A STUDY ON RECENT PROGRESS IN ELECTROLYTE

FOR ZINC-AIR BATTERY: A MINI REVIEW

Project report submitted to Christ College (Autonomous), in partial fulfilment of the

Curriculum for the fourth semester of

MASTER OF SCIENCE IN CHEMISTRY

SUBMITTED BY:
KRISHNA SREENIVASAN
(Reg. No: CCATMCH008)

UNDER THE GUIDANCE OF:

Dr. JIBIN A. K.
ASSISTANT PROFESSOR

PG AND RESEARCH DEPARTMENT OF CHEMISTRY

CHRIST COLLEGE (AUTONOMOUS), IRINJALAKUDA
THRISSUR-680125
2019-2021

1
 CERTIFICATE

This is to certify the project named “RECENT PROGRESS IN ELECTROLYTE FOR

ZINC-AIR BATTERY” is an authentic record of project done by KRISHNA SREENIVASAN
under guidance of Dr. JIBIN A. K. Assistant professor, Department of Chemistry, Christ
college, Irinjalakuda (Autonomous) submitted to university of Calicut in partial fulfilment of
the requirement for the degree of Master of Science in Chemistry.

Signature of the Head of the Department Signature of Internal Guide

External Examiner
Date:

2
 DECLARATION

I, KRISHNA SREENIVASAN hereby declare that this project work entitled “RECENT
PROGRESS IN ELECTROLYTE FOR ZINC –AIR BATTERY” is the original work done by
me and submitted to University of Calicut in partial fulfilment for the award of M. Sc.
Chemistry.

Place:
Date:

3
 ACKNOWLEDGEMENT

I am grateful to Dr. JIBIN A.K., assistant professor, department of chemistry

Christ college (Autonomous) Irinjalakuda, for his guidance, constant encouragement and
timely suggestions for successful completion of this work.

I record my sincere thanks to DR. V.T Joy, associate professor and the head of
department of chemistry, Christ College (Autonomous), Irinjalakuda for providing me the
necessary facilities to carry out the present work and for her constant encouragement. I would
like to express my sincere gratitude to Fr. Dr. Jolly Andrews, the principal, Christ
college,Irinjalakuda, for providing this opportunity to carry out this work.

I wish to express my deep sense of gratitude to our lab assistants, Department of

chemistry, Christ College, Irinjalakuda for their help and suggestions. I would like to extend
my thanks to all teachers of the Department of chemistry, Christ College, Irinjalakuda, for their
full hearted co-operation.

I take this opportunity as a proud privilege to express my deep sense of gratitude

to my parents for their constant blessings and continuous encouragement.

4
 TABLE OF CONTENTS

1. Introduction ………………………………………………………………..7-10
2. Battery configuration and operation principle……………………………11-12
3. Major parts of a Zn-air battery…………………………………………....12-14
3.1. Zinc electrode
3.2. Air electrode
3.3. Separator
3.4. Electrolyte
4. Electrolyte used for Zn-air batteries………………………………………14-28

4.1 Aqueous electrolyte

4.1.1. Effective electrolyte additives

4.1.1.1. Organic additives
4.1.1.2. Polymer additives
4.1.1.3. Surfactant additives
4.1.1.4. Electrode additives

4.2. Non- aqueous electrolyte

4.2.1. Solid electrolyte

Classification of solid electrolyte
4.2.1.1. Inorganic solid electrolyte
4.2.1.2. Organic solid electrolyte
4.2.1.3. Quasi-solid flexible electrolyte

4.3. Room temperature ionic liquid (RTILs)

5. Advantages and shortcomings of a Zn-air battery……………………….........29
5.1. Advantages
5.2. Shortcomings
6. Applications of Zinc-air batteries…………………………………………….29
7. Conclusion……………………………………………………………………30
8. References………………………………………………………………....31-35

5
 LIST OF FIGURES

Fig.1. Characteristics of Metal-air batteries.

Fig.2. Schematic representation of a zinc-air batteries.
Fig.3. Schematic principle of operation for zinc-air batteries.

LIST OF TABLES
Table 1. Alkaline electrolyte additive for zinc-air battery.

Table 2. Quasi-solid flexible electrolyte additive for zinc-air battery.

6
 Review on recent progress in electrolyte for zinc-air battery

Abstract

In the past few years, there has been a growing level of interest in the research and
development of energy storage systems such as batteries. This is a direct consequence of the
soaring rise in global energy demand across various commercial and industrial sectors. Lithium
ion batteries have set out a feasible horizon for widespread deployment as small-scale energy
storage devices due to their high efficiency and cyclability. However, the availability and cost
of lithium have limited the commercial deployment of large-scale systems. On the other hand,
zinc-air batteries have demonstrated comparable efficiencies and have been reported to be
suitable replacements for lithium batteries in large-scale applications. Nevertheless, more
research has been undertaken to address the issues associated with the cycling processes of
these batteries. Secondary zinc-air batteries are yet to be commercially proven feasible due to
the low charge/discharge cycle life of electrodes. The main problems of secondary alkaline
zinc–air batteries are dendritic growth resulting in an alternation of morphology and structure,
self-dissolution and the consequent occurrence of hydrogen evolution reactions. However, by
and large, inefficient electrolytes are the main culprits responsible for the reduced performance
of zinc-air batteries. We highlight the recent developments of three different electrolytes in
zinc-air battery: aqueous electrolyte, non-aqueous electrolyte, room temperature ionic liquid.
Furthermore, the general perspective is proposed for designing and fabricating electrolytes to
improve the performance and prolong the life time of Zn-air batteries.
Key words

Zinc-air battery, Electrolytes: Aqueous electrolyte, Non-aqueous electrolyte, Room

temperature ionic liquids (RTILs).

1. Introduction

7
 There has been an increasing demand for clean and renewable energy due to the rise in
the energy consumption in modern societies and the continual birth of advanced technologies.
There have been great efforts to improve the existing and/or devise new advanced energy
storage systems. With the inherently intermittent nature of wind and solar energies, there has
been a growing research interest in the development of various types of batteries as energy
storage devices. Such research; however, needs to consider the abundancy of resources, cost,
energy density, safety aspects and cycle life for feasible large-scale implementation. Despite
the great success of lithium-ion batteries in the current market, the limited global resources of
lithium, as well as the corresponding high costs, both restrict their practical and industrial
applications. Therefore, alternative low-cost and abundantly-available elements must be
identified, researched and developed for commercially-feasible applications.

Research on metal air batteries commenced much earlier than lithium ion battery. Zn
air battery is a century old technology. It was first re-posted by Smee in 1840. Maiche
demonstrated functionable primary zinc air battery in 1878 using porous platinized carbon as
cathode. It was first introduced to the market in 1932. Zn air battery is considered as one of the
most promising candidates for next generation batteries for energy storage due to safety, high
energy density and low cost. There are many challenges in electrolyte for developing high
performance rechargeable zinc air cells as well as electro-catalysts. An electrolyte is the crucial
part of a rechargeable zinc air battery that determine their capacity, cycling stability, and life
time. Unlike lithium, zinc is abundant, lighter, more stable, inexpensive, safer and
environmentally friendly. It also demonstrates a relatively high specific capacity (i.e. energy
density). High theoretical specific energy density of zinc-ion batteries (i.e. five times higher
than their lithium-ion counterparts), plus easy re-generation from aqueous electrolyte via
electrode positing method, well justifies their use as secondary batteries. Theoretical specific
capacities and specific energies of metal-air batteries are given in (Fig.1).

8
Fig. 1. Characteristics of metal-air batteries

In general, metal-air batteries have demonstrated the potential for being further
developed into potentially preferential technologies in energy storage; they present high energy
densities, are reliant on the freely-available atmospheric oxygen to work and are lightweight to
build, hence a significant reduction in the costs. Although Al-air (8.1kWh/kg) and Mg-air
(6.81kWh/kg) batteries demonstrate high theoretical energy densities, Al and Mg are not
rechargeable due to corrosion, short shelf life as well as cell irreversibility. As a consequence,
more research has been centred on Li- and Zn-air batteries. The growing interest in Li-air
batteries directly stems from the very high theoretical energy density (11.680 kWh/kg) of these
devices: approximately 30 times higher than that of the Li-ion batteries and 11 times the Zn-
air batteries’ (1.084kWh/kg). Lithium, with a theoretical specific capacity of 3860 m Ah/g and
a low potential of -3.040 V, is known to be the most effective anode compared to other
electrodes. Compared to Zn batteries, the key limiting factors in widespread deployment of Li
batteries are the scarcity of resources, high production costs and stringent safety considerations.
On the top of that, lithium is very sensitive to humidity and the presence of oxygen, hence
operability limitations under controlled environments.

