CN112635698B

CN112635698B - Negative pole piece of zinc secondary battery and preparation method and application thereof

Info

Publication number: CN112635698B
Application number: CN202011525647.8A
Authority: CN
Inventors: 穆延璐; 葛广路; 李德兴; 周天易
Original assignee: National Center for Nanosccience and Technology China
Current assignee: National Center for Nanosccience and Technology China
Priority date: 2020-12-22
Filing date: 2020-12-22
Publication date: 2022-05-13
Anticipated expiration: 2040-12-22
Also published as: CN112635698A

Abstract

The invention provides a negative pole piece of a zinc secondary battery and a preparation method and application thereof. The negative pole piece comprises a zinc-containing substrate and a composite protective layer positioned on the surface of the substrate; the composite protective layer includes metal nanoparticles and zinc fluoride. The invention can effectively form a stable composite protective layer formed by embedding metal nano particles into a zinc fluoride coating on the surface of the zinc metal cathode through an in-situ chemical replacement method, and simultaneously can provide abundant nucleation sites for uniform deposition of zinc, so that the deposition of zinc is more uniform and compact, the corrosion of an electrolyte and the growth of zinc dendrites of a zinc secondary battery in charge and discharge cycles can be effectively inhibited, and the effects of greatly improving the cycle performance and safety of the zinc secondary battery are achieved.

Description

Negative pole piece of zinc secondary battery and preparation method and application thereof

Technical Field

The invention belongs to the technical field of zinc secondary batteries, and relates to a negative pole piece of a zinc secondary battery, and a preparation method and application thereof.

Background

The rapid transition from the traditional fossil energy as the main energy to low-carbon energy is a great transition of the national energy structure. In order to further improve the flexibility, economy and safety of energy storage and meet the rapid development of society, the development of a novel large-scale energy storage technology is a primary task faced by modern scientists. Therefore, the development of an energy storage system which is environmentally friendly and harmless and has a high energy density is an urgent necessity for realizing the national green energy strategy. Recently, aqueous Zinc Ion Batteries (ZIB) have received great attention as the most favorable candidate, with high theoretical capacity and excellent stability in water due to the low redox potential of the zinc anode. Meanwhile, the metal zinc has the advantages of abundant resources, low toxicity, easy treatment and the like. Therefore, ZIB which is low in price, high in safety, free of environmental pollution and high in power is an ideal green battery system.

Zinc batteries, one of the oldest batteries, have greatly solved the problem of safety as a sustainable electrochemical system in aqueous electrolytes, compared to zinc ion batteries (LIBs) using combustible organic electrolytes. Recently, rechargeable zinc secondary batteries have gained renewed interest as a safe, environmentally friendly electrochemical system. Over decades, there has been considerable research into zinc ion batteries, including vanadium oxideThe research on the electrode materials of manganese oxide, prussian blue analogue, organic materials and the like has been well established. In contrast, research on the anode is urgently in need of development. In the water-based zinc ion secondary battery, the metal zinc is rich in source, low in price, low in oxidation-reduction potential (minus 0.76V relative to SHE) and high in theoretical capacity (820 mAhg)^-1) And become excellent candidates for anodes. Despite these advantages, zinc metal anodes still suffer from uneven deposition of metal cations which can lead to dendrite formation. Furthermore, the corrosion caused by the electrolyte on its surface and the formation of electrochemically inert and irreversible by-products may cause gassing and surface passivation. Therefore, there is an urgent need to develop a highly stable zinc anode with uniform zinc deposition.

CN108807910A discloses a water system zinc ion battery, which comprises a positive electrode, a negative electrode, an electrolyte and a diaphragm arranged between the positive electrode and the negative electrode, wherein the negative electrode is a graphene-assisted zinc negative electrode, the electrolyte comprises a solvent and a solute, the solvent is water, and the solute comprises soluble zinc salt and manganese salt. The zinc battery prepared by the document is easy to have safety problems of dendrite caused by uneven deposition of zinc and flatulence caused by corrosion of electrolyte

CN109980226A discloses a zinc cathode with a polyamide brightener layer, belonging to the technical field of energy materials. The method is characterized in that polyamide is dissolved in anhydrous formic acid for remodeling, and a solid brightener layer is constructed on the surface of a zinc cathode. None of the methods mentioned in this document fundamentally solves the problem of uneven deposition caused by concentration gradients in the solution, and moreover the method only works to a certain extent in inhibiting the growth of zinc dendrites.

None of the above-mentioned methods can fundamentally solve the problem of uneven deposition caused by concentration gradient in the solution, and furthermore, these methods can only achieve the effect of inhibiting the growth of zinc dendrite to a certain extent, and at the same time, their preparation process is complicated, cost is high, and it is difficult to apply them to practical production.

Therefore, how to fundamentally overcome the safety problems of dendritic crystal growth caused by uneven zinc deposition in the charging and discharging processes of the existing zinc metal cathode, gas expansion caused by electrolyte corrosion and the like is a technical problem which is urgently needed to be solved at present.

Disclosure of Invention

The invention aims to provide a negative pole piece of a zinc secondary battery, and a preparation method and application thereof. According to the invention, by the in-situ chemical replacement method, a stable composite protective layer consisting of metal nanoparticles and zinc fluoride can be effectively formed on the surface of the zinc metal cathode, and meanwhile, uniform nucleation sites during zinc deposition can be effectively provided, so that the zinc deposition is more uniform, corrosion caused by electrolyte and growth of zinc dendrites in charge-discharge cycles of the zinc secondary battery are inhibited, and the effects of greatly improving the cycle performance and safety of the zinc secondary battery are achieved.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides a negative electrode plate of a zinc secondary battery, which comprises a substrate containing zinc metal and a composite protective layer positioned on the surface of the substrate; the composite protective layer includes metal nanoparticles and zinc fluoride.

The surface of the zinc cathode substrate is provided with a stable composite protective layer consisting of metal nano particles and zinc fluoride, which is beneficial to uniformly providing nucleation sites during zinc deposition, so that the zinc deposition is more uniform, the corrosion caused by electrolyte and the growth of zinc dendrites in charge-discharge circulation of the zinc secondary battery are inhibited, and the cycle performance and the safety of the zinc secondary battery are greatly improved.

The metal nano particles play a role in regulating and controlling zinc ion deposition and inhibiting dendritic crystals in the composite protective layer, and the zinc fluoride can play a role in preventing the corrosion of a zinc cathode.

Preferably, the thickness of the composite protective layer is 1 to 5 μm, such as 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 4 μm or 5 μm, and preferably 1.5 to 2.5 μm.

In the invention, the composite protective layer is too thin to fully play a role in preventing surface corrosion, and too thick can cause difficulty in ion transmission and cause overpotential rise.

Preferably, the zinc-containing metal comprises zinc flakes and/or zinc powder.

Preferably, the metal nanoparticles comprise any one or a combination of at least two of copper, silver, indium or aluminum.

In a second aspect, the present invention provides a method for preparing a negative electrode plate of a zinc secondary battery according to the first aspect, wherein the method for preparing the negative electrode plate comprises:

and soaking the substrate containing the zinc metal into a metal fluoride solution, standing and drying to obtain the negative pole piece of the zinc secondary battery.

According to the invention, by the in-situ chemical replacement method, a stable composite protective layer consisting of metal nanoparticles and zinc fluoride can be effectively formed on the surface of the zinc metal cathode, and meanwhile, nucleation sites during uniform zinc deposition can be effectively provided, so that the zinc deposition is more uniform, corrosion caused by electrolyte and growth of zinc dendrites in charge-discharge cycles of the zinc secondary battery are inhibited, and the effects of greatly improving the cycle performance and safety of the zinc secondary battery are achieved.

Preferably, the metal fluoride comprises any one of copper fluoride, silver fluoride, indium fluoride or aluminum fluoride or a combination of at least two thereof.

Preferably, the metal fluoride in the metal fluoride solution is added in an amount of 0.5 to 5 wt%, such as 0.5 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.5 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt%, etc., of the solvent in the metal fluoride solution, preferably 1 to 2 wt%.

When the content of the metal fluoride is less than 0.5 wt%, a displacement reaction cannot occur, thereby affecting the formation of a protective layer; when the content of the zinc salt is more than 5 wt%, the solubility limit of the fluoride in the solvent is exceeded, and the composition, compactness and other properties of the modification layer cannot be affected.

Preferably, the solvent in the metal fluoride solution comprises any one of or a combination of at least two of anhydrous ethanol, anhydrous methanol, N' N dimethylformamide, or tetrahydrofuran.

Preferably, the standing time is 12-48 h, such as 12h, 15h, 16h, 18h, 20h, 24h, 25h, 28h, 30h, 35h, 36h, 40h, 44h, 45h or 48 h.

Preferably, the standing is followed by ultrasonic cleaning and then drying.

As a preferred technical scheme, the preparation method of the negative pole piece of the zinc secondary battery comprises the following steps:

soaking a substrate containing zinc metal into a metal fluoride solution, standing for 12-48 h, ultrasonically cleaning, and drying to obtain a negative pole piece of the zinc secondary battery;

wherein the metal fluoride comprises any one or a combination of at least two of copper fluoride, silver fluoride, indium fluoride or aluminum fluoride; the addition amount of the metal fluoride in the metal fluoride solution is 1-2 wt% of the solvent in the metal fluoride solution.

In a third aspect, the present invention further provides a zinc secondary battery, wherein the zinc secondary battery comprises a positive electrode plate, the negative electrode plate as described in the first aspect, a diaphragm and an electrolyte; wherein the diaphragm is positioned between the positive pole piece and the negative pole piece.

Preferably, the positive electrode piece comprises a titanium foil current collector and a positive electrode membrane.

Preferably, the positive electrode membrane includes a positive electrode active material, a conductive agent, and a binder.

Preferably, the positive electrode active material includes manganese dioxide and/or vanadium pentoxide.

Preferably, the separator comprises any one of or a combination of at least two of glass fiber, cellulose, or polyvinylidene fluoride.

Preferably, the electrolyte comprises any one of or a combination of at least two of zinc bis (trifluoromethyl) sulfonyl imide, zinc sulfate or zinc trifluoro methyl sulfonate.

Compared with the prior art, the invention has the following beneficial effects:

(1) the surface of the zinc cathode substrate provided by the invention is provided with a stable composite protective layer consisting of metal nano particles and zinc fluoride, which is beneficial to uniformly providing nucleation sites during zinc deposition, so that the zinc deposition is more uniform, the corrosion caused by electrolyte and the growth of zinc dendrite in charge-discharge circulation of the zinc secondary battery are inhibited, the cycle performance and the safety of the zinc secondary battery are greatly improved, the cycle time reaches 500 hours or more under the condition of no dendrite generation, and when the addition of metal fluoride is further optimized, the cycle time can reach more than 700 hours.

(2) The invention can effectively form a stable composite protective layer consisting of metal nano particles and zinc fluoride on the surface of the zinc metal cathode by an in-situ chemical replacement method, and the preparation method is simple, easy to operate and cost-saving.

Drawings

Fig. 1 is an SEM image of the zinc fluoride-copper composite protective layer in example 1.

FIG. 2 is a scanning electron microscope image of the surface topography of the negative electrode tab in example 1 after 20 cycles in 2mol/L zinc sulfate electrolyte.

FIG. 3 is a partially enlarged view of a scanning electron microscope image of the surface topography of the negative electrode tab in example 1 after 20 cycles in 2mol/L zinc sulfate electrolyte.

FIG. 4 is a scanning electron microscope image of the surface topography of the negative electrode tab in comparative example 1 after 20 cycles in 2mol/L zinc sulfate electrolyte.

FIG. 5 is a partially enlarged scanning electron micrograph of the surface topography of the negative electrode tab of comparative example 1 after 20 cycles in 2mol/L zinc sulfate electrolyte.

FIG. 6 is a graph showing long cycle performance of the symmetrical batteries prepared in example 1 and comparative example 1 in a zinc sulfate electrolyte of 2 mol/L.

Fig. 7 is a long cycle performance curve diagram and corresponding coulombic efficiency of the zinc-vanadium pentoxide full cell prepared in example 1 and comparative example 1 in 2mol/L zinc sulfate electrolyte.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Example 1

The embodiment provides a negative electrode plate of a zinc secondary battery, which comprises a zinc sheet and a composite protective layer positioned on the surface of the zinc sheet; the composite protective layer includes copper nanoparticles and zinc fluoride.

The thickness of the composite protective layer is 2 μm.

