery capacity and stability of a MnO2/C–Zn battery increase

37
correspondingly, and the performance is optimal when the concentration of MnSO4 reached 0.5M,

as exhibited in Figure 8f [102]. Moreover, other ionic additives also have similar functions. A

typical example is the addition of 0.2 mol CoSO4 additive to suppress the dissolution of Co in the

Co(III) rich-Co3O4 cathode [56]. The Co(III) rich-Co3O4 cathode will dissolve in the solution in a

weakly acidic electrolyte until it reaches the equilibrium of dissolution, which will lead to the

capacity decline of the first few cycles, however, pre-adding Co ion additives can prevent this

process.

In addition to inhibiting the dissolution mechanism, Mn2+ additives also have the protective

layer mechanism. The JaekookKim team deems that Mn2+ additives can undergo the

deposition/dissolution reaction to form MnOx layer on the surface of ZnMn2O4 cathode, then, the

MnOx layer deposited by Mn2+ additive can prevent the dissolution of ZnMn2O4 (Figure 8g), and

the corresponding deposition equation is exhibited in Equation 9 [8].

𝑀𝑛2+ (𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑙𝑦𝑡𝑒) + 𝑥𝐻2 𝑂 ↔ 𝑀𝑛𝑂𝑥 (𝑠𝑢𝑟𝑓𝑎𝑐𝑒) + 2𝑥𝐻 + + 2𝑒 − (9)

Where the 𝑥 can be thought of as 2. As shown in the Equation 9, Mn2+ additives can be

deposited on the electrode surface to produce the MnOx protective layer mechanism to replace the

direct contact between ZnMn2O4 and the solution, thereby improving the stability of the cathode.

In addition, as for the protection of V-based cathodes, the dissolution problem of the

vanadium-based cathode is also very serious. At present, the dissolution of vanadium-based

cathodes mainly includes the dissolution of vanadium and the dissolution of alkali metal and

alkaline earth metal ions (such as Na+, Mg2+) in V-based cathodes, and the dissolution of the

imbedded ions will accelerate the further dissolution of vanadium. Some typical additives such as

Na+ and Mg2+ have been employed to inhibit the dissolution of the vanadium-based cathode to

38
reduce its capacity decay rate. In MgxV2O5•nH2O cathode, adding MgSO4 additive can play a role

similar to Na+ additive. On the one hand, by changing the equilibrium reaction of MgxV2O5•nH2O

dissolving Mg2+ to the electrolyte, the dissolution of MgxV2O5•nH2O is inhibited; on the other hand,

Mg2+ can be inserted into the vanadium oxide layer to play the ‘pillar effect’ role to maintain the

stability of the MgxV2O5•nH2O structure (Figure 8h) [38]. The dissolution balance between

NaV3O8•1.5H2O cathode and Na+ in the electrolyte can be maintained by adding Na2SO4 additive to

the ZnSO4 electrolyte, thereby inhibiting the dissolution of NaV3O8 • 1.5H2O [31]. Therefore,

NaV3O8 • 1.5H2O cathode has higher cycle stability in electrolytes containing Na+ additives (Figure

8i).

In addition, the solvation structure of the solution also has a certain effect on the stability of the

cathode structure. Hou et al. reported that in the birnessite cathode, Zn2+ and solvated water

molecules could be co-inserted into the cathode layer structure, but excessive intercalation of water

molecules would cause the collapse of cathode structure. By introducing strong ligand urea

additives [36], the solvation structure of zinc ions can be transformed into [Zn(H2O)2(urea)3]2+

complexes, thereby reducing the number of water molecules in the solvation structure. Less

intercalation of coordinated water molecules will reduce the deformation degree of the cathode

structure and bring down the structure damage of the cathode material. In short, additives can

stabilize the cathode by adjusting the solvation structure, mainly though reducing the destroy to the

crystal structure caused by the co-intercalation of water molecules.

To sum up, cathodic protection mainly refers to inhibiting the dissolution of the cathode,

including V dissolution and Mn dissolution. From the perspective of electrolyte additives,

dissolution balance control, surface coating and solvation structure regulation are third commonly

39
used methods. However, it is worth noting that from the perspective of thermodynamics, the

dissolution equilibrium reaction of different cathodes should be different, which corresponds to

different solution ion concentrations in electrolyte. Regrettably, the current ion concentration is

roughly set to 0.1M, and no fine distinction is made. In addition, Additives forming the cathode

interface protective film, such as MnOx film, can also effectively inhibit cathode dissolution.