Zinc-air batteries are one of many potential next generation batteries that could hold
more energy while being cheaper and safer than existing devices. Zinc-air batteries have high
specific energy 1218 whKg-1. The performance of electrolytes directly determines the ionic
conductivity and interfacial properties of zinc-air battery in operation. It consist of a porous air

9
cathode and a zinc metal anode separated by using a membrane filled with concentrated
alkaline electrolyte. For developing high performance rechargeable zinc battery, selection of
electrolyte and electro-catalyst are most important. The catalyst facilitates reduction of Oxygen
to oxide ion. If don’t have a catalyst, the power density will be very poor. The main part of a
zinc-air battery is an electrolyte. The performance of an electrolyte gives the ionic conductivity
and interfacial properties of zinc-air battery. It also affects the charging and discharging
capacity of the cell and cycling stability. Zinc-air batteries have high energy density but poor
power output. Zinc-air batteries have higher energy density than many other types of battery
because atmospheric air is one of the battery reactants in contrast to battery types that require
a material such as manganese dioxide (MnO2) in combination with Zinc. Zinc-air battery
generate electricity through the electrochemical reaction of Zinc and Oxygen. During discharge
of the battery zinc anode is oxidized and produces zincate ((Zn [OH]42-) and later changes to
zinc oxide (ZnO) whilst, at the cathode oxygen from the atmosphere undergoes reduction. This
is the basic working principle of zinc-air battery (fig.2.).

Zinc-air batteries present several drawbacks, mainly originating from the use of
aqueous electrolytes-ultimately adversely impacting the performance of zinc electrodes.
Electrically rechargeable zinc-air batteries are associated with dendrite formation, hydrogen
evolution reaction (HER), deformation and limited cycle lives. However, the limited cycle life
and dendrite formation are typically addressed by altering the system in the mechanically
rechargeable zinc-air batteries. While the undesirable humidity in the ambient air can lead to
flooding in the air electrode, dry air, on the other hand, could negatively accelerate electrolyte
evaporation. They widely used in medical and telecommunication applications such as hearing
aids and pagers. Zinc-air batteries are still far from fulfilling their full potential. This is because
the corrosion and dendrite growth of zinc metal upon recharge results in poor cyclability of
most available zinc anode.

Zinc-air battery mostly operate in alkaline media such as potassium hydroxide (KOH)
and sodium hydroxide (NaOH) for the sake of higher activity of both the zinc electrode and air
electrode. KOH is usually preferred over NaOH because of its better ionic conductivity and
lower viscosity. Moreover, its reaction products with atmospheric carbon dioxide (CO2)-
K2CO3 or KHCO3 have higher solubility than their sodium counterparts and can therefore
alleviate the carbonate precipitation problem which is a serious challenge for zinc-air battery.
Most commonly 7M or 30 wt % KOH is employed for its maximum electric conductivity.
Recently, the viability of aprotic electrolytes, especially ionic liquids for zinc-air batteries has

10
been proposed and evaluated. These electrolytes are beneficial to the cyclability of zinc
electrodes. They are also able to suppress the self -corrosion of zinc, slow down the drying out
the electrolyte and eliminate its carbonation.

Fig.2.Schematic representation of zinc-air battery

2. Battery configuration and operation principle

It is comprised of a negative zinc electrode, a membrane separator and a positive air

electrode assembled together in an alkaline electrolyte. Upon battery discharge, the oxidation
of zinc occurs, giving rise to soluble zincate ions (i.e., Zn(OH)42-). This process usually
proceeds until they are supersaturated in the electrolyte, after which the zincate ions decompose
to insoluble zinc oxide as shown by the equations below.
Negative electrode: Zn + 4OH- Zn (OH)42- + 2e-
Zn (OH)42- ZnO + H2O + 2OH-
Positive electrode: O2 +4e- + 2H2O 4OH-
Overall reaction: 2Zn +O2 2 ZnO
Parasitic reaction: Zn+2H2O Zn (OH)2 + H2

11
Fig. 3. Schematic principle of operation for zinc-air batteries

In parallel with the oxidation reaction at the negative electrode, an undesired parasitic
reaction between zinc and water can occur resulting in hydrogen gas generation. This causes a
gradual self-corrosion of the zinc metal, and lowers the active material utilization. At the
positive electrode, oxygen from the surrounding atmosphere permeates the porous gas
diffusion electrode (GDE) and gets reduced on the surface of the electro-catalyst particles in
intimate contact with the electrolyte. The oxygen reduction reaction (ORR) taking place at the
air electrode of zinc–air batteries is similar to the ORR in alkaline hydrogen fuel cells with
hydroxide ions being the primary product. Not surprisingly, these two energy conversion
systems share a similar electrode architecture and catalyst material design principle. Many
good ORR catalysts for fuel cells are also promising candidates for zinc–air batteries.
Zinc–air batteries have a standard potential of 1.65 V. In practice, their working
voltages are markedly lower, typically < 1.2 V in order to get considerable discharge current
densities. For rechargeable batteries, electrochemical reactions can’t be reverted until a large
charging voltage of 2.0 V or higher is applied. Significant deviation of both charge and
discharge voltages from the equilibrium value are mostly contributed by the substantial over
potentials of oxygen electro-catalysis at the positive electrode. As a result, electrically
rechargeable zinc–air batteries usually have a low round-trip energy efficiency of < 60%.
Besides challenges with positive and negative electrode materials, a major operating constraint
to zinc–air batteries as well as to alkaline fuel cells is their sensitivity to the CO2 concentration
in the feed gas stream. The reaction of CO2 with electrolyte leads to the formation of carbonates
by the following reactions, which decreases the electrolyte conductivity. Precipitation of

12
carbonates on the air electrode also clogs pores, negatively affecting the performance of the air
electrodes and batteries.
2KOH + CO2 - K2CO3 + H2O and/or KOH + CO2 - KHCO3

3. Major parts of a zinc-air batteries

3.1. Zinc electrode
Since the invention of the first battery by Volta in 1796, metallic zinc has been the
negative electrode material of choice for many primary systems such as zinc–carbon, zinc–
manganese dioxide, zinc–nickel and zinc–air.1 It possesses a unique set of attributes including
low equivalent weight, reversibility, high specific energy density, abundance and low toxicity,
and is the most electropositive metal that is relatively stable in aqueous and alkaline media
without significant corrosion. In principle, high surface area zinc particles are preferred for
better electrochemical performance. As the electrode surface area increases, the corrosion rate
of the zinc electrode generally becomes more significant. This side reaction consumes
electrolyte, lowers the utilization efficiency of the zinc electrode, and eventually shortens
battery lifetime. Many efforts have been made to slow down or suppress self-corrosion. In the
early days, a partial remedy was amalgamation of the zinc. With the addition of mercury, a
new phase of zinc-rich amalgam was formed at the initiation of hydrogen evolution. Baugh and
co-workers observed that when the mercury level exceeded 100 mg cm_2, corrosion of the zinc
was inhibited to less than 40% of unamalgamated zinc. However, because of concerns over its
high toxicity and negative environmental impact, the use of mercury nowadays is restricted in
many products including batteries. The anode materials of any Zn-air battery is simply zinc,
employed in different forms such as powder or fibres to increase efficiency. During discharge
of the battery, the following chemical reaction scheme describes the process involved at the
zinc anode in alkaline solutions;
Zn Zn2++2e-
Zn2+ + 4OH- Zn(OH)4 2-
Zn(OH)4 2- ZnO + H2O + 2OH-
ZnO + 2H2O Zn(OH)2 + H2

In particular during discharge, the oxidation of zinc electrode can involve several processes
including oxidation of surface zinc atoms, ion solvation in the solution, ion diffusion in the
electrolyte and precipitation into a solid phase when solubility limit is reached.
3.2. Air electrode
13
Gas diffusion electrode
Zinc–air batteries have close interactions with the surrounding environment. Too low
or high humidity may lead to the gradual drying-out of the electrolyte or flooding of the air
electrode, either of which is detrimental to battery performance. Well balanced hydrophobicity
and hydrophilicity in the air electrode can help slow down water evaporation loss or resist
flooding under extreme conditions. They can be tuned by varying the carbon supports used, the
carbon to PTFE ratio and the fabrication conditions. A successful example of a commercial
GDE design is the Toray carbon paper first developed by Toray Industries, Inc in 1980. In this
material, carbon fibers are bound together by layers of graphitized carbon to ensure high
porosity and electrical conductivity, and then treated with PTFE as the wet-proofing agent for
varying research purposes .In order to maximize the oxygen gas permeability, GDEs usually
have to be as thin as possible. The cathode is of course, an air electrode and performs the
reduction of oxygen to complete the redox reaction of the battery. Being a gas electrode the
cathode gas to be porous and electrolytically active. The cathodic electrochemical reaction can
be written as
O2 + 2H2O +4e- 4OH-
Since an alkaline solution is typically employed in Zn-air batteries, represent the typically
favoured mechanism.

