PVDF-HFP Microporous Membranes as

Effective Electrode Coatings for

High-performance
Rechargeable Aqueous Zinc-ion Batteries

by

ERIC ZHOU

THESIS
Presented to University of Waterloo
Department of Chemistry
as partial fulfillment of
CHEM 494 research project
supervised by professor Pu Chen

Waterloo, Ontario, Canada, 2023

1
 Acknowledgements

First, I want to offer my gratitude to my supervisor professor Pu Chen, for his guidance,

support, and encouragement throughout the CHEM 494 research course. His expertise and

knowledge in the battery field have been invaluable, and I am grateful for the opportunity to be

part of the biomedical engineering and energy storage research group at University of Waterloo.

Second, I would like to express my appreciation to my mentor Mei Han, for her

continuous patience, understanding, and support throughout the research process. Not only was

she responsible for her own research objectives, but she also kept her colleagues on the right

research trajectories for the collective benefit of the group. Therefore, her guidance and insights

were essential in keeping me on track for my research objectives. I am very grateful for the

opportunity to have worked under her mentorship.

I would also like to thank all the members of Pu Chen lab, especially my colleagues

Kylie and Ray, for showing me the laboratory essentials and helping me to get started with my

own research project. I thank them for their friendship, and for providing a supportive and

stimulating work environment.

Finally, I would like to express my appreciation to my family members for their

unwavering support during my CHEM 494 research journey.

2
 Table of Contents

Acknowledgements 2

Table of Contents 3

1. Historical 4

2. Introduction 5

3. Experimental 9

4. Results and Discussion 14

References 19

3
1. Historical

Advancement of green, renewable and sustainable energy systems are crucial for

developing long-lasting solutions to urgent climate change and environmental issues. Battery

technology plays a critical role in paving the way to minimize non-renewable energy sources.

Since 1991, Lithium-ion (Li-ion) batteries have become the most commercially successful

rechargeable batteries [16]. They power much of the world’s energy grids, consumer portable

devices, electrical vehicles and renewable energy sources. Advantages of these secondary

batteries include: high capacity, high power & energy density, long cycle life, low self-discharge

rate [19] and no memory effect [18]. However, Li-ion batteries are relatively expensive, pose

risks of thermal runaways due to non-aqueous electrolytes [17], and have a variety of

environmental impacts associated with production, usage and disposal of materials [13]. As a

result, the imperative research & development of non-lithium, aqueous rechargeable batteries is

becoming prevalent as they are generally safer and low-cost.

Nowadays, aqueous rechargeable batteries based on divalent-ions have attracted much

attention as they show potential as alternatives to Li-ion batteries. The use of aqueous

electrolytes allows high theoretical ionic conductivities (up to 1 S/cm) as opposed to lower ionic

conductivities (1-10 mS/cm) for most non-aqueous Li-ion batteries [1]. As well, divalent metals

can theoretically yield higher capacity, power & energy densities as they partake in 2 electrons

transfer per ion [22]. In particular, Zinc divalent ions (Zn2+) utilized in rechargeable aqueous

Zn-ion batteries (RAZB) have several advantages over Li-ion batteries due to properties of Zn

and its intrinsic safety in water-based electrolytes [1]. Zn is highly abundant, inexpensive (see

Fig. 1a), relatively safe & non-toxic (compared to alkali metals and divalent alkaline earth

metals) and demonstrated satisfactory performances as anode materials [1]. It is also relatively

4
stable in water and has a low standard reduction potential of -0.76 V (see Fig. 1b), which favors

spontaneous redox reactions [1].

Figure 1 | a. Zinc has the lowest metal spot price (≈ $3.00 USD/kg) as established by global
metal exchanges [14]. b. Zinc has a low standard reduction potential (−0.76 V versus standard
hydrogen electrode (SHE) at 25 °C) suitable for electrochemical reactions [15].

While RAZBs do have their merits of being potentially feasible, there are still persistent

problems that prevent them from widespread commercialization, as they are still inferior to

Li-ion batteries in terms of capacity, power & energy density and cycle life.

2. Introduction

2.1. Challenges faced by rechargeable aqueous Zn-ion batteries

The assembly of any RAZB is analogous to that of a secondary electrochemical cell, in

which a complete, reversible circuit is formed between the separated anode and the cathode, both

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in electrolytes (Fig. 2). The combinations of different cathode materials with the Zn anode in

aqueous electrolytes result in different redox mechanisms for RAZBs, through which a series of

challenges and issues occur during these reversible reactions.