The preparation method of the negative pole piece of the zinc secondary battery comprises the following steps:

and soaking the polished zinc sheet in an absolute ethyl alcohol solution of copper fluoride, wherein the addition amount of the copper fluoride is 1.5 wt% of the absolute ethyl alcohol solution, soaking for 24h, taking out the zinc sheet, carrying out ultrasonic cleaning, drying, and cutting the dried zinc sheet into small round sheets with the diameter of 12mm to obtain the negative pole piece of the zinc secondary battery.

It can be seen from fig. 1 that the surface of the modified zinc sheet is uniformly covered with a layer of zinc fluoride-copper particles, the size of the primary particles is about 1 μm, wherein the zinc fluoride and the copper particles are tightly combined and mutually wrapped to form a uniform and compact composite protective layer on the surface of the zinc cathode.

Example 2

The embodiment provides a negative pole piece of a zinc secondary battery. The negative pole piece comprises a zinc sheet and a composite protective layer positioned on the surface of the zinc sheet; the composite protective layer includes indium nanoparticles and zinc fluoride.

The thickness of the composite protective layer is 2 μm.

And soaking the polished zinc sheet in an absolute methanol solution of indium fluoride, wherein the addition amount of the indium fluoride is 1.5 wt% of absolute ethanol, soaking for 12h, taking out the zinc sheet, carrying out ultrasonic cleaning, drying, and cutting the dried zinc sheet into small round sheets with the diameter of 12mm to obtain the negative pole piece of the zinc secondary battery.

Example 3

The embodiment provides a negative pole piece of a zinc secondary battery. The negative pole piece comprises a zinc sheet and a composite protective layer positioned on the surface of the zinc sheet; the composite protective layer includes copper nanoparticles and zinc fluoride.

The thickness of the composite protective layer is 1.5 μm.

The difference between this example and example 1 is: in this example, the amount of copper fluoride added was 1 wt% based on the anhydrous ethanol, and the standing time was 48 hours.

The remaining preparation methods and parameters were in accordance with example 1.

Example 4

The thickness of the composite protective layer is 2.5 μm.

The difference between this example and example 1 is: the amount of copper fluoride added in this example was 2 wt% of absolute ethanol.

Example 5

The thickness of the composite protective layer is 1 μm.

The difference between this example and example 1 is: the amount of copper fluoride added in this example was 0.5 wt% based on the anhydrous ethanol.

When the concentration of the copper fluoride solution is reduced to 0.25 wt%, a uniform and compact protective layer cannot be formed on the surface of the zinc cathode, and only part of particles are scattered on the surface.

Example 6

The thickness of the composite protective layer is 5 μm.

The difference between this example and example 1 is: the amount of copper fluoride added in this example was 5 wt% of absolute ethanol.

Example 7

The thickness of the composite protective layer is 0.5 μm.

The difference between this example and example 1 is: the amount of copper fluoride added in this example was 0.25 wt% based on the anhydrous ethanol.

Comparative example 1

The surface of the zinc sheet is simply polished by abrasive paper, and the zinc sheet is directly cut into small round sheets with the diameter of 12mm, so that the negative pole piece of the zinc secondary battery is obtained.

After the negative pole piece of example 1 and the pole piece of comparative example 1 are circulated in 2mol/L zinc sulfate electrolyte for 20 weeks, surface morphology characterization (fig. 2 and fig. 4) is respectively carried out, and as can be seen from fig. 3, after the zinc negative pole surface containing the composite protective layer is circulated for 20 circles, the surface of the zinc piece is smoother and more compact, which shows that the composite protective layer effectively improves the deposition morphology of the metal zinc negative pole, inhibits the generation of dendrites, and thus greatly improves the cycle life and the safety performance of the battery. Compared with the long cycle performance of the symmetrical battery, the cycle life of the symmetrical battery is greatly prolonged by finding that the zinc cathode containing the composite protective layer. Comparing fig. 5, it can be seen that the cycle life of the symmetric battery is very short without the zinc cathode surface protection layer, and after 20 cycles of cycling, the battery is disassembled, it is known that the surface of the zinc sheet has a serious pitting phenomenon, and the zinc is deposited in a sheet shape and has a lot of dendritic crystals on the surface of the zinc sheet, and in the following cycle, the dendritic crystals will continue to grow and pierce the separator, causing a short circuit of the battery, thereby affecting the cycle life of the zinc battery and creating a potential safety hazard.

As can be seen from fig. 6, the cycle life of the zinc cathode symmetric battery containing the composite protective layer is significantly improved, and the cycle overpotential is significantly lower than that of the common zinc sheet. The composite protective layer has a regulating effect on the growth of zinc dendrites, reduces the generation of 'dead zinc', and greatly improves the problem of ion transmission obstruction caused by surface passivation.

As can be seen from fig. 7, the cycle life, capacity retention rate and associated coulombic efficiency of the zinc cathode full cell containing the composite protective layer are significantly improved. The composite protective layer has a regulating effect on the growth of zinc dendrites, reduces the generation of dead zinc and has a great inhibiting effect on the corrosion of the metal zinc cathode by the electrolyte.

Comparative example 2

The present comparative example provides a negative electrode tab of a zinc secondary battery. The negative pole piece comprises a zinc sheet and a protective layer positioned on the surface of the zinc sheet; the protective layer is a zinc fluoride layer.

The thickness of the protective layer is 2 μm.

The preparation method of the negative pole piece comprises the following steps:

preparing 1 wt% ammonium bifluoride-dimethyl sulfoxide (DMSO) solution, completely soaking the polished zinc foil in the solution for 24h, ultrasonically cleaning and drying the modified zinc foil by using ethanol, and cutting the zinc foil into a wafer with the diameter of 12mm to obtain the negative pole piece of the zinc secondary battery.

Comparative example 3

The present comparative example provides a negative electrode tab of a zinc secondary battery. The negative pole piece comprises a zinc sheet and a protective layer positioned on the surface of the zinc sheet; the protective layer is a copper nanoparticle layer.

The thickness of the protective layer is 2 μm.

preparing 1 wt% copper chloride (CuCl)₂) An aqueous solution. And ultrasonically cleaning and drying the polished zinc foil by using ethanol, and cutting the zinc foil into a wafer with the diameter of 12mm for later use. And uniformly dripping 500 microliters of the copper chloride solution with the concentration on the surface of the zinc foil, washing the surface clean with tertiary water after 5 minutes, and uniformly modifying the surface with a layer of copper nanosheet to obtain the negative pole piece of the zinc secondary battery.

Two same negative electrode plates of the zinc secondary batteries prepared in the examples 1 to 7 and the comparative examples 1 to 3, 2mol/L zinc sulfate electrolyte and a glass fiber diaphragm are assembled into a zinc-zinc symmetrical battery for cycle performance test. The test results are shown in table 1.

A zinc-vanadium pentoxide full cell is assembled by mixing a negative electrode plate of a zinc secondary cell prepared in examples 1-7 and comparative examples 1-3, a commercial vanadium pentoxide, carbon black and an adhesive in a ratio of 8:1:1, mixing the slurry, coating the obtained positive electrode plate on an aluminum foil, 2mol/L zinc sulfate electrolyte and a glass fiber diaphragm, and testing. The test comprises the full-battery charging and discharging test and the corresponding coulombic efficiency.

And (3) testing the cycle performance: adopting a Xinwei battery test system to carry out long-time charge-discharge cycle test, wherein the circulating current density is 0.5mA/cm²The amount of zinc metal circulating is controlled to be 0.5mAh/cm²The test temperature was controlled at 25 ℃.

And (3) full-battery charge and discharge test: adopting a Xinwei battery test system to carry out long-time charge-discharge cycle test, wherein the current density of charge and discharge is 10Ag^-1The test temperature was controlled at 25 ℃.

TABLE 1

The dendrite-free cycle time in the table refers to the cycle time without dendrite generation in the cycle process of the negative pole piece.

From the data results of examples 1 and 7, it is known that when the amount of copper fluoride added is too small, the formed protective layer is not dense enough and cannot uniformly cover the surface of the zinc negative electrode, so that the unprotected portion of the surface is likely to act as a dendrite formation site during the cycle, and further the cycle life is shortened and the coulombic efficiency is reduced. The lower the concentration of the copper fluoride solution used, the thinner the texture of the protective layer formed, and the poorer the protective effect. However, when the amount of copper fluoride added is too large, the protective layer having an excessively thick surface may hinder ion transport, resulting in an increase in cyclic overpotential, resulting in a decrease in energy density and power density of the battery.