Unfortunately, there are relatively few reports on SEI films on the cathode side of aqueous zinc-ion

batteries. The function and role of the SEI film on the cathode side may be a hot topic in the future

zinc ion system. Furthermore, regarding the influence of the solvation structure on the stability of

the cathode, the main reason is to reduce the co-intercalation of solvated water. However, whether

the change of the solvation structure will affect other properties on the cathode side, such as the

interface electric double layer etc., is still unclear.

Figure 8. The protection and stabilization of cathode by electrolyte additive. Inhibiting the
40
dissolution of manganese through (a) the dissolution equilibrium mechanism and (b) cathodic

protection film. (c) Schematic diagram of Mg2+ additive inhibiting Mg2+ dissolution of

MgxV2O5·nH2O cathode. Reprinted with permission from Zhang et al. [38] Copyright 2020

Springer Nature. (d) Cycling performance of Zn/MnO2 battery in 2M ZnSO4 electrolyte at 61.6

mAh g-1 and corresponding analysis of manganese dissolution and equivalent capacity loss. (e)

Zn/MnO2 battery cycle performance comparison without and with 0.1 M MnSO4 at 102.7 mA g-1

and 308 mA g-1. Reprinted with permission from Pan et al. [2] Copyright 2016 Springer Nature. (f)

Cycle performance comparison of MnO2/C cathode in different Mn2+ additive concentration at 300

mA g-1. Reprinted with permission from Li et al. [102] Copyright 2020 The Royal Society of

Chemistry. (g) Protective layer mechanism of Mn2+ additive on ZnMn2O4 cathode. Reprinted with

permission from Soundharrajan et al. [8] Copyright 2019 Elsevier B.V.. (h) Effect of Mg2+ additive

on cyclic stability of MgxV2O5·nH2O cathode. Reprinted with permission from Zhang et al. [38]

Copyright 2020 Springer Nature. (i) Effect of Na+ additives on the cycle stability of

NaV3O8•1.5H2O cathode. Reprinted with permission from Wan et al. [31] Copyright 2018 Springer

Nature.

5.2 Improvement of Capacity and Voltage

In addition to the battery cycle lifespan, the capacity and operating voltage properties are other

two very important battery parameters, which are the basic factors that determine the energy density

of the battery. However, unfortunately, for aqueous ZIBs, due to the limitations of cathode materials,

it is hard to have both high capacity and high working voltage. Although the vanadium-based

cathode has high capacity, the voltage platform is low and not obvious [17, 103]. The Prussian blue

cathode has high and obvious voltage platform, but it has low capacity [104]. The main reasons for

41
limiting the capacity and voltage of the cathode include: 1) The redox center of the cathode. For

example, the valence state of V in V2O5 can range from +5 to +3 [105], while the Fe in Prussian

blue can only range from +3 to +2 [104], so the vanadium base has a higher capacity than Prussian

blue. In addition, Mn center in manganese-based materials tend to have higher voltages than V

center in vanadium-based materials [106]; 2) The influence of structural factors, including the

influence of crystal structure and the size of cathode particles [107, 108]. For example, the vanadate

of the layered structure has higher capacity than the tunnel [109], and the nanostructure particle has

a higher capacity than the bulk [110]. 3) Limitation of electrolyte nature. The voltage window of the

cathode is limited by the voltage window of the electrolyte, namely the hydrogen evolution reaction

(HER) and oxygen evolution reaction (OER) voltages. So far, some methods have appeared to

regulate the voltage and capacity of the cathode; these include increasing the number and types of

redox centers [104], compounding with graphene [14], addition of additive ions [37], etc. Among

these improved methods, the regulation of the electrolyte via additives is the simplest and most

convenient. There are many additives, such as Na+ [31], Mg2+ [38], Al3+ [37], Br- [59], which can be

used to improve the capacity and voltage properties by increasing the use of reactants (Figure 9a),

hybrid ion insertion or change of contact potential (Figure 9b).

It was reported that the additives such as Br- can unlock the redox active substance capacity of

the zinc flow battery [59], In the zinc-iodine redox flow battery, Br- additive can be added to the

electrolyte on the cathode side to stabilize free iodine through complexation to form iodine bromide

ions (I2B-), which could make the iodide release more capacity (Figure 9c), and the corresponding

reaction formula is shown in Equation 10-12 [59].

2𝐼 − − 2𝑒 − ↔ 𝐼2 (𝑎𝑞) (10)

42
 𝐼 − + 𝐼2 ↔ 𝐼3 − (11)

2𝐼 − + Br − − 2𝑒 − ↔ 𝐼2 𝐵𝑟 − (12)

In the case of no Br- additive, only 2/3 I- participates in the reaction to emit electrons (Equation 10),

while the remaining 1/3 I- is used to stabilize I2 to form I3- (Equation 11). In the presence of the Br-

additive, the Br- additive can stabilize I2 to generate I2Br- so that I- can be released full capacity

(Equation 12). From the above analysis, 1/3 capacity could be excavated by the introduction of Br-

additive, which reminds us that improving cathode utilization by electrolyte additives in ZIBs also

owns enormous potentiality to upgrade capacity compared with exploiting new cathode materials.

Improvement of capacity and voltage is generally achieved through metal cation additives. A

typical example improving capacity is that the Mn2+ in the solution can provide additional capacity

through the deposition/dissolution reaction [2, 89]. The unique phenomenon also occurs in

vanadium-based cathodes, but via the hybrid ion insertion mechanism. Both Na+ and Mg2+ additives

can be inserted into the vanadium-based electrode like Zn2+, the capacities are consequently

increased [31, 38]. For example, the stability and capacity of the battery in the electrolytes of

ZnSO4 + MgSO4 are higher than those of pure 2M ZnSO4 electrolyte and pure 2M MgSO4

electrolyte (Figure 9d) .

It is generally difficult to increase the battery voltage, but it has been reported that the voltage

can be increased by electrolyte additives [37]. Adding Al3+ to the electrolyte was a typical example

to increase the operating platform of the aqueous zinc-manganese battery. As shown in Figure 9e,

the working voltage platform using Al(CF3SO3)3/Zn(CF3SO3)2 electrolyte is 0.3V higher than that

of Zn(CF3SO3)2 electrolyte [37]. Unfortunately, the underlying mechanism has not been explored in

detail. In our opinion, the possible reason may be the difference in contact potential between

43
MnO2/Al3+ interface and MnO2/Zn2+ interface, or the difference in bond energy between Al-O bond

in AlxMnO2 and Zn-O bond in ZnxMnO2. A deeper understanding is needed to analyze the energy

storage behavior of the zinc-manganese battery under this electrolyte.

In short, electrolyte additives can effectively improve the capacity and voltage performance of

cathode materials. For liquid flow batteries, additives can increase the utilization of reactants and

thus increase capacity, such as, Br- additive increase I- utilization ratio. For vanadium-based or

manganese-based materials, multi-ion electrolytes have a higher capacity than single-ion

electrolytes due to the complex ion intercalation effect, such as, Na+/Zn2+ electrolyte or Mg2+/Zn2+

electrolyte can promote higher discharge capacity than single Zn2+ electrolyte; The Al3+-containing

electrolyte has a higher working voltage than the single Zn2+ electrolyte, but the mechanism

analysis has not been explained in detail. The possible reason is the change of the

electrolyte/electrode interface structure or the bonding energy. Taking into account the versatility of

Na+, Mg2+, Al3+, etc., the role of other cations or anions such as Fe3+, Ni3+, NH4+, Cl-, NO3- may

also be the issues worth studying.

Figure 9. The capacity and voltage enhancement of cathode by electrolyte additive. (a)
44
Capacity unlock effect of bromide-key to iodide. Reprinted with permission from Weng et al. [59]

Copyright 2017 The Royal Society of Chemistry. (b) Schematic diagram of the effect of additives

on the capacity and voltage of the cathode. (c) Comparison of GCD curve in zinc-iodine redox flow

battery with or without Br- additive. Reprinted with permission from Weng et al. [59] Copyright

2017 The Royal Society of Chemistry. (d) Effect of additives with different Mg2+ concentration on

rate performance of MgxV2O5·nH2O cathode. Reprinted with permission from Zhang et al. [38]

Copyright 2020 Springer Nature. (e) GCD curve comparison of Zn/MnO2 battery in 2M

Zn(CF3SO3)2 mono-cation electrolyte and 1M Al(CF3SO3)3/1M Zn(CF3SO3)2 bi-cation electrolyte.