Figure 2 | Schematic representation of rechargeable aqueous Zn-||MnO2 batteries, with Zinc foil
as the anode material (left) and ε-MnO2 as the cathode material (right)

One challenge is the selection of suitable cathode materials to pair with Zn anode and a

given electrolyte for designing highly functional batteries. There exists many cathode materials

for RAZBs, but they mostly show low conductivity, poor cycling stability and/or have

complicated synthesis procedures [3]. Hence, the exploration and exploitation of novel cathode

materials are continuously being experimented. Another challenge is that although aqueous

electrolytes has a higher theoretical ionic conductivity (up to 1 S/cm) compared to organic

electrolytes (1-10 mS/cm), their electrochemical potential stable windows (EPSW, 1–1.6 V) are

much lower than those of organic electrolytes (3–4 V) [6]. Thus, RAZBs usually have a high

power density (1500–9000 W/kg), but a limited energy density (80–150 Wh/kg). As well,

different aqueous electrolytes (i.e. different pH) result in different electrode behaviors and

working principles, which affects the reversibility of the Zn anode [21].

The most problematic issue is the hard-to-control Zn dendrites, which form after repeated

charging/discharging cycles, in which Zn-ions deposit unevenly onto the anode surface, forming

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problematic structures that may eventually pierce the separator to cause short circuit [5].

Moreover, undesirable side reactions such as the hydrogen evolution reaction (HER) can

introduce by-products that hinder deposition and/or form passive layers around the electrodes

[5]. Some other typical problems include active materials dissolution, corrosion, shape change

etc. All of which can drastically reduce the overall performance and opportunities for RAZBs to

scale-up production towards more extensive applications. Here, we tackle these problems and

challenges by experimenting with coin-cell RAZBs of the Zn anode and MnO2 cathode.

2.2. Coin-cell type rechargeable aqueous Zn-ion batteries: Zn-||MnO2

The coin-cell battery type consists of (see Fig. 3, assemble from bottom to top) the

positive case, an insulating layer of Polyethylene (PE) membrane, a cathode (i.e. MnO2 with

active material facing the top), a

separator (wetted with electrolytes), an

anode (i.e. Zn), a spring, a spacer and

the negative case. The separator is

important as it serves as an

ion-permeable membrane to physically

separate the electrodes while allowing

selective ions to flow between them.

For the cathode, MnO2 based material

is preferred due to its relatively high

conductivity, high specific capacity,

high energy density, ease of synthesis ,

low cost, and low toxicity [11].

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Furthermore, MnO2 is often studied due to its polymorphic properties, and the underlying energy

storage mechanisms under different circumstances remain controversial [12].

2.3. Electrochemistry of rechargeable aqueous Zn-ion batteries: Zn-||MnO2

Since MnO2 exists in many crystal forms, their microstructures and interactions with

different electrolytes & ions can all significantly affect the electrochemistry of rechargeable

aqueous Zn-||MnO2 batteries. Several mechanisms have been observed and proposed, including

intercalation/deintercalation, dual dissolution/deposition etc [21]. While the exact

charging/discharging process of rechargeable aqueous Zn-||MnO2 batteries varies, the generic

electrochemistry can be described by the following redox reactions:

Anode (discharging): Zn → Zn2+ + 2e-

Cathode (discharging): MnO2 + Zn2+ + 2e- → ZnMnO2

Cathode (charging): ZnMnO2 → MnO2 + Zn2+ + 2e-

Anode (charging): Zn2+ + 2e- → Zn

Here, the proposed mechanism is the intercalation/deintercalation of Zn2+ ions. During

discharging, the system is a galvanic cell as chemical energy is being converted to electrical

energy. The Zn anode spontaneously oxidizes and provides 2 electrons for the MnO2 cathode to

be reduced (Mn4+ → Mn2+). Then, the dissolved Zn2+ diffuses through the separator to reach the

cathode (MnO2 2-), allowing the subsequent intercalation of Zn2+ into the holes of the crystal

lattices of the MnO2 cathode (ZnMnO2). Specifically, ε-MnO2 with layers of MnO6 octahedra is

chosen because it is theoretically able to store more charges, with more active sites inside 1 by 1

and 2 by 1 tunnels (see Fig. 2).

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 During charging, the system becomes an electrolytic cell as electrical energy is being

applied to do work on Zn2+ ions. The deintercalation of Zn2+ occurs at the holes of the cathode

and reverse reactions happen, in which they deposit back onto the Zn anode by reducing.

2.4. Research Objective

Two of the most critical performance metrics for coin-cell RAZBs are defined by their

discharge specific capacity (mAh/g) and cycle life. Higher discharge specific capacities indicate

more Zn-ion charges readily intercalate into the ε-MnO2 lattice. Higher cycle numbers are

indicative of a stable discharge specific capacity (maintain the same amount of Zn-ions in

ε-MnO2 lattices over time) for long charge/discharge cycles without dropping in reversibility.

However, as the cycles go on, effective Zn-ion charges are lost and the coulombic efficiency

(discharge capacity/charge capacity ratio) is decreased due to corrosion/dissolution, shape

change, passivation, dendrite formation, H2 evolution side reactions etc.

In this research project, the overall goal is to prolong the cycling performance and

maximize the specific capacity of coin-cell rechargeable aqueous Zn-||MnO2 batteries. Different

methods of preparations, such as applying polymer-based porous membranes and/or doping to

the electrodes are investigated. By modifications of MnO2 cathode materials and/or Zn anode,

the battery functionalities may be improved and provide insights to aforementioned problems.

3. Experimental

3.1. Synthesis of cathode material and preparation of cathode - Bi-MnO2 (4 mol%)

Studies suggest that doping of bismuth (Bi) into MnO2 stabilizes its internal structure

[23], and thus, increasing the cathode’s electrical conductivity and retention of capacity at high

cycles. Here, ε-MnO2 cathodes with 4 mol% Bi doping are synthesized. First, at room

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temperature, powdered ε-MnO2 and bismuth nitrate pentahydrate (Bi(NO)3·5H2O) are weighed

out (i.e. 5.000 g ε-MnO2, 1.116 g Bi(NO)3·5H2O). Then, a suitable beaker containing a magnetic

stir bar and an adequate amount of DI water (i.e. 150 ml for the given material) is put onto a hot

plate with a stirring rate of ~700 rpm. Next, the weighed out ε-MnO2 is slowly poured into the

stirring beaker, followed by the slow addition of Bi(NO)3·5H2O. This mixture is then

magnetically stirred and dispersed for 2 hours at room temperature. After that, a total of three

rounds of centrifugation and washing of DI water and ethanol is performed on the mixture.

Afterwards, the dried Bi-MnO2 precursors are placed in a muffle furnace and calcined at 450°C

for 4 hours. Lastly, the Bi-MnO2 (4 mol%) powdered mixture is obtained as the cathode material

for coating onto polyethylene (PE) films (conductive, impregnated with carbon acetyl black).

To allow adhesion and facilitate conductivity of the powdered Bi-MnO2 (4 mol%)

mixture onto the PE film, conductive and binding materials are required, which are carbon

(acetyl black) and 5 wt% polyvinylidene-fluoride (PVDF) in n-methyl-2-pyrrolidone (NMP)

solvent, respectively. In the 7:2:1 mass ratio, Bi-MnO2 (4 mol%), carbon, and PVDF are

combined into one container, respectively (see Tab. 1). They are then grinded and centrifuged at

Table 1 | The components of the ε-MnO2 cathode material in Zn-||MnO2 batteries

2000 rpm for 2-3 minutes. The resulting viscous mixture is then poured onto a PE film for

coating with a thin-film thickness of 500 μm. Subsequently, the PE film coated with Bi-MnO2 (4

mol%) is dried overnight in a 60°C oven. Finally, the entire cathode film is cut into smaller,

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disc-shaped pieces using coin-cell electrode cutters, each with a diameter of 12.7mm. These

cathodes are the control samples and can be further modified (see Fig. 4).

Figure 4 | Schematic of the preparation of ε-MnO2 cathodes in Zn-||MnO2 batteries

3.2. Spin Coating - PVDF-HFP microporous membranes on Bi-ε-MnO2 (4 mol%) cathodes

The Bi-MnO2 (4 mol%) cathode is further coated with a polymer membrane to

investigate its impact on capacity and cycling performance. Polyvinylidene-fluoride

hexafluoropropylene (PVDF-HFP) is chosen due to its compatibility with the nature of the

electrolyte and the cathode. By applying spin coating, fine PVDF-HFP microporous membranes

with tunable porosity can be obtained by variations of water content. PVDF crystalline phase

keeps good mechanical stability, while the amorphous HFP phase helps to capture and retain

more liquid electrolytes [25]. Compared with PVDF, PVDF–HFP has a relatively lower

crystallinity due to the copolymerization effect, and increased solubility in common

polar/organic solvents (i.e. Acetone), due to the presence of highly electronegative fluorine

atoms in its backbone [24], [25]. Although both are hydrophobic, PVDF-HFP allows slightly

higher ionic conductivity than just PVDF alone, since water molecules are able to form hydrogen

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bonds with the extra polar fluorine functional groups, which creates more interconnected water

channels that allow ions to travel through the membrane [24], [25]. To form the microporous

membrane onto the cathode, PVDF-HFP is first dissolved in analytical grade acetone to prepare

the PVDF-HFP (5 wt%) stock solution. From the stock, 6 samples are taken, and are diluted and

dispersed with DI water. Solutions of H2O:PVDF-HFP in mass ratios of 0.2:1, 0.5:1, 0.7:1, 1:1,

1.5:1 and 2:1 are prepared. Then, spin coatings of polymer films are applied to numerous

cathodes for each ratio of H2O:PVDF-HFP solutions (see Fig. 5).

Figure 5 | Spin coating of PVDF-HFP membranes onto ε-MnO2 cathodes in Zn-||MnO2 batteries

A dynamic dispense is employed, in which 2 drops (50µL) of coating solution is pipetted onto

the center of the cathode substrate while spinning, followed by an increase in spin speed. As

volatile acetone evaporates, the hydrophobic PVDF-HFP self-assembles onto the cathode,

forming a thin and uniform polymer layer with different porosity corresponding to different

H2O:PVDF-HFP ratios.

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 The optimal water ratio to control the pore sizes of microporous PVDF-HFP are

determined from Scanning Electron Microscope (SEM) from the results section. Experimentally,

only solutions of H2O:PVDF-HFP in mass ratios of 0.2:1, 0.5:1 and 0.7:1 (3 ratios) remained of

interest for investigation (see Fig. 6 - 7). To attempt to further increase specific capacity and

ionic conductivity, a repeated set of PVDF-HFP microporous membranes are prepared with

1wt% carbon doping for each of the 3 ratios (see Fig. 6 - 7).

Figure 6 | Spin coated PVDF-HFP membranes on ε-MnO2 cathodes prepared from solutions of
H2O:PVDF-HFP in mass ratios of 0.2, 0.5, 0.7. Left: undoped. Right: doped with 1wt% carbon

Figure 7 | Spin coated PVDF-HFP membranes on both control and experimental groups
Top: spin coated PVDF-HFP membranes on only the PE film. The membranes are clearly visible
with increasing water content ratios. Bottom: spin coated PVDF-HFP membranes on ε-MnO2
cathodes prepared from solutions of H2O:PVDF-HFP in mass ratios of 0.2:1, 0.5:1, 0.7:1. The
membranes are not clearly visible for the undoped set (0.2:1, 0.5:1, 0.7:1) and the doped set
(0.2:1, 0.5:1, 0.7:1 with 1wt% carbon).

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3.3. Assembly and testing of coin-cell rechargeable aqueous Zn-||MnO2 batteries
Upon completion of the preparation of PVDF-HFP coated cathodes, each battery is

assembled into a coin-cell with a Zn anode, Bi-MnO2 (4 mol%) cathode, and 4 drops (100 µL) of

1M ZnSO4 + 0.4M MnSO4 electrolyte casted into the separator. The electrolyte chosen here not

only provides more charges, but it also provides a lower pH, protonated/mildly acidic

environment that suppresses Zn passivation, shape change and dendrite formation. All batteries

are tested using Neware battery testing system A211-BTS-3S and charged/discharged under a

current density of 50 mA/g. One batch of batteries use Bi-MnO2 (4 mol%) cathodes without

polymer coatings, which act as controls. Other batches use Bi-MnO2 (4 mol%) cathodes with the

applied polymer coatings at 3 different H2O:PVDF-HFP ratios (0.2:1, 0.5:1, 0.7:1). The capacity

and cyclability of all batteries, including both controls and polymer-coated batteries of 3 ratios,

are observed at the 50 mA/g current density.

4. Results and Discussion

Initially, microporous membranes are prepared from solutions of H2O:PVDF-HFP in

mass ratios of 0.2:1, 0.5:1, 0.7:1, 1:1, 1.5:1 and 2:1. From these results, the optimal water ratio to

control the pore sizes are determined from Scanning Electron Microscope (SEM, see Fig. 8).

From the SEM results, it is observable that the pore sizes increase as water content increases. At

ratios of 1, it is noticeable that there is swelling in the porous structures. As water content

increases furthermore, the pores become larger and the porous structures become more

amorphous. It is evident that at ratios of 1.5 and 2, the porous structure completely loses its

crystallinity and no pores are visible. Whereas at ratios of 0.2, 0.5, 0.7, the pores are clearly

visible, which theoretically should allow ions to travel between the anode and the cathode while

preventing short circuit. Therefore, coating solutions of H2O:PVDF-HFP with ratios of 0.2, 0.5,

14
0.7 are prepared and coated onto the cathodes for testing, as too much water content will degrade

the porous structure.