From the data results of example 1 and comparative example 1, it can be seen that the negative electrode plate is not treated, the comparison of the results is very significant, and the bare zinc plate without the protective layer is subjected to severe dendrite and pitting phenomena when the bare zinc plate is circulated for 40 hours, which causes short circuit of the symmetrical battery, thus proving that the protective layer is necessary to be added.

From the data results of example 1 and comparative examples 2-3, it can be seen that neither the metal nanoparticles alone as a protective layer nor the metal fluoride alone as a protective layer, wherein the addition of the metal fluoride alone as a protective layer, only partially prevents corrosion, but due to the absence of the controlled nucleating agent, severe dendrite and pitting effects are generated, resulting in failure of the battery. In addition, metal nanoparticles are independently added to serve as a protective layer, so that effects of regulating zinc ion deposition and inhibiting dendritic crystals can be achieved, but corrosion of electrolyte on the surface of a zinc cathode cannot be prevented (even corrosion is more serious due to the existence of another metal), so that when the battery is circulated for more than 500 hours, serious side reaction can occur on the surface, accumulation of a surface passivation layer is caused, ion transmission is difficult, circulating overpotential is gradually increased, and when the overpotential exceeds a certain range, the surface of an electrode becomes extremely unstable, short circuit is gradually caused, and failure of protection is caused.

The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims

1. The negative pole piece of the zinc secondary battery is characterized by comprising a substrate containing zinc metal and a composite protective layer positioned on the surface of the substrate; the composite protective layer comprises metal nanoparticles and zinc fluoride; the thickness of the composite protective layer is 1-5 mu m; the metal nanoparticles comprise any one of copper, silver, indium or aluminum or a combination of at least two thereof.

2. The negative electrode plate as claimed in claim 1, wherein the thickness of the composite protective layer is 1.5-2.5 μm.

3. The negative electrode sheet of claim 1, wherein the zinc-containing metal comprises zinc flakes and/or zinc powder.

4. The method for preparing the negative electrode plate of the zinc secondary battery according to any one of claims 1 to 3, wherein the method for preparing the negative electrode plate comprises the following steps:

5. The method for producing a ceramic tile according to claim 4, wherein the metal fluoride includes any one of copper fluoride, silver fluoride, indium fluoride, or aluminum fluoride, or a combination of at least two thereof.

6. The method according to claim 4, wherein the metal fluoride in the metal fluoride solution is added in an amount of 0.5 to 5 wt% based on the solvent in the metal fluoride solution.

7. The method according to claim 5, wherein the metal fluoride in the metal fluoride solution is added in an amount of 1 to 2 wt% based on the solvent in the metal fluoride solution.

8. The method according to claim 4, wherein the solvent in the metal fluoride solution comprises any one or a combination of at least two of anhydrous ethanol, anhydrous methanol, N' N dimethylformamide, and tetrahydrofuran.

9. The preparation method of claim 4, wherein the standing time is 12-48 h.

10. The method according to claim 4, wherein the standing is followed by ultrasonic cleaning and then drying.

11. The method of manufacturing according to claim 4, comprising:

12. A zinc secondary battery, characterized in that the zinc secondary battery comprises a positive electrode sheet, a negative electrode sheet of the zinc secondary battery according to any one of claims 1 to 3, a separator and an electrolyte; wherein the diaphragm is positioned between the positive pole piece and the negative pole piece.

13. The zinc secondary battery of claim 12, wherein the positive electrode tab comprises a titanium foil current collector and a positive electrode membrane.

14. The zinc secondary battery according to claim 13, wherein the positive electrode membrane includes a positive electrode active material, a conductive agent, and a binder.

15. The zinc secondary battery according to claim 14, wherein the positive electrode active material includes manganese dioxide and/or vanadium pentoxide.

16. The zinc secondary battery of claim 12, wherein the separator comprises any one of glass fiber, cellulose, or polyvinylidene fluoride, or a combination of at least two thereof.

17. The zinc secondary battery of claim 12, wherein the electrolyte comprises any one of or a combination of at least two of zinc bis (trifluoromethylsulfonyl) imide, zinc sulfate, or zinc triflate.