Reprinted with permission from Li et al. [37] Copyright 2020 American Chemical Society.

5.3 Modification of Interface Compatibility

Interfacial compatibility is the basis of cathode and electrolyte adaptation. First, the excellent

compatibility can make low impedance and high ion conductivity at interface [92]. Second, the

compatibility of the interface affects the stability of the electrolyte and the electrochemical window.

The improvement of the interface compatibility is helpful to prevent the electrolyte from further

degradation, therefore improving the electrochemical window. Third, fair interface compatibility is

the basis of the excellent performance, and can make the battery have the longer service life and

higher energy output.

It was reported that using electrolyte additives is a common and effective method to improve

interface compatibility [19]. Currently, there have been some studies on electrolyte additives to

improve the interface compatibility of cathodes. Electrolyte additives can promote a compatible

cathode interface film (cathode electrolyte interface, CEI) to ameliorate the cathode/electrolyte

interface [111]. In general, electrolyte additives enabling interface compatibility can be divided into

45
unstable additives and stable additives. Unstable additives undergo chemical reaction degradation

during film formation, while stable additives generally form films by physical adsorption. For the

unstable additive, the HOMO energy level of additives that aid the CEI film is higher than the

cathode chemical potential 𝜇𝐶 . This will cause the additive to have higher oxidizability than the

cathode, so the additive will preferentially get electrons from the cathode to chemically react and

deposit on the cathode surface to form a stable CEI membrane [85]. This CEI film can improve the

interface compatibility by protecting the cathode, reducing the interface impedance, and inhibiting

further decomposition of the electrolyte [84]. A typical example about unstable additives is that the

Mn2+ additives can be oxidized and deposited on the surface of manganese-based material to form

MnOx layer to promote the battery performance [8].

In addition, there are also high-stability additives such as surfactant, perfluorooctyl (PFA)

compounds, SDBS surfactant additive and so on, to form CEI films by generating the

self-passivating film at the interface under surface adsorption effect to improve the interface

compatibility [19, 112]. With the help of SDBS surfactant additive, the enhancement of interface

compatibility between the cathode and the electrolyte has been proved. It could greatly increase the

ions diffusion rate by cathode surface adsorption effect [19]. In the Zn/LiFePO4 battery with 1 M

Zn(SO3CF3)2 and 1 M Li(SO3CF3) hybrid electrolyte, contact angle experiments show that the

contact angle between the electrolyte containing SDBS additives and the cathode is significantly

smaller than that of the electrolyte without additives (Figure 10a and b), which means SDBS

additive can enhance the hydrophilicity of LiFePO4 to water. Molecular dynamics simulations show

that the tail of the SDBS surfactant can be adsorbed on the LiFePO4 surface, which can promote the

adhesion of water molecules, thereby aiding the diffusion of Li+ at the interface (Figure 10c). In

46
addition, the overpotential of LiFePO4 with SDBS additive is significantly lower than that of LFP

without additives, indicating that SDBS additives can reduce the electrochemical reaction resistant

(Figure 10d).

In this aspect, there are mainly two types of additives to increase interface compatibility,

including unstable and stable types. The unstable additives can reduce interface impedance by

transforming the incompatible electrode/electrolyte interface into the compatible electrode/interface

film and interface film/electrolyte double interface. Stable additives can promote interfacial ion

transport by acting as the medium for ion and cathode. Although additives have a significant impact

on the improvement of interface compatibility, unfortunately, research on electrolyte additives

assisting the cathode interface compatibility is still relatively scarce in aqueous ZIBs. The

electrolyte additives may be the breakthrough to process interface compatibility issues. Therefore,

more functional additives that improve the compatibility of the cathode interface of aqueous ZIBs

should be further researched.

47
Figure 10. Interfacial modification of cathode by electrolyte additives. The contact angle

between LFP and electrolyte (a) without additive and (b) with SDBS additive. (c) Molecular

dynamics simulation at the interface between LFP and electrolyte without additives and with SDBS

additives. (d) GITT test and partial enlarged image in electrolyte without additives and with SDBS

additives. Reprinted with permission from Hao et al. [19] Copyright 2019 WILEY-VCH.

6 Summary and Outlooks

In this review, we have made a systematic summary and in-depth understanding of the

electrolyte additives and their functions currently used in aqueous ZIBs. We particularly highlighted

the fundamental functions of electrolyte additives; these include: (1) To modify the properties of
48
electrolyte including the modified electrolyte's ionic conductivity, electrochemical window, and

other electrolyte characteristics. (2) To improve the reversibility of zinc anode, which mainly

consists of the regulation of zinc deposition process and the suppression of side reactions. (3) To

optimize cathode chemistry that is focused on the mechanism of stabilizing the cathode, increasing

the capacity and voltage, and enhancing interface compatibility.

Importantly, the fundamental sciences of electrolyte additives in zinc-ion battery have been

summarized in this review, and the basic requirements for the use of additives can follow the below

principles. In electrolyte aspect, the concentration and conductive ion species of the ionic additives

need to be increased on the basis of considering the synergistic effect or antagonistic effect of each

component for enhancing ionic conductivity; For widening electrochemical stable window, organic

additives should be hydrophobic and need to be adsorbed at the electrode interface to isolate the

contact between water and the electrode, while the ionic additives should stabilize the solvation

structure of water or form the competitive reaction with water; For the high temperature and high

voltage, additives should possess the features that form the stable interface SEI film to prevent

further side reactions; For low temperature properties, additives need form the fast ion conductive

interface SEI film to improve of interface conductivity. In terms of anode aspect, the ionic, organic,

inorganic and metal additives should be polar ions or molecules to form the electrostatic shield

effect, or be adsorbed or deposited on the anode surface to increase the zinc over-potential or limit

the Zn2+ 2D diffusion, or increase the ratio of (002) plane surface texture for the suppression of

dendrites; For suppressing side reactions such as corrosion, passivation, and hydrogen evolution,

additives need form the surface film to regulate the regional galvanic battery reaction. In term of

cathode aspect, for the protection and stabilization of the cathode, the ionic additives that can

49
participate in the dissolution equilibrium reaction, or the cathode interface film generation, or the

solvation structure, will work; For enhancing the capacity and voltage, the ionic additives that can

be inserted into the cathode or have different ion intercalation energy can be used in this field; For

modification of cathode interface compatibility, the ionic or organic additives should be adsorbed or

decomposed into the interface film to enhance the interface compatibility.

Although electrolyte additives have a huge impact on the electrolytes, anodes and cathodes of

aqueous ZIBs, the current research on electrolyte additives is still in its infancy, and the electrolyte

structure influence of additive and many of the reaction mechanisms are still unclear. At present, the

problems of aqueous environment, especially the low chemical stability, low electrochemical

stability, and low thermal stability of the electrolyte are severe challenges. With the continuous

improvement of requirements for battery performance, it is very necessary to enhance the

compound function of electrolyte additives. Furthermore, in addition to additive type, researchers

should pay more attention to the topic of additive solubility which is important parameter but easily

ignored. In addition, considering that gel or quasi-solid electrolytes is the further development

direction of electrolyte system, so the interrelated research about the additive effect and mechanism

on these electrolytes system is necessary. In view of the above basic issues, future research on

zinc-ion electrolyte additives may mainly focus on the following aspects, as shown in Figure 11:

50
 Future Research

Structure Extension and

and Stability Application Gel Solid
Structural Insight Application in Other
of Electrolyte Rule and Electrolyte System
Innovation

Promotion of Compound Additive Design of Novel

Electrolyte Stability Effects Electrolyte

Figure 11. The schematic illustration of the future research on zinc-ion electrolyte additives.

6.1 Structural Insight of Electrolyte

The characterization of electrolyte is always difficult problem due to the nature of liquid,

which is different from cathode and anode with regular structure. However, the structure is

fundamental cause that influence ultimate performance. Therefore, structural insight of electrolyte,

particularly with the functional additives, is very necessary. This research includes the analysis of

solvated structure, interaction relationship of each component, and the evolution of interface double

electrode layer structure. And relevant investigation can be commenced from some regular research

means, such as Fourier transform infrared spectroscopy (FTIR), Raman Spectroscopy, Magnetic

resonance imaging (MRI) etc., and some advanced characterization and theories, such as first

principles calculation, molecular dynamics simulation, finite element modelling, and in situ

microscopic observation, etc. It is meaningful and worthwhile to prove up that how the electrolyte

additive affects these parameters of electrolyte essential structures and how these parameters affect

the electrochemical performance. It will be profitable for us to establish more profound

comprehension about structure and properties.

51
6.2 Promotion of Electrolyte Stability

The instability of water solvent is most vulnerable link in the aqueous ZIBs. On the one hand,

the effumability of water makes it hard to operate for a long time, especially in high temperature

condition. On the other hand, the peculiarity of decomposing easily leads to the emergence of

sophisticated side reaction, therefore, causing low coulombic efficiency. With regard to this, it

should be settled preferentially that how to enhance the steadiness of water. The practicable

methods are that introducing additive that have intensive interaction with water, such as high

valence ion, strong absorbent resin, etc. and utilizing additives that cut off the immediate contact

between electrolyte and electrode, such as surfactant.

6.3 Compound Additive Effects

Despite the wide range of functions of electrolyte additives, the function of single electrolyte

additive is relatively simple. How to develop electrolyte additives with more comprehensive

functions and better effectiveness is the important direction for the development of electrolyte

additives. With this in mind, compound electrolyte additives may be a viable solution. For example,

imidazole and PEG can produce a synergistic effect to inhibit zinc corrosion, and quaternary mixed

additives (PEG, CTAB, BA, and TU) can effectively inhibit the hydrogen evolution reaction.

However, there may be synergistic or antagonistic effects among the composite additive. Therefore,

it is of great significance to prove the interaction discipline between additives for the development

of ZIB electrolyte additives.

6.4 Design of Novel Electrolyte

Inspired by the additive conclusion of this review, according to the required battery

functionality, the new electrolyte with corresponding effect can be theoretically designed. This

52
purposeful electrolyte fabrication is the tendency of future electrolyte development, however, this

needs completely comprehensive recognition about the role of electrolyte additive. Unfortunately, at

present, the corresponding research of zinc ions battery electrolyte additive is still scanty. Therefore,

the investigation of more electrolyte additives types and their effect is crucial objective. What’s

more, the distinct comprehension about the relationship of electrolyte status, composition, additive

content will be also conducive to design novel electrolyte.

6.5 Application in Other Electrolyte System

Many additives, such as inorganic additive and metal additive, are mainly studied in alkaline

electrolyte, could similar feature be achieved in acid electrolyte system? It is the worth exploring

issue that whether the function of electrolyte additive will vary with the change of electrolyte

component. In addition, Within the scope of this review, aqueous electrolyte system is primary

research object. Whether this additives in the aqueous electrolyte can be applied to other electrolyte

system, such as gel electrolyte and solid electrolyte? It is very feasible to explore electrolyte

additive to break the bottleneck in the design of gel or quasi-solid electrolyte. For example,

introducing small molecule additive to gel electrolyte can increase the mobility of long-chain

molecule; applying the additive that can cause defect and vacancy of crystal lattice could enhance

the ionic conduction of solid electrolyte. Therefore, it will be overwhelming and indispensable for

electrolyte additive in the further research of gel or solid electrolyte.

Conflict of Interest

The authors declare no conflict of interest.

53
Acknowledgments

This work was supported by the National Natural Science Foundation of China (Grant no.

52072411, 51932011), and the Innovation and Entrepreneurship Support Project for 2020 College

Students of Central South University (Grant No. 160230003).

Declaration of interest statement

The authors declare that they have no known competing financial interests or personal relationships

that could have appeared to influence the work reported in this paper.

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 TOC Entry

A systematic and comprehensive summary of the types and functions of electrolyte additives

for aqueous zinc-ion batteries was introduced. We particularly highlighted the fundamental

scientific understanding of the effects of electrolyte additives on the electrolyte, anode side and

cathode side.

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