3.3. Separator
The separator in batteries physically keeps apart the positive and negative electrodes. It
is an electrochemically inactive component but has a direct impact on key battery parameters.
Separators for zinc–air batteries must have a low ionic resistance and high electrical resistance.
They should have a high adsorption capacity of the alkaline electrolyte but display sufficient
chemical resistance against the corrosive electrolyte and oxidation. Moreover, in light of the
possible dendritic growth of zinc deposits in rechargeable batteries, separators should also have
strong structural resistance to the perforation of zinc dendrites for the sake of safety and long-
term reliability. One drawback of porous separators is that their open structure allows the easy
permeation of soluble zincate ions from the negative electrode, giving rise to an increased
polarization and decreased battery cycling efficiency.

3.4. Electrolyte
14
 Zinc-air batteries mostly operate in alkaline media, such as KOH and NaOH, for the
sake of higher activity of both the zinc electrode and air electrode. KOH is usually preferred
over NaOH because of its better ionic conductivity, higher oxygen diffusion coefficients, and
lower viscosity. Moreover, its reaction products with atmospheric CO2 – K2CO3 or KHCO3–
have higher solubilities than their sodium counterparts, and can therefore alleviate the
carbonate precipitation problem which is a serious challenge for zinc–air batteries. Most
commonly, 7 M or 30 wt% KOH solution is employed for its maximum electric conductivity.
For open systems like zinc–air batteries, water loss from the liquid electrolytes is an important
cause of performance degradation. They usually require regular topping up with water. It has
been found that gelling of the electrolyte can help minimize water loss, and enhance battery
performance and life. Recently, the viability of aprotic electrolytes, especially ionic liquids, for
zinc-air batteries has been proposed and evaluated. These electrolytes are beneficial to the
cyclability of the zinc electrodes. With them, dendrite-free zinc deposition has been
demonstrated. They are also able to suppress the self-corrosion of zinc, slow down the drying-
out of the electrolyte and eliminate its carbonation.

4. Electrolytes for zinc-air battery

Usually the electrolytes used for zinc-air batteries are,

 Aqueous electrolyte
 Non-aqueous electrolyte
 Room temperature ionic liquid (RTIL)

Among them alkaline electrolytes is still widely used due to low cost and high ionic
conductivity and assure the stability of zinc electrode. It is also susceptible to environmental
CO2 and relative humidity. It has advantage because of carbonation. The alkalis such as NaOH
and KOH are good capture of CO2 and carbon monoxide (CO). These will react with alkalis to
form corresponding carbonates. They will be held as a solid and it is very difficult to remove.
Hence, whenever we use KOH in zinc-air battery and exposed to environment, they form
carbonates and stick on the pores. Then they will not have the proper access of oxygen. Battery
performance will be declined. Room temperature ionic liquids and solid electrolytes are very
effective to solve the above problem. However, their performance was not that much good,
because of their low ionic conductivity and unqualified interface.

15
 Metal-air battery can be fabricated in two types of electrolyte; (a) aqueous and (b) non-
aqueous. Aqueous electrolytes are water based electrolyte i.e., any practical devices it is easy
to work with water. Water is a universal solvent, it don’t have any issue unless it is
contaminated with undesired components. Otherwise it is easy to handle with battery
application, electrolysis application or any other applications. If the situation demands other
than water as an electrolyte, then we have difficulty in handling of electrolyte. That is
essentially non-aqueous. In zinc-air battery zinc is very much stable with water.

4.1. Aqueous electrolyte

Sodium hydroxide, lithium hydroxide (LiOH), KOH are the most widely used
electrolytes for zinc-air batteries. Alkaline electrolytes are well matched with zinc electrodes
and catalyst material. In zinc-air battery, zinc is used as anode and Oxygen as cathode.
Electrolyte can be very much KOH. The cathode is exposed to air. This lets Oxygen in the air
come into contact with cathode and react with it forming hydroxyl ion [Eq.1]. These ions then
migrate to the ion which is in the form of paste as zinc is saturated with electrolyte. These ions
combine with zinc paste to form zincate [Eq.2]. If the concentration of zincate is large, it will
decompose into ZnO [Eq.3]. The complete reaction of zinc electrode is [Eq.4],

O2 + 2H2O + 4e- 4OH-1 E = 0.40 V [1]

Zn + 4OH-1 Zn (OH)4 2- + 2e- E = 1.25 V [2]

Zn (OH)4 2- ZnO + H2O + 2OH-1 [3]

Zn + 2OH-1 ZnO + H2O + 2e- E = 1.65 V [4]

We should careful to the adverse effect of high concentration of KOH electrolyte on

the zinc electrode. Because current exchange density of zn/zn2+ reaches 0.21 A cm-2 when the
concentration of KOH is 6M. Also solubility of ZnO increases KOH concentration. Excess Zn
(OH)4 2 are formed due to high concentration of ZnO and it precipitates after the discharge,
which increases the passivation resistance of zinc electrode. Beside the Oxygen reduction,
kinetic parameters of zinc were very high resulting in the dissolution, migration and re-
deposition of zinc under various conditions. There are two ways to solve this problem;

1. Change the composition and structure of zinc electrode

2. Find appropriate electrolyte additives.

16
Proper additives in electrolyte can improve the shape change of zinc electrode and the
performance of zinc-air battery (Table 1.). Table 1 summarized the recent work on alkaline
electrolyte additive. If we can reduce the concentration of KOH as far as possible without
affecting the ionic conductivity of electrolyte, the performance of zinc-air battery will be
further improved.

The zinc-air battery is considered as a semi-open system. It needs rich Oxygen from
the environment. Removal of CO2 is very difficult in a moist atmosphere. Through air electrode
CO2, penetrate to the battery from outer environment and react with OH-1 in the electrolyte.

CO2 + OH-1 HCO3-

HCO3- + OH-1 CO3 2- + H2O

Table 1. Alkaline electrolyte additive for zinc-air battery

The ionic conductivity of electrolyte decreases due to the formation of HCO3- and CO32-. When
it deposit on the cathode the Oxygen access will be blocked and the battery performance will
be declined.

The flow electrolyte system is a very good method for zinc-air batteries. Electrolyte
pumped and circulated through a power system of external pipes. This can improve OH-
transfer and reduce concentration gradient other than removing precipitated carbonate and by-
products. It needs electrical energy and electrical pumping system. Hence, when it comes to
practical application, it is difficult to apply in a huge scale energy storage system with strict
space and weight requirement.

4.1.1 Effective Electrolyte Additives

17
 Use of additives is a promising approach to control zinc dendrite formation, zinc
dissolution and also zinc electro deposition. Low-cost electrolyte additives with high
efficiencies are desirable for application in Zn-based batteries. Suitable additives facilitate the
formation of a compact and uniform zinc electro deposition, enhancing and improving the
cyclability of batteries. Additives help to reduce material build-up on anode as a result of
enhanced dissolution of the zinc deposition during each cycle. This, in turn, helps to maintain
a constant concentration of zinc ions at a stable level. Also, additives facilitate the reduction of
Zn (OH)42- solubility via the adsorption onto the active hydrogen evolution sites, leading to
early ZnO precipitation. Additives mainly fall into three categories of 1) organic additives
(e. g. formaldehyde, perfluorocarboxylic acids, malonic acid, polyamine, tetraalkylammonium
salt, surfactants , ethanol, DMSO and etc.), 2) metallic oxide additives (e.g. HgO , PbO, Ga2O3,
Tl2O3, CdO, Ca (OH)2 and In(OH)3, Bi2O3, In2O3, In(OH)3, CdO, SiO2) and 3) structural
electrode modifiers (e.g. Hg, Cd, Bi, Sn, In, Mg, Al, Ni, Pb).
It is believed that most additives are effective in improving battery performance.
However, additives may also have several adverse impacts as well. These include increasing
the impedance on the cathode electrodes, reaction with electro catalysts, significant H2 gas
generation and precipitation of solid products over cathode’s surface. The role of an additive
depends on the type of the functional groups that are incorporated with individual additives. In
order to enhance battery’s performance, the property of the battery has to be tuned with the
help of the associated functional group. The amount of additives should be carefully adjusted
in order to prevent the occurrence of any undesired effects more especially, the cell impedance.
A good deal of effort is still required to be made in additive development for future optimum
battery performance.
4.1.1.1. Organic Additives
Organic additives (commonly referred to as levellers, accelerator and/or suppressor) are
employed in order to 1) modify the crystal growth, promoting the deposition on sites with low
current density (i.e. cavities) and improving the adsorption on electro-active surface sites for
levelling deposition rates, 2) brighten the deposits, 3) shift the electrochemical mechanism
from instantaneous to a more progressive one, 4) induce a reduction in grain size (low tendency
to tree form) and 5) reduce stress and pitting. Organic additives are mostly used to inhibit
dendrite formation. Organic acids, containing hydrophilic groups such as -COOH, can promote
hydrogen bonding with water molecules along the Helmholtz layer formed on the
electrode/electrolyte surface. The formed bonding via adsorbed organic molecules effectively
blocks the electrode’s surface and hinders the transportation of ions into the solution. This

18
adversely inhibits growth within these regions. The acidic additives such as phosphoric acid,
tartaric acid, succinic acid and citric acid were tested in aqueous solutions of KOH (8.5M).
The results indicated a noticeable rise in hydrogen evolution in the order of tartaric acid
> succinic acid > phosphoric acid > citric acid. However, the prevention of dendrite formation
followed the order of citric acid > succinic acid > tartaric acid > phosphoric acid. The
prevention of dendrite formation is essential in order to effectively maintain the structure of
anode after cycling processes. Additives not only reduce dendrite formation but they also
increase the potential required for hydrogen evolution. Nartey et al. 1994 investigated various
organic corrosion inhibitors such as a-diphenylglyoxime, tripropylene glycol, diaminepyridine,
polyethylene glycol (600) and polyethylene glycol (200) in rechargeable zinc batteries. The a-
diphenylglyoxime and polyethylene glycol (600) corresponded to the best observed
performance compared to the other additives used. Thiourea and polyacrylamide were
employed to modify the crystal orientation of nanocrystalline zinc in an aqueous zinc
ammoniacal electrolyte during pulse electrodeposition . Dimethyl sulfoxide (DMSO), a green
solvent, exhibits a good stability throughout charge/discharge cycles with minimal hydrogen
evaluation, while increasing the wettability of electrode surface. The use of ethanol has been
linked to an improvement of the discharge performance; the addition of 5-10% (v/v) ethanol
could effectively suppress passivating layer formation on the active surface 20 of the zinc
anodes. Various types of tetra-alkyl ammonium hydroxides (TAAHs) have been reported to be
effective additives in preventing zinc dendrite formation. TAAHs can significantly inhibit
dendrite formation. The ability of inhibiting Zn dendrite formation is dependent on two key
factors: the alkyl group size and the additive concentration. The mechanism of zinc dendrite
formation can be attributed to the physical adsorption of TAAHs, covering the surface of the
zinc electrode, and blocking active sites (more suitable for zinc dendrite). This happens as the
alkyl groups can be attached to the zinc surface. Furthermore, increasing TAAHs concentration
and the size of the alkyl groups may enhance the inhibition effect alike. The polarity of TAAHs
(i.e. organic additives) also plays a key role. This effect is more pronounced with larger alkyl
groups.

4.1.1.2. Polymer Additives

Polymer additives such PEG, PMMA, polycarbonate, polyaniline, polypyrrole and poly
(vinyl acetate) restrict the dissolution of discharge products. These are effective in slowing
down dendrite formation and deformation (i.e. structural change). Polymer additives
polyethylene glycol (PEG 600) and polyoxyethylen alkyl phosphate ester acid

19
(GAFACRA600) have shown inhibition properties for zinc in strong alkaline solutions (8.5M).
However, PEG600 has been reported to be more efficient than GAFAC RA600.
Polyethylenimine (PEI) effectively hinders dendritic growth in rechargeable Zn batteries. PEI
adsorption onto Zn surface slows down the Zn electro-deposition kinetics, and as a
consequence, inhibits propagation of dendrite tips. Banik et al., investigated the use of
branched polyethylenimine (PEI) as additive to prevent dendrite growth (electro-deposition) in
alkaline media. They found out that a PEI concentration of 50 ppm was very effective as a
result of the adsorption of additives onto the zinc anode surface which served as a physical
barrier to zinc dendrite formation.

4.1.1.3. Surfactant Additives

Surfactant molecules are typically made up of a hydrophilic and a hydrophobic tail. The
hydrophobic tail is a hydrocarbon, siloxane and fluorocarbon that can be oriented towards the
electrode surface. Upon adsorption, it will create a barrier to prevent the surface accumulation
of ions. Surfactants can therefore, help to avoid dendrite formation. They are widely employed
to establish and maintain a smooth dendrites-free surface. Some surfactants have shown the
ability to provide barriers on the electrode surface for the reactants (zincate) to balance their
uneven deposition on the electrode surface. The introduction of surfactants can significantly
decrease the contact angle and increase the wettability between the electrode and the
electrolyte. The effects of wettability are induced by changing the conductivity and viscosity
of the electrolyte. Adding 2% sodium dodecyl benzene sulfonate (SDBS) to KOH solutions
improved the discharge capacity of zinc anode by 35%. This was due to the formation of a
loose and porous passive film, facilitating the diffusive ion exchange. The formed layer varied
from dense (compact) to loose (porous) with the application of SDBS. The effects of sodium
dodecyl sulphate (SDS) and Triton X-100 surfactants was investigated in order to study
dendrite formation in zinc-polyaniline batteries. A significant improvement was observed in
the cycling performance (i.e. 80% retention after 38 cycles) with SDS and 79 cycles with Triton
X-100, compared to additive-free electrolytes (i.e. 23 cycles) .Using cetyltrimethylammonium
bromide (CTAB), sodium dodecyl sulphate (SDS), thiourea (TU) and polyethylene-glycol
(PEG-8000) organic additives showed distinctively different crystallographic orientation and
surface texture. Except for CTAB, the use of SDS, TU and PEG-8000 improved the
performance. In comparison, high capacity retention (i.e. 1000 cycle), low corrosion and low
dendrite formation rates were recorded for sample containing SDS (Zinc-SDS). The majority
of zinc-SDS surface planes were (103) and (002) and more inert in which the dendrite

20
formation is much less likely. Adsorption of dodecyltrimethylammonium bromide (DTAB)
over zinc surface has proven to hold a positive impact of successfully inhibiting zinc corrosion
with up to 80.2% recorded efficiency.
Non-ionic surfactants such as pluronic F-127 (P127) revealed an increase in the specific
discharge capacity compared to anionic surfactant SDS. This was due to the presence of
multiple anchoring groups per P127 molecule, creating superior interactions and enhanced
adsorption with zinc anode, whilst SDS possess a single anchoring group with weaker surface
adsorption. These finding highlight the fact that the chemical structure of surfactants influences
the formation of dendrite and the passivation layer. It has been reported that the use of non-
ionic surfactants with multiple anchoring groups was advantageous as they bind onto the
anode’s surface, forming a passivation layer - unlike cationic and anionic surfactants.
Moreover, anionic surfactants outperform cationic surfactants as the negatively-charged polar
group coordinates to zinc ions at the electrode/electrolyte surface to reduce ZnO formation.
However, the positively-charged polar group of cationic surfactants exhibits weak interactions
with zinc ions, leading to an increased formation of ZnO.

4.1.1.4. Electrode Additives

In addition to electrolytes, additives can be also added to anodes in order to improve
the cyclability performance. Carbon materials, bimetals and polymers have been studied as
additives for Zn electrodes in order to decrease dendrite formation. Modification of zinc
electrodes is a promising approach to negate the adverse effects of dendrite growth and
structural change. Fabrication of anode comprising zinc and polymer has been suggested to
inhibit the growth of dendrites. Porous zinc electrode coated with polyaniline was found to be
useful in stabilizing the capacity of the electrode (i.e. cycling). The fibrous network of the
coated polymer allows the flow of the OH- ions and while restricting zincate ion diffusion.
Electrochemical polymerization of pyrrole on zinc foil in aqueous medium (sodium tartrate)
has led to the production of less-corrosive zinc in alkaline media. The addition of bismuth (Bi)
(10% wt) and calcium (Ca) into a pasted zinc electrode enhanced the discharge behaviour.
Bismuth improves electronic conductivity while little structural change and small dendrite
growth were observed in calcium zincate as a result of low solubility. Alloy of indium, nickel
and zinc with an optimum composition of 2.5%, 7.5% and 90%, respectively, resulted in
minimal dendrite formation with a reversibility of more than 100 cycles. . Among the
intrinsically conducting polymers, polypyrrole (PPy) and polyaniline (PANI) were found to be
most suitable due to their wide range of conductivities, tuneable properties and high stabilities.

21
Conductive polymers as additives can be added to anode to improve the overall performance
of rechargeable batteries. PANI-coated zinc was used to mitigate the self –discharge behaviour,
inhibit HER and corrosion reactions by preventing direct contact between zinc and the KOH
electrolyte. Electro deposited ZnO on carbon mesh with a protecting layer (i.e. Ionomeric
Hydroxide-Conducting Polymer) has yielded excellent cycling stability.
It is a consequence of the diffusion of zincate species into the electrolyte. The composite
electrode showed a high utilization rate of the active material (~93%), leading to an enhanced
capacity retention. Nano-porous CaCO3 coated zinc provides a uniformly of zinc dissolution
and deposition due to the high porosity of CaCO3 layer. The uniform and high porous CaCO3
layer induces steady flux of electrolyte and zinc dissolution/precipitation rate over the zinc
surface. Coating of zinc surface or inducing additives into zinc electrode enhances zinc
electrode’s performance. This may improve electrical conductivity, surface structure and
current distribution - which may prevent dendrite growth. The migration of zincate ions can be
limited in order to minimize the deformation of the electrode and irreversible reactions (i.e.
ZnO).

4.2 Non-aqueous electrolytes

4.2.1. Solid electrolytes
There have been some efforts to replace non-aqueous electrolytes e.g. polymer-based
or solid electrolytes. As a result, research has been undertaken to address the challenges facing
the application of solid state, solid polymer- and/or gel polymer-electrolytes in metal-air
batteries. The use of polymer matrix in composite solid electrolytes improve the flexibility of
solid composite electrolytes. It can reduce resistance at the electrode-electrolyte interface. It
also simplifies the large-scale manufacturing processes. Solid-state electrolytes can be
inorganic solid oxide-, solid sulphide - or solid nitride-based. The solid electrolytes serve two
key roles; it acts as an aqueous electrolyte (for ion conduction) and as a separator (i.e.
preventing internal short-circuit). Different approaches have reported to fabricate polymeric
electrolytes by impregnating basic polymer backbone with OH− functional group and by
integrating alkaline salts into the inert polymer matrix.
Classification of solid electrolytes
4.2.1.1. Inorganic Solid Electrolytes
Ceramic-based solid electrolytes haves demonstrated several advantages including high
energy densities, negligible electrolytes leakage, flame resistance, good reliability, high
electrochemical stability, long cycle performance and feasibility for large-scale batteries. The

22
oxide-based electrolytes show good stabilities under ambient conditions with large interfacial
resistance between the solid electrolyte and the electrode. The ionic conductivity of solid oxide
electrolytes is <1×10-4 S/cm at room temperature which is not suitable for applications in
batteries. Also, a dense and uniform electrolyte is challenging to directly produce at high
temperatures. Unlike oxide-based electrolytes, solid sulphide-based electrolytes have low
thermodynamic stabilities (in ambient conditions and even in polar solvents). The presence of
sulphides can lead to the generation of toxic H2S when exposed to moisture. Nevertheless,
these electrolytes have shown excellent ionic conductivities of around 1×10-2 S/cm at room
temperatures. Sulphide groups can corrode the grain boundaries, causing the appearance of
cracks in ceramics as well as solid-state electrolytes. Nitride-based electrolytes demonstrate
ionic conductivities <10-3 S/cm at room temperatures but low electrochemical decomposition
potentials and poor stabilities hinder their employment in practical applications. The
conductivities of the solid-state electrolytes are induced via the ionic motions across crystalline
lattice sites. Unlike liquid electrolytes, solid electrolytes fail to infiltrate into cathode pores and
therefore, the accumulation of electrostatic charges on electrodes/electrolyte interface causes
considerable polarization of electrodes. By the addition of polymer to solid state electrolytes,
stability, performance and electrode/electrolyte interface features can be improved. Due to
insufficient ionic conductivity at room temperatures, fragility, instability and poor interfacial
contacts, their rapid growth is still ongoing business.
The interfacial resistance, a critical parameter, dictates the corresponding commercial
applications. The interface resistance is directly related to the chemical stability of the materials
at the electrolyte/electrode interface. Recent studies have reported on reducing the interfacial
resistance via several proposed methods e.g. coating/sputtering transition layers (polymers as
soft contact, silicon, Al2O3, graphene oxide, Li3N), employment of advanced structural design
of the anode metal (i.e., 3D) to made uniform deposition/discharge cycles, use of suitable
electrolytes for enhancing wetting ability over anode electrode, modifying internal particles in
the cathode to improve the ionic conductivity inside the cathode, and fine-tuning the thickness
of the cathode’s layer.
4.2.1.2. Organic Solid Electrolytes
Organic solid electrolytes have several advantages over their inorganic counterparts.
These include better flexibility, great interfacial contacts between the electrolyte and the
electrode, lightness and simplified large-scale fabrication. Electrolytes with a combination of
polymers and salts are known as salt-in-polymer (or polymer-in-salt) electrolytes depending
on compositional ratios. Solid polymer electrolytes (SPE) have been linked to better operating

23
temperature ranges, electrical recharge-abilities, good mechanical strengths, simple
fabrication, negligible leakage and being solvent-free. However, several disadvantages such as
low ionic conductivity (i.e. 10-8 to 10-5 Scm-1), the instability of the electrode/electrolyte
Interface and salt depletion at the electrode/electrolyte interface are yet to be addressed to pave
the way for practical applications in metal-air batteries. SPE contains a salt with a low lattice
energy and hosts a polymer with a high dielectric constant to facilitate ionic dissociation and
transportation. The salts act as a source of mobile ions, while the polar groups of the polymers
are bonded with ions (cations, anions), according to the Lewis acid–base theory. A solid
electrolyte with the high flexibility of polymer chain and fast segmental dynamics can be
formed by adding conductive salts to the polymer matrix. The function of the amorphous phase
depends on the salt content as well as the preparation method. The selection of polymer host
depends on the existence of polar functions with good proton donors and a low hindrance to
bond rotation. The nature of the functional groups attached to the polymer backbone (e.g. OH,
CO, NH2, CH3, F, Cl), molecular weight, compositions and distance between the functional
groups, nature and charge of metal cation, degree of branching and counter ions are the
important factors influencing the polymer-metal ion interactions.
The optimum salt concentration is key to achieve high performance. This is due to the
fact that a strong interaction between ions (salt) and polymer results in further dissolvement of
the salt. However, high salt concentration obstructs ionic movements. Therefore, both weak
ions’ coordination to the polymer chains and segmental motions, contribute to fast ionic
transport. For this reason, excessively high concentrations of ions may lead ionic aggregation,
hampering the ionic movements. There have been also technical challenges in establishing an
accessible metal-ion path at solid electrolyte interface (SEI) in batteries. It has been reported
that the SEI layer on the anode surface is continuously regenerated by the spontaneous
reactions between reactive anode (metal) and organic electrolytes and breaks during cycling.
The SEI layer shows some advantages as it is permeable to metal ions and prevents further
corrosion. However, dendrite formation takes place as a result of anode deposition and
dissolution. The SEI is a passivating layer formed on the anode surface, primarily during the
first cycle, and originates from the mismatch between the electrochemical stability window
(i.e. oxidation/reduction limits) of the electrolyte and the electrochemical potential of the
electrodes. The SEI usually comprises the products that are generated from solvent reduction
in the electrolyte and salt degradation. A stable passivating SEI layer protects the electrode
from further reactions with the electrolyte, thereby, avoiding undesired electrolyte
consumption. However, it also limits the kinetics of the ion transport processes. Therefore,

24
understanding the formation mechanism as well as the chemical composition of the SEI is the
key to improve the performance of batteries. The reversibility of batteries is limited due to the
poor buffering properties of the SPEs for the zincate ion discharge products. This zincate builds
up during the discharge and leads to passivation, imposing limitations on the SPEs during
subsequent charging. This makes it difficult to maintain an ideal surface contact between the
metal anode and the solid electrolyte membrane.
4.2.1.3. Quasi-solid flexible electrolyte

With the increasing demand for flexible wearable electronic devices, the research on
flexible batteries, especially quasi-solid electrolytes, has put forward higher requirements.
Compared with other metal-air batteries, zinc-air batteries with high volume energy density
have the characteristic of low cost and high safety. In contrast, Zn-MnO2 batteries using
polymer electrolytes were commercially produced using printing technology. Therefore, it is
necessary to carry out scientific research on the structure and performance of a flexible Zn-air
battery, and the production of this type of battery and the matching quasi-solid electrolyte needs
to be continuously optimized.

The quasi-solid flexible electrolyte can be prepared from alkaline aqueous solutions
and polymers like polyvinyl alcohol (PVA), polyacrylic acid (PAA), gelatin, and related graft
copolymer, which are required to meet the stable configuration, cathode and anode separation,
and qualified ionic conductivity. During the preparation process, most of the quasi-solid
flexible electrolyte can form a cross-linked network with large number of hydrophilic
functional groups such as hydroxyl group which enables higher water retention and ionic
conductivity in quasi-solid flexible electrolyte. In primary zinc –air cell, alkaline gel electrolyte
can effectively reduce the leakage and volatilization of electrolyte and has been applied. In the
case of rechargeable flexible zinc-air battery, zinc electrode in the quasi-solid flexible
electrolyte, they can carry only a little amount of ZnOH42-. Then the reduction of ZnO to
ZnOH42- is blocked. Hence, it is a big challenge to rechargeable battery to work in a large
current. Flexible power density and cycle performance of the Zn-air battery have been highly
favoured. However there are several important aspects in the bi-functional catalyst for electro
chemical oxygen reaction, the ionic conductivity of the quasi-solid flexible electrolyte, and the
performance of the electrolyte-electrode interface. The ionic conductivity of the electrolyte
depends on the type of polymer and electrolyte additives. Fan et al., (2019) Prepared a porous
PVA + SiO2 electrolyte with large ionic conductivity of 57.3 ms cm-1 and excellent cycling
performance and power density, Li et al., (2019) fabricated the polymer dielectric TEAOH-

25
PVA which still had ionic conductivity of 30ms cm-1 after two weeks, showing excellent
service and working life. It is not difficult to find that a single polymer can hardly become a
flexible electrolyte of a quasi-solid state with excellent performance. Small number of additives
can improve the performance of electrolytes, which is also a process of polymer
functionalization. This is because, additives can optimize the cross-linked network of polymer
electrolyte, increase water retention ability of electrolyte which is greatly affect the ionic
conductivity. There is a challenge to improve the performance of the electrolyte-air electrode
interface in the flexible zinc-air battery.

Table 2. Quasi-solid flexible electrolyte additive for zinc-air battery

Table 2 lists more compared performances to provide more meaningful roots for the
development of quasi-solid flexible electrolytes for zinc-air battery. It is necessary to establish
a unified evaluation standard for flexible zinc-air battery to evaluate the performances of the
corresponding electrolyte better.

The flexible zinc-air battery is divided into one dimensional (1D) and two dimensional
(2D) structures. Ma et al., (2019) prepared a dual network hydrogel electrolyte (polyacrylate
hydrogel cross-linked by cellulose chain and N, N-methylene-bis acrylamide anchors) and
optimized the structure of zinc and air electrodes to assemble zinc-air battery with excellent
tensile property. The composition of the electrolyte in flexible zinc-air battery is mostly in the
polymer + KOH solution mode. The wettability of quasi-solid flexible electrolyte is reduced,

26
then make more difficult for the catalyst to perform its function than in the alkaline electrolyte
of the water system.

4.2.2 Gel Polymer Electrolytes

Developing alternative polymer matrices at a low cost with wide electrochemical
windows and devising simple synthetic methods are key factors in the development of high
performance batteries. In order for polymeric electrolytes to compete with their liquid organic
counterparts, they should demonstrate superior properties such as good ionic conductivities in
the proximity of liquid electrolytes, high chemical, thermal and electrochemical stabilities
(large potential windows) and high mechanical stabilities (i.e. to prevent short-circuits). The
second category of electrolytes (i.e. gel polymer electrolyte) are characterized by a higher
ambient ionic conductivity than SPEs. They; however, exhibit lower mechanical properties.
Gel polymer electrolytes (GPE) are known to be a transition between solid polymer and liquid
electrolytes. GPEs consist of a solvent with a high ionic conductivity, encapsulated in the
polymeric matrix with a good ionic conductivity (10-4 to 10- 3 S/cm) at ambient temperatures.
GPEs can be produced by immobilizing organic solvents e.g. DME, diethyl carbonate (DEC),
ethylene carbonate (EC), and 1, 3-dioxolane (DOL) and etc. in a polymeric network. GPEs are
more flexible compared to solid polymer electrolytes; they can be more readily scaled up and
fabricated in various shapes. However, the mechanical strength of GPEs drops during the
plasticizing process with organic solvents. Achieving high ionic conductivities, ensuring good
contacts with the electrodes and good chemical and electrochemical stabilities are the major
challenges in designing hydrogel networks. Of the use of an optimal polymer host, alkali salt
and their optimised compositions have been reported to successfully address the mechanical
strength of GPEs. The problems associated with low mechanical strengths can be rectified by
combining inorganic solids (or other inorganic fillers) with host polymers to improve the
mechanical strength. Porous structures in polymer matrices play an important role in GPEs as
they are responsible for the uptake of liquid electrolytes. However, it is worth mentioning that
too large pores are detrimental for battery performance as they often induce internal short
circuits. PVA doped with KOH has been widely used as PGEs in various applications e.g.
super-capacitors, anion exchange membranes, zinc batteries and fuel cells. (PGE) films, based
on acrylate-KOH–K2S2O8 have shown an ionic conductivity of 0.288 S/cm and good
performance for application in zinc-air batteries.
GPE electrolytes based on PVA/KOH, exhibited good cycling stabilities for 6 and 12
hours in sandwich- and cable-type zinc air batteries, respectively. GPE based on PAA revealed

27
the highest conductivity may be due to its high hydrophilicity as well. A cross-linked GPE,
using PEO and PVA polymers (i.e., the host polymer) demonstrated a high ionic conductivity
of 0.3 S/cm. In order to increase the water retention capability of GPEs, several methods have
been proposed to create and enhance the porous structure such as the addition of SiO2 to PVA/
PEG. Fu et al., 2015 reported a flexible and rechargeable ZAB using porous polyvinyl alcohol
(PVA) as the GPE. The porous GPE showed an outstanding stability over 120 cycles at a rate
of 50 A/kg. Xu et al., 2015 also reported a rechargeable, flexible and stretchable ZAB with a
PVA/poly (ethylene oxide) (PEO)-based alkaline GPE. At the voltage plateau of 1.0 V, the
discharge current density reached 1 A/g and was effectively maintained for 30 discharge/charge
cycles. In order to obtain gel polymer electrolyte with high water retention capability, Li et al
suggested the use of tetraethyl ammonium hydroxide (TEAOH) instead of KOH as the ionic
conductor. Compared to KOH-PVA, a significant improvement in the shelf life of the
TEAOH−PVA electrolyte was successfully achieved. Gel polymer electrolytes demonstrate
the ability to suppress dendrite, owing to their uniform ionic flux distribution and single-ion
transport. Indeed, gel polymer electrolytes can mitigate the ion concentration gradient (i.e., the
main key factor in dendrite growth). Also, the intermolecular solvent channels can enhance the
uniformity of current distribution leading to homogenous zinc deposition.

4.3. Room temperature ionic liquid (RTIL)

They are molten salts that exist as liquid below room temperature .It has a wide
electrochemical window and it not easily ignited. Therefore, more and more attention was paid
to RTILs as substitute for alkaline electrolytes. The use of RTILs in zinc-air batteries can
effectively solve the difficulties of zinc electrode damage, CO2 damage, electrolyte evaporation
in zinc air battery. In aprotic RTILs, the absence of proton can avoid the corrosion of zinc
electrode caused by H2 evolution. Therefore, RTILs, as an electrolyte for zinc-air batteries,
have put on the list in recent years.

Zinc oxidise to Zn2+ during discharge in zinc-air cell when RTILs are used as an
electrolyte. In appropriate RTILs form insoluble substances with Zn2+ and it cannot be reduced
effectively. The air electrode mechanism in RTIL electrolyte is, Oxygen gains electron and
forms a superoxide (O2-) when Oxygen reduction occurs in RTILs electrolyte. It is a quasi-
reversible reaction. There is no further transfer of electrons due to the formation of superoxide
in the case of aprotic RTILs. While in protic RTILs, superoxide is act as a strong nucleophile

28
 .
and it react with protons in RTILs to form perhydroxy radical (HO2 ). It also react with
superoxide to form peroxide (HO2-).

O2 + e- O2 . -

O2 . - + H+ HO2.

HO2. + O2.- HO2- + O2

HO2. + e- HO2-

HO2- + H+ H2O2

Above one is the summary of Oxygen reduction and Oxygen precipitation reactions in RTILs.
As an electrolyte, RTILs in the zinc-air battery still faces enormous challenges. The high cost
of RTILs make it unaffordable to use on a large scale. On the other hand, the RTILs dual
electron reaction mechanism reduces the energy density of the battery, coupled with its high
viscosity and low current. It means zinc-air battery only work at low current.

Further, the applications of more types of RTILs in zinc-air batteries should be

investigated, including the beneficial effect of additives in RTILs. It also necessary to develop
specific bi-functional catalyst to reduce the energy barrier of oxygen reduction reaction and
oxygen evolution reaction. Although the RTIL electrolyte needs further study in terms of
interface properties, the electrochemical reaction mechanism of oxygen and the migration path
of active substances, various pieces of evidence indicate that RTILs are the promising
electrolytes for Zn-air batteries.

5. Advantages and shortcomings of zinc-air batteries

5.1. Advantages

* High energy density but low power

* Inexpensive material

* The zinc-air system, when sealed, has excellent shelf life, with self –discharge rate of only

2% per year

* In relation to their physical size, zinc-air batteries store more energy per unit of weight than

29
 almost any other primary type.

* Primary cells available in a range of button and coin cell sizes.

* Rechargeable high power cells available for traction applications.

5.2. Shortcomings

* Sensitive to extreme temperature and humid conditions.

* Carbon dioxide from the air forms carbonate which reduces conductivity.

* High self-discharge

* Although recharging is possible it is also inconvenient and is only suitable for high power

types.

* High internal resistance which means zinc air batteries must be huge to satisfy high current
needs.

6. Applications of Zn-air batteries

* Commercial, primary Zn-air batteries have been used for many years:

- Initially used as railroad signalling, remote communications, and ocean navigational units

requiring long term, low rate discharge.

-With the development of thin electrodes used in small, high capacity primary cells, such as

hearing aids, small electronics, etc.

7. Conclusion

With the demand for high-power, long life, and flexibility of rechargeable Zn-air
batteries, the development of electrolytes meet the opportunities and challenges. Electrolyte,
as a crucial part of Zn-air battery, has a profound influence on circulation efficiency, power
density, and capacity performance. Up to now, alkaline electrolytes are the mainstream because
of their excellent ionic conductivity and interfacial properties. However, alkaline electrolytes
are susceptible to the effect of carbon dioxide content and relative humidity in the external
environment. On the one hand, the suitable type and proportion of additives should be explored
to improve the properties of alkaline electrolyte. On the other hand, room temperature ionic

30
liquid, as an electrolyte for Zn-air batteries, have high threshold of aging, and its protection
and safety for zinc electrodes are apparent. Moreover, the research on quasi solid flexible
electrolyte is more conducive to making portable and flexible Zn-air batteries, which provide
that the shortcomings in interface performance and ionic conductivity need to be addressed.
Finding the right RTILs and polymers make sense to improve the performance of the
electrolyte.

Furthermore, we think that the electrolytes mentioned above may be integrated with
different features. Suitable electrolyte additives can also promote the application of RTILs and
quasi solid electrolyte in Zn-air batteries, and the combination of RTILs and polymers can also
improve the performance of electrolytes. The research on electrolyte should be paid more
attention to make Zn-air batteries meet the demand for a new generation of energy storage.

8. References
[1] Schmitt, T, Arlt, T, Manke, I, Latz, A, & Horstmann, B Zinc electrode shape-change in
secondary air batteries: A 2D modeling approach. Journal of Power Sources, 2019:432:119-
132.
[2] Deng, Ya-Ping, Yi Jiang, Ruilin Liang, Shao-Jian Zhang, Dan Luo, Yongfeng Hu, Xin
Wang, Jun-Tao Li, Aiping Yu, and Zhongwei Chen. "Dynamic electro-catalyst with current
driven oxyhydroxide shell for rechargeable zinc-air battery." Nature Communications 11, no.
1 (2020): 1-10.

31
[3] Mainar, A. R., Iruin, E., Colmenares, L. C., Kvasha, A., de Meatza, I.Bengoechea,M. and
Blazquez, J. A. An overview of progress in electrolytes for secondary zinc-air batteries and
other storage systems based on zinc. Journal of Energy Storage, 2018; 15: 304-328.
[4] Reddy, T. B. (2011). Linden's handbook of batteries (Vol. 4). New York: McGraw hill.
[5] Sun, Y., Liu, X., Jiang, Y., Li, J., Ding, J., Hu, W., & Zhong, C. Recent advances and
challenges in divalent and multivalent metal electrodes for metal–air batteries. Journal of
Materials Chemistry A, 2019; 7(31):18183-18208.
[6] Gu, P., Zheng, M., Zhao, Q., Xiao, X., Xue, H., & Pang, H... Rechargeable zinc–air
batteries: a promising way to green energy. Journal of Materials Chemistry A, 2017;
5(17):7651-7666.
7] Alexander H. TULLO , C&EN NEW YORK CITY, Batteries that breathe
air,;https://cen.acs.org/articles/95/i9/Batteries-breathe-air.html
[8] Garche, J., Dyer, C. K., Moseley, P. T., Ogumi, Z., Rand, D. A., & Scrosati, B. (Eds.).
(2013). Encyclopedia of electrochemical power sources. Newnes.
[9] Zhang, J., Zhou, Q., Tang, Y., Zhang, L., & Li, Y. Zinc–air batteries: are they ready for
prime time? . Chemical Science, 2019; 10(39): 8924-8929.
[10]Stamm, J., Varzi, A., Latz, A., & Horstmann, B. Modeling nucleation and growth of zinc
oxide during discharge of primary zinc-air batteries. Journal of Power Sources, 2017; 360; 136
149.
[11] Fu, J., Cano, Z. P., Park, M. G., Yu, A., Fowler, M., & Chen, Z. Electrically rechargeable
zinc–air batteries: progress, challenges, and perspectives. Advanced materials, 2017; 29(7):
1604685.
[12] Deng, Y. P., Liang, R., Jiang, G., Jiang, Y., Yu, A., & Chen, Z. (2020). The Current State
of Aqueous Zn-Based Rechargeable Batteries. ACS Energy Letters, 5(5), 1665-1675.
[13] Schröder, D., & Krewer, U. Model based quantification of air-composition impact on
secondary zinc air batteries. Electrochimica Acta, 2014; 117: 541-553.
[14] Li, Y., & Dai, H. Recent advances in zinc–air batteries. Chemical Society Reviews, 2014;
43(15): 5257-5275.
[15] Popov, K. I., Živković, P. M., & Nikolić, N. Electrochemical aspects of formation of
dendrites. Zaštita materijala, 2016; 57(1); 55-62.
[16] Diggle, J. W., Despic, A. R., & Bockris, J. M. The mechanism of the dendritic
electrocrystallization of zinc. Journal of the Electrochemical Society, 1969; 116(11):1503-
1514.

32
[17] Pei, A., Zheng, G., Shi, F., Li, Y., & Cui, Y. (2017). Nanoscale nucleation and growth of
electrodeposited lithium metal. Nano letters, 17(2), 1132-1139.
[18] Guo, L., Guo, H., Huang, H., Tao, S., & Cheng, Y. (2020). Inhibition of zinc dendrites in
zinc-based flow batteries. Frontiers in Chemistry, 8.
[19] Huang, C., Shi, R., Amini, A., Wu, Z., Xu, S., Zhang, L. and Wang, N. Hierarchical ZnO
nanostructures with blooming flowers driven by screw dislocations. Scientific reports, 2015;
5: 8226.
[20] Wang, R. Y., Kirk, D. W., & Zhang, G. X. Effects of deposition conditions on the
morphology of zinc deposits from alkaline zincate solutions. Journal of the Electrochemical
Society, 2006; 153(5): C357-C364. 55
[21] Yufit, V., Tariq, F., Eastwood, D. S., Biton, M., Wu, B., Lee, P. D., & Brandon, N. P.
Operando Visualization and Multi-scale Tomography Studies of Dendrite Formation and
Dissolution in Zinc Batteries. Joule, 2019; 3(2):485-502.
[22] Riede, J. C., Turek, T., & Kunz, U. (2018). Critical zinc ion concentration on the electrode
surface determines dendritic zinc growth during charging a zinc air battery. Electrochimica
Acta, 269, 217-224.
[23] Yufit, V., Tariq, F., Wu, B., Biton, M., Merla, Y., Eastwood, D., and Brandon, N. P. In-
Operando X-ray Tomography Studies of Dendrite Formation in Zinc-Air Batteries. In Meeting
Abstracts the Electrochemical Society 2014; 4: 229-229
[24]Biton, M., Tariq, F., Yufit, V., Chen, Z., & Brandon, N. Integrating multi-length scale high
resolution 3D imaging and modelling in the characterisation and identification of mechanical
failure sites in electrochemical dendrites. Acta Materialia, 2017; 141: 39-46.
[25] Wang, K., Pei, P., Ma, Z., Chen, H., Xu, H., Chen, D., & Wang, X. (2015). Dendrite
growth in the recharging process of zinc–air batteries. Journal of Materials Chemistry A, 3(45),
22648-22655.
[26] Cao, J., Zhang, D., Zhang, X., Sawangphruk, M., Qin, J., & Liu, R. (2020). A universal
and facile approach to suppress dendrite formation for a Zn and Li metal anode. Journal of
Materials Chemistry A, 8(18), 9331-9344.
[27] Yufit, V., Tariq, F., Eastwood, D. S., Biton, M., Wu, B., Lee, P. D., & Brandon, N. P.
(2019). Operando visualization and multi-scale tomography studies of dendrite formation and
dissolution in zinc batteries. Joule, 3(2), 485-502.
[28] Stock, D., Dongmo, S., Miyazaki, K., Abe, T., Janek, J., & Schröder, D. Towards
zincoxygen batteries with enhanced cycling stability: The benefit of anion-exchange ionomer
for zinc sponge anodes. Journal of Power Sources, 2018; 395:195-204.

33
[29] Michlik, T., Schmid, M., Rosin, A., Gerdes, T., & Moos, R. Mechanical coating of zinc
particles with Bi2O3-Li2O-ZnO glasses as anode material for rechargeable zinc-based
batteries. Batteries, 2018; 4(1):12.
[30] Wongrujipairoj, K., Poolnapol, L., Arpornwichanop, A., Suren, S., & Kheawhom, S.
Suppression of zinc anode corrosion for printed flexible zinc‐air battery. physica status solidi
(b), 2017; 254(2):1600442.
[31] Thomas, S., Cole, I. S., Sridhar, M., & Birbilis, N. (2013). Revisiting zinc passivation in
alkaline solutions. Electrochimica Acta, 97, 192-201.
[32] Liu, M. B., Cook, G. M., & Yao, N. P. (1981). Passivation of zinc anodes in KOH
electrolytes. Journal of the Electrochemical Society, 128(8), 1663-1668
[33] Sun, K. E., Hoang, T. K., Doan, T. N. L., Yu, Y., Zhu, X., Tian, Y., & Chen, P. Suppression
of dendrite formation and corrosion on zinc anode of secondary aqueous batteries. ACS applied
materials & interfaces, 2017; 9(11), 9681-9687.
[34] The Nernst Equation and Pourbaix diagram, ' TLP Library, DoITPoMS, University of
Cambridge, https://www.doitpoms.ac.uk/tlplib/pourbaix/index.php
[35] Park, J., Park, M., Nam, G., Lee, J. S., & Cho, J. (2015). All‐solid‐state cable‐type flexible
zinc–air battery. Advanced Materials, 27(8), 1396-1401.
[36] Hosseini, S., Han, S. J., Arponwichanop, A., Yonezawa, T., & Kheawhom, S. (2018).
Ethanol as an electrolyte additive for alkaline zinc-air flow batteries. Scientific reports, 8(1),
11273.
[37] McLean, G. F., Niet, T., Prince-Richard, S., & Djilali, N. (2002). An assessment of
alkaline fuel cell technology. International Journal of Hydrogen Energy, 27(5), 507-526.
[38] Huang, C. L., Wang, P. Y., & Li, Y. Y. (2020). Fabrication of electrospun CO2 adsorption
membrane for zinc-air battery application. Chemical Engineering Journal, 125031.
[39] Xu, S., Das, S. K., & Archer, L. A. (2013). The Li–CO 2 battery: A novel method for CO2
capture and utilization. RSC Advances, 3(18), 6656-6660. 56
[40] Jörissen, L. (2006). Bifunctional oxygen/air electrodes. Journal of Power Sources, 155(1),
23-32.
[41] Drillet, J. F., Holzer, F., Kallis, T., Müller, S., & Schmidt, V. M. (2001). Influence of CO2
on the stability of bifunctional oxygen electrodes for rechargeable zinc/air batteries and study
of different CO 2 filter materials. Physical Chemistry Chemical Physics, 3(3), 368-371.
[42] Othman, R., Basirun, W. J., Yahaya, A. H., & Arof, A. K. (2001). Hydroponics gel as a
new electrolyte gelling agent for alkaline zinc–air cells. Journal of power sources, 103(1), 34-
41.
34
[43] Mohamad, A. A. (2006). Zn/gelled 6 M KOH/O2 zinc–air battery. Journal of power
sources, 159(1), 752-757.
[44] Mitha, A., Mi, H., Dong, W., Cho, I. S., Ly, J., Yoo, S. and Chen, P. (2019). Thixotropic
gel electrolyte containing poly (ethylene glycol) with high zinc ion concentration for the
secondary aqueous Zn/LiMn2O4 battery. Journal of Electroanalytical Chemistry, 836, 1-6.
[45] Pal, B., Yang, S., Ramesh, S., Thangadurai, V., & Jose, R. (2019). Electrolyte selection
for supercapacitive devices: a critical review. Nanoscale Advances, 1(10), 3807-3835.
[46] Xu, M., Ivey, D. G., Xie, Z., & Qu, W. (2015). Rechargeable Zn-air batteries: Progress in
electrolyte development and cell configuration advancement. Journal of Power Sources,
283,358-371.
[47] Khor, A., Leung, P., Mohamed, M. R., Flox, C., Xu, Q., An, L. and Shah, A. A. (2018).
Review of zinc-based hybrid flow batteries: From fundamentals to applications. Materials
today energy, 8, 80-108.
[48] Wei, X., Desai, D., Yadav, G. G., Turney, D. E., Couzis, A., & Banerjee, S. (2016). Impact
of anode substrates on electrodeposited zinc over cycling in zinc-anode rechargeable alkaline
batteries. Electrochimica Acta, 212, 603-613.
[49] Yi, J., Liang, P., Liu, X., Wu, K., Liu, Y., Wang, Y., ... & Zhang, J. (2018). Challenges,
mitigation strategies and perspectives in development of zinc-electrode materials and
fabrication for rechargeable zinc–air batteries. Energy & Environmental Science, 11(11), 3075-
3095.
[50] Varzi, A., Raccichini, R., Passerini, S., & Scrosati, B. (2016). Challenges and prospects
of the role of solid electrolytes in the revitalization of lithium metal batteries. Journal of
Materials Chemistry A, 4(44), 17251-17259.
[51] Balbuena, P. B. (2014, June). Electrolyte materials-Issues and challenges. In AIP
Conference Proceedings (Vol. 1597, No. 1, pp. 82-97). American Institute of Physics.
[52] Ortiz-Aparicio, J. L., Meas, Y., Trejo, G., Ortega, R., Chapman, T. W., & Chainet, E.
(2013). Effects of organic additives on zinc electrodeposition from alkaline electrolytes.
Journal of Applied Electrochemistry, 43(3), 289-300.
[53] Lee, C. W., Sathiyanarayanan, K., Eom, S. W., Kim, H. S., & Yun, M. S. (2006). Novel
electrochemical behavior of zinc anodes in zinc/air batteries in the presence of additives.
Journal of Power Sources, 159(2), 1474-1477.
[54]Nartey, V. K., Binder, L., & Kordesch, K. (1994). Identification of organic corrosion
inhibitors suitable for use in rechargeable alkaline zinc batteries. Journal of power sources,
52(2), 217-222.

35
[55] Youssef, K. M., Koch, C. C., & Fedkiw, P. S. (2004). Influence of additives and pulse
electrodeposition parameters on production of nanocrystalline zinc from zinc chloride
electrolytes. Journal of the Electrochemical Society, 151(2), C103-C111.
[56] Hosseini, S., Abbasi, A., Uginet, L. O., Haustraete, N., Praserthdam, S., Yonezawa, T., &
Kheawhom, S. (2019). The Influence of Dimethyl Sulfoxide as Electrolyte Additive on Anodic
Dissolution of Alkaline Zinc-Air Flow Battery. Scientific Reports, 9(1), 1-12.
[57]Lan, C. J., Lee, C. Y., & Chin, T. S. (2007). Tetra-alkyl ammonium hydroxides as
inhibitors of Zn dendrite in Zn-based secondary batteries. Electrochimica acta, 52(17), 5407-
5416.
[58] Ein-Eli, Y., Auinat, M., & Starosvetsky, D. (2003). Electrochemical and surface studies
of zinc in alkaline solutions containing organic corrosion inhibitors. Journal of power sources,
114(2), 330-337.
[59] Banik, S. J., & Akolkar, R. (2015). Suppressing dendritic growth during alkaline zinc
electrodeposition using polyethylenimine additive. Electrochimica Acta, 179, 475-481.
[60] Zhou, D., Shanmukaraj, D., Tkacheva, A., Armand, M., & Wang, G. (2019). Polymer
electrolytes for lithium-based batteries: advances and prospects. Chem, 5(9), 2326-2352.

36
37