Figure 8 | SEM images of spin coated PVDF-HFP membranes on PE films show the porous
structure at different H2O:PVDF-HFP ratios, with 0.2, 0.5, 0.7 ratios to be optimal

The specific discharge capacity and cyclability curves of all coin-cell rechargeable

aqueous Zn-||MnO2 batteries, including both controls and polymer-coated batteries of 3 ratios,

are obtained at the 50 mA/g current density. For the batteries tested with spin coated cathodes

(membranes applied on cathodes), but without carbon doping (see Fig. 9 top), the results

obtained generally follow the trend of longer cycles, lower capacity, compared to the control

samples without any membrane applied. Since the added PVDF-HFP is not electrically

conductive, it most likely induces resistance for the ions, thus lowering the capacity. However,

the pores allow a much more stable charge transfer process, which is indicative of the stable

discharge specific capacity over a longer cycle number. For the batteries tested with spin coated

cathodes (membranes applied on cathodes), and with carbon doping (see Fig. 9 bottom), the

results obtained are similar, following the trend of longer cycles, lower capacity, compared to the

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control samples without any membrane applied. Overall, the batteries with spin coated and

carbon doped cathodes have slightly higher capacity, but slightly shorter cycles than without

carbon doped. Still, they all obtained longer and more stable cycles than the control samples with

no coatings at all. Therefore, carbon doping onto PVDF-HFP membranes of the MnO2 cathode

can increase the discharge specific capacity by about 50 mAh/g at the cost of decreasing the

cycle numbers, which is inconsistent across different results.

Figure 9 | Top: Performance of rechargeable aqueous Zn-|| MnO2 batteries with cathodes spin
coated at different H2O:PVDF-HFP wt% ratios (0.2:1, 0.5:1, 0.7:1, respectively) under 50 mA/g
current. Top: no carbon doping. Bottom: with 1 wt% carbon doping

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Experimentally, more consistent results are obtained for the batteries with spin coated and

without carbon doped cathodes. Whereas the results are inconsistent for spin coated cathodes

with carbon doping.

Further experiments show that applying polymer membranes to the cathode can also

suppress Zn dendrites formation on the anode (see Fig. 10), whereas Zn dendrite grows more

rapidly on blank MnO2 cathodes without any microporous membranes applied.

Figure 10 | SEM images show Zn dendrite inhibition on Zn anode when membrane is applied at
the 10th cycle in a charged state

The hypothesis is that since ions must travel between the porous membranes, the porous

membranes may alter the path in which ions move back and forth between the anode and

cathode, and this optimal path make the current density more uniform, which results in less

dendrites formation and longer cycles and stability.

In conclusion, polymer membranes can suppress the zinc dendrites formation, which can

increase cycle number. And the pore sizes can either increase or decrease the cycles as well. The

best pore sizes are formed when water is added to the coating solution with ratios of 0.5, 0.7.

With lower water content, like 0.2, the ionic conductivity is lower, since the pore sizes are

smaller and the Zinc charges experience more resistance and gets trapped inside the MnO2 lattice

17
after discharging. But if too much water content is added, such as ratios of 1.5, 2, the membrane

might degrade or might not form a defined structure.

In summary, the environmental and economical concerns of Li-ion batteries over the

years had facilitated the research of Zn-ion batteries. Although Zn-ion ARBs show promising

results as feasible alternatives to Li-ion batteries, there are still many drawbacks to be overcome,

such as ineffective cathodes, problematic formation of dendrites, undesirable side reactions etc.

In this work, coin-cell type Zn-||MnO2 ARBs are investigated to better understand

existing problems and to aid in the collective effort of Zn-ion batteries research. In an attempt to

increase the overall capacity and cycle life of these batteries, various types of MnO2 cathodes are

prepared with different modifications, including: doping of Bi, spin coating of polymer film

(H2O:PVDF-HFP) using different ratios, spin coating of polymer film doped with carbon. The

best pore sizes for the membrane on cathodes are prepared with water to PVDF-HFP ratios of

0.2, 0.5, 0.7. It is observed that Zn anodes also have inhibited dendrite formation when the

polymer membranes are applied, which leads to increased battery performances.

For further work, the experimental conditions can be improved and optimized. Cracking

of more accuracy and precision in coating. More tests can be performed using different thickness

of Zinc anodes and modifications of MnO2 cathodes to test them under different current.

Potentially, polymer membranes can be deemed effective for high performance rechargeable

aqueous zinc-ion batteries.

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