A method for manufacturing a zincophilic symmetrically wound battery

Abstract

This invention relates to the field of electrochemical energy technology and discloses a method for manufacturing a zinc-loving wound symmetrical battery, comprising the following steps: mixing a negative electrode active material, zinc-loving additives, auxiliaries, dispersants, binders, and deionized water to prepare a negative electrode slurry; coating the negative electrode slurry onto a current collector; drying, rolling, and cutting to obtain a pre-fabricated negative electrode sheet; coating the binder onto the surface of a water-retaining membrane; and then laminating hydrophilically treated side membranes onto both sides of the water-retaining membrane; drying and cutting to obtain a pre-fabricated sandwich membrane. This method for manufacturing a zinc-loving wound symmetrical battery uses a winding process to prepare a symmetrical battery, accurately simulating the actual winding charge-discharge environment of commercial nickel-zinc batteries. It solves the problem of the disconnect between the test results of traditional beaker-type symmetrical batteries and practical applications. The polarization phenomenon caused by the negative electrode can be directly observed through the battery charge-discharge curve, providing a practical test carrier for negative electrode modification research.

Description

Technical Field

[0001] This invention relates to the field of electrochemical energy technology, specifically to a method for manufacturing a zinc-loving wound symmetrical battery. Background Technology

[0002] Nickel-zinc batteries, with their advantages of high specific capacity, environmental friendliness, readily available raw materials, and low cost, have become a highly promising rechargeable battery system in the fields of energy storage and portable power supplies, attracting significant attention in application exploration in consumer electronics, new energy storage, and other scenarios. As a core component of nickel-zinc batteries, the deposition and stripping behavior of the zinc anode during charging and discharging directly determines the battery's cycle life, safety, and electrochemical performance. Therefore, research on the modification and performance testing of the zinc anode has become a crucial aspect of nickel-zinc battery technology development.

[0003] In the research of zinc anode modification, symmetrical batteries have become an important testing platform for evaluating the zinc affinity and cycle stability of zinc anodes because they can eliminate interference from the positive electrode system and accurately focus on the performance of the anode. However, the current industry mainly relies on beaker-type symmetrical batteries for testing the performance of zinc anodes. This testing system is an open, unsealed structure, which differs significantly from the actual wound-type sealed charge and discharge environment of commercial nickel-zinc batteries. The ion transport, electrode interface reaction, and electrolyte distribution during the testing process cannot simulate the actual application scenario. As a result, the data on anode polarization, cycle life, etc. obtained from the test are seriously out of sync with the actual working performance of the battery, making it difficult to use as an effective reference for anode modification research. This greatly restricts the R&D efficiency and practical transformation value of zinc anode modification technology. Summary of the Invention

[0004] (a) Technical problems to be solved To address the shortcomings of existing technologies, this invention provides a method for manufacturing a zinc-loving wound symmetrical battery, which solves the problems of existing traditional testing systems being open and unsealed structures, disconnected from practical applications, and having low reference value for test results.

[0005] (II) Technical Solution To achieve the above objectives, the present invention provides the following technical solution: a method for manufacturing a zinc-loving wound symmetrical battery, comprising the following steps: S1: Preparation of negative electrode sheet: The negative electrode active material, zinc-loving additive, auxiliary agent, dispersant, binder and deionized water are mixed to prepare negative electrode slurry. The negative electrode slurry is coated on the current collector, and after drying, rolling and cutting, a pre-made negative electrode sheet is obtained. S2: Preparation of sandwich membrane: The adhesive is coated on the surface of the water-retaining membrane, and then the hydrophilic side membranes are laminated on both sides of the water-retaining membrane. After drying and cutting, the prefabricated sandwich membrane is obtained. S3: Winded battery assembly: Pre-formed positive electrode sheet, pre-formed sandwich separator and pre-formed negative electrode sheet with the same formula as the pre-formed negative electrode sheet are stacked in sequence, and the cell is made by winding process. After injecting electrolyte into the cell, it is sealed to obtain zinc-loving wound symmetrical battery.

[0006] Preferably, the negative electrode active material in S1 is zinc oxide, the zinc-loving additive is graphene, and the mass ratio of the zinc-loving additive to the negative electrode active material is 80:(0.5-3).

[0007] Preferably, the additives in S1 include Bi2O3, In2O3, Al2O3 and KF, the current collector is a tin-plated copper mesh, and the binder is polyvinyl alcohol.

[0008] Preferably, the negative electrode slurry in S1 is prepared by mixing the raw materials at high speed until they are uniform, the drying temperature is 80-120℃, the electrode sheet surface density is uniform after rolling, and the cutting size is compatible with the battery assembly specifications.

[0009] Preferably, the binder in S2 is 0.5% polyvinyl alcohol by mass, the drying temperature is 60-90°C, and the size of the cut interlayer diaphragm matches the pre-fabricated negative electrode sheet.

[0010] Preferably, the hydrophilic treatment in S2 is plasma hydrophilic treatment, which improves the hydrophilicity of the polypropylene membrane and makes it suitable for the strong alkaline aqueous electrolyte system of nickel-zinc batteries.

[0011] Preferably, the preparation process of the pre-formed positive electrode sheet in S3 is completely consistent with the preparation process of the pre-formed negative electrode sheet, which is obtained by slurry preparation, coating, drying, rolling and cutting.

[0012] Preferably, the preparation process of the pre-fabricated positive electrode sheet in S3 is completely consistent with the preparation process of the pre-fabricated negative electrode sheet, which is obtained by slurry preparation, coating, drying, rolling and cutting; the winding process is constant tension winding, and the cell has no interlayer displacement and no edge folds after winding; the electrolyte is a strong alkaline zinc-based aqueous electrolyte; and the sealing is vacuum sealing treatment. Preferably, the electrolyte in step S3 is a strong-alkali zinc-based aqueous electrolyte, specifically a mixed electrolyte of KOH and Zn(OH)2, wherein the molar concentration of KOH is 6-8 mol / L, the amount of Zn(OH)2 added is 0.2-0.5 mol / L, and the ratio of electrolyte injection volume to cell volume is 1.2-1.5:1, ensuring that the cell is fully wetted and there is no excessive electrolyte overflow; the sealing is a vacuum sealing process.

[0013] (III) Beneficial Effects Compared with the prior art, the present invention provides a method for manufacturing a zinc-coil-type symmetrical battery, which has the following beneficial effects: 1. The method for fabricating this zinc-loving wound symmetrical battery uses a winding process to prepare the symmetrical battery, which accurately simulates the actual winding charge and discharge environment of commercial nickel-zinc batteries. It solves the problem of the disconnect between the test results of traditional beaker-type symmetrical batteries and practical applications. The polarization phenomenon caused by the negative electrode can be directly observed through the battery charge and discharge curve, providing a practical test carrier for negative electrode modification research.

[0014] 2. The fabrication method of this zinc-loving wound symmetrical battery adopts a symmetrical structure design with the same formula for both positive and negative electrodes, which completely eliminates the interference of sub-nickel electrode polarization and high-voltage hydrogen evolution in nickel-zinc full batteries. It allows for direct observation of the deposition and peeling morphology of the pure zinc negative electrode during charge and discharge, accurately explores the zinc-loving characteristics of the negative electrode material and the powder shedding during charge and discharge, and can directly reflect the cycle life of the negative electrode, providing clear negative electrode-level evidence for nickel-zinc battery fault analysis.

[0015] 3. The method for fabricating this zinc-loving wound symmetrical battery involves adding graphene zinc-loving additives to the negative electrode. These additives compete with the separator for zinc deposition sites, inducing zinc to preferentially and uniformly deposit on the negative electrode surface. This eliminates the problem of zinc depositing on the separator and forming dendrites for short circuits, significantly improving the battery's cycle life. At the same time, the precise ratio of the additives to the negative electrode active material ensures uniform zinc deposition while also maintaining the electrode's conductivity and reducing electrode polarization.

[0016] 4. The fabrication method of this zinc-loving wound symmetrical battery involves designing a sandwich structure membrane consisting of a positive and negative electrode side separator and a water-retaining separator. The water-retaining separator increases the electrolyte retention, ensuring ion transport during electrode charging and discharging. The side separator, after plasma hydrophilic treatment, is compatible with strongly alkaline aqueous electrolytes, and the sandwich structure further blocks zinc dendrite penetration. Combined with the effect of zinc-loving additives, this achieves long-term stable cycling of the battery. At the same time, the binder and process parameters for separator preparation are optimized to ensure the structural stability and adhesion of the sandwich separator.

[0017] 5. The manufacturing method of this zinc-loving wound symmetrical battery precisely limits the electrolyte composition, concentration, and injection amount, adapting to the electrochemical reaction requirements of the strong alkaline system of nickel-zinc batteries. It ensures that the cell is fully wetted while avoiding excessive electrolyte overflow, reducing side reactions during charging and discharging. The constant tension winding and vacuum sealing process design ensures the regularity of the cell structure, avoiding battery failure caused by interlayer misalignment, edge folding, and poor sealing, further improving the stability and accuracy of battery testing. Attached Figure Description

[0018] Figure 1 The charge-discharge cycle curves of the symmetrical batteries prepared in Example 1 and Comparative Example 1 of this invention at a current of 1C are shown. Figure 2The surface morphology of the positive and negative electrodes and the separator of the symmetrical batteries prepared in Example 1, Comparative Example 1 and Comparative Example 2 of the present invention after 100h of charge-discharge cycle at a current of 1C is shown in (a) for the negative electrode and separator of Comparative Example 1, (b) for the negative electrode and separator of Example 1, (c) for the positive electrode of Comparative Example 1, and (d) for the positive electrode of Example 1. Figure 3 Performance test tables for Examples 1 to 3; Figure 4 Performance test tables for Examples 4 to 8 and Comparative Examples 1 to 4. Detailed Implementation

[0019] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0020] Example 1 Please see Figure 1 - Figure 2 As shown, one embodiment of the present invention provides a method for manufacturing a zinc-loving wound symmetrical battery, comprising the following steps: S1: Preparation of negative electrode sheet: The negative electrode active material, zinc-loving additive, auxiliary agent, dispersant, binder and deionized water are stirred at high speed until uniform to obtain a negative electrode slurry; the negative electrode slurry is uniformly coated on the surface of tin-plated copper mesh current collector, dried in an environment of 80-120℃, and rolled to ensure uniform electrode surface density. Finally, it is cut into sheets according to battery assembly specifications to obtain pre-fabricated negative electrode sheets. The negative electrode active material is selected from one or more of ZnO / C, ZnO, and Zn powder, preferably ZnO; the zinc-loving additive is selected from one of graphene, g-C3N4, and boron nitride, preferably graphene, and the mass ratio of zinc-loving additive to negative electrode active material is 80:(0.5-3); the auxiliary agent includes Bi2O3, In2O3, Al2O3 and KF, and the binder is preferably polyvinyl alcohol; S2: Prepare a sandwich diaphragm by uniformly coating the surface of the water-retaining diaphragm with an adhesive of 0.5% by mass. The adhesive is selected from polyvinyl alcohol, 502, styrene-butadiene rubber, and potassium polyacrylate, preferably polyvinyl alcohol. After the side diaphragm is subjected to plasma hydrophilic treatment, it is laminated to both sides of the water-retaining diaphragm to form a sandwich structure. It is dried in an environment of 60-90℃ and cut to a size that matches the pre-made negative electrode sheet to obtain a pre-made sandwich diaphragm. The side diaphragm is selected from polypropylene membrane, polytetrafluoroethylene membrane, and hydrophilic PVDF membrane, preferably hydrophilic treated polypropylene membrane. The water-retaining diaphragm is selected from glass fiber membrane, vinylon, and non-woven fabric, preferably vinylon membrane. S3: The battery is assembled by winding. A pre-formulated positive electrode with the same formula is prepared according to the same process as the pre-formulated negative electrode. The pre-formulated positive electrode, pre-formed sandwich separator, and pre-formulated negative electrode are stacked in sequence and the cell is prepared by constant tension winding process to ensure that the cell has no interlayer displacement and no edge folding. A strong alkaline zinc-based aqueous electrolyte is injected into the cell. The ratio of electrolyte injection volume to cell volume is 1.2~1.5:1. Finally, the cell is vacuum sealed to obtain a zinc-loving wound symmetrical battery. The strong alkaline zinc-based aqueous electrolyte is a mixed electrolyte of KOH and Zn(OH)2. The molar concentration of KOH is 6~8 mol / L and the amount of Zn(OH)2 added is 0.2~0.5 mol / L to ensure that the cell is fully wetted and there is no excessive electrolyte overflow. Preparation of negative electrode sheet: 62 parts ZnO, 6.7 parts Zn, 1.7 parts Bi2O3, 0.03 parts In2O3, 2.9 parts Al2O3, 0.14 parts KF, 0.15 parts dispersant, 4.4 parts binder, 2 parts graphene, and 19.98 parts deionized water are mixed evenly to obtain a negative electrode slurry; the negative electrode slurry is evenly coated on a tin-plated copper mesh, dried, and rolled to obtain a pre-fabricated negative electrode. Preparation of separator: 0.5% polyvinyl alcohol is used as a binder and coated on a vinylon membrane. Then, a hydrophilic polypropylene membrane is laminated on both sides of the vinylon membrane to form a sandwich structure. After drying and cutting, a pre-fabricated separator is obtained.

[0021] Example 2 Example 2 and Example 1 follow most of the same steps, except that the two parts graphene in the negative electrode preparation are replaced with two parts acetylene black. Acetylene black has good conductivity and can build a conductive network in the negative electrode, improving electron transport efficiency and reducing the charge transfer resistance of the electrode to some extent. However, acetylene black lacks zinc affinity and cannot compete with the separator for zinc deposition sites, thus failing to induce zinc ions to preferentially and uniformly deposit on the surface of the negative electrode. The resulting battery had an overpotential of 0.46V and a cycle time of 730h. After cycling, disassembly revealed a large area of ​​exposed tin-plated copper mesh on the electrode, indicating uneven zinc deposition.

[0022] Example 3 Most of the steps in Example 3 are the same as those in Example 1, except that the two parts of graphene in the negative electrode preparation are replaced with two parts of Ketjen black. Ketjen black has an extremely high specific surface area and excellent conductivity, which can effectively improve the electron conduction rate inside the electrode and reduce the battery overpotential to 0.39V, showing a good conductivity modification effect. However, Ketjen black does not have zinc affinity and has no inducing effect on zinc ion deposition. During charging and discharging, zinc ions are prone to disordered deposition in the separator and local areas of the electrode, resulting in the shedding of active material from the electrode and exposure of the current collector. The battery cycle time is only 680h, and the zinc deposition state is uneven.

[0023] Example 4 Most of the steps in Example 4 are the same as those in Example 1, except that the two parts of graphene in the preparation of the negative electrode are replaced with two parts of carbon nanotubes. Carbon nanotubes are one-dimensional nano-conductive materials that can form continuous conductive pathways in the negative electrode slurry, greatly improving the electron transport efficiency of the electrode and reducing the battery overpotential to as low as 0.38V, with a significant conductive modification effect. However, carbon nanotubes do not have zinc affinity and cannot guide zinc ions to be uniformly deposited on the surface of the negative electrode. During charge-discharge cycles, zinc dendrites are prone to grow and pierce the separator. The battery cycle time is 710 hours. After disassembly, it was observed that a large area of ​​the current collector on the electrode was exposed and the zinc deposition was uneven.

[0024] Example 5 Example 5 and Example 1 follow most of the same steps, except that the two parts of graphene in the negative electrode preparation are replaced with two parts of zinc-loving TiO2. TiO2 has good zinc-loving properties and can compete with the separator for zinc deposition sites, inducing zinc ions to preferentially and uniformly deposit on the surface of the negative electrode. After cycling for 50 hours, the battery was disassembled and no large area of ​​exposed current collector was observed. The zinc deposition state was uniform, effectively avoiding the growth of zinc dendrites on the separator. However, TiO2 is a semiconductor material with poor conductivity, which will increase the polarization of the electrode, causing the battery overpotential to rise to 0.47V, increasing energy loss during charging and discharging. The battery cycle time was 815 hours.

[0025] Example 6 Most of the steps in Example 6 are the same as in Example 1, except that the two parts of graphene in the negative electrode preparation are replaced with two parts of zinc-loving talc. Talc has zinc-loving properties, which can effectively induce zinc ions to be uniformly deposited on the surface of the negative electrode and prevent zinc dendrites from growing on the separator. After cycling for 50 hours, the battery was disassembled and no large area of ​​current collector was exposed on the electrode, and the zinc deposition state was uniform. However, talc is an insulating material with extremely poor conductivity, which will significantly increase the polarization effect of the electrode, causing the battery overpotential to reach 0.49V. Energy loss is serious during charging and discharging, and the battery cycle time is 780 hours.

[0026] Example 7 Most of the steps in Example 7 are the same as in Example 1, except that the two parts of graphene in the negative electrode preparation are replaced with two parts of zinc-repellent barium titanate. Barium titanate is a zinc-repellent material, which will repel the deposition of zinc ions on the surface of the negative electrode, forcing zinc ions to migrate to the separator area and grow disorderly. At the same time, barium titanate has poor conductivity. These two factors lead to a significant increase in electrode polarization, and the battery overpotential rises to 0.63V. During charge and discharge cycles, zinc dendrites grow rapidly on the separator and pierce the separator, causing micro-short circuits inside the battery. The battery cycle time is only 600h. After disassembly, it was found that a large area of ​​the current collector on the electrode was exposed, and the zinc deposition state was uneven.

[0027] Example 8 Most of the steps in Example 8 are the same as in Example 1, except that the two parts of graphene in the negative electrode preparation are replaced with two parts of antimony dioxide, which repels zinc. Antimony dioxide is a typical zinc-repellent material, which strongly repels the deposition of zinc ions on the surface of the negative electrode, resulting in a large amount of zinc ions deposited on the surface of the separator. At the same time, antimony dioxide has poor conductivity, which further aggravates the polarization effect of the electrode, and the battery overpotential is as high as 0.58V. During the charge and discharge cycle, zinc dendrites on the separator grow rapidly and pierce the separator in a short time, causing the battery to short-circuit. The battery cycle time is only 420h, which is the shortest among all examples. After disassembly, a large area of ​​the current collector of the electrode is exposed, and the zinc deposition state is uneven.

[0028] Comparative Example 1 Comparative Example 1 and Example 1 share most of the same steps, except that the two parts of additives in the negative electrode preparation are replaced with two parts of deionized water. The negative electrode has no functional additives and is composed solely of basic active materials. The internal conductive network of the electrode is generally normal, and there are no zinc-loving sites to induce zinc deposition. The battery overpotential is 0.38V. However, during the charge and discharge process, zinc ions are randomly deposited and stripped on the surface of the negative electrode, the active materials are easily detached, the current collector is exposed over a large area, the zinc deposition is uneven, zinc dendrites grow rapidly and pierce the separator, and the battery short-circuit after 700 hours. The cycle life is much lower than that of Example 1.

[0029] Comparative Example 2 Comparative Example 2 and Example 1 follow most of the same steps, except that the vinylon separator is only composited with a hydrophilic polypropylene membrane on one side. The single-sided composite separator structure disrupts the symmetrical ion transport environment between the electrode and the separator. The fibers of the vinylon separator easily intertwine with the deposited zinc ions, causing a severe polarization effect. The battery overpotential rises sharply to 4V, far exceeding the hydrogen evolution potential of the electrolyte. The battery heats up severely during charging and discharging. High temperature causes the polypropylene separator to fail rapidly and cannot isolate the positive and negative electrodes. The battery cycle time is only 20 hours. After disassembly, it was observed that a large area of ​​the current collector on the electrode was exposed and the zinc deposition was uneven.

[0030] Comparative Example 3 Comparative Example 3 and Example 1 followed most of the same steps, except that the hydrophilic polypropylene membrane was replaced with a hydrophilic PVDF membrane. The hydrophilic PVDF membrane has certain hydrophilicity and ion transport capabilities, which can induce zinc ions to be uniformly deposited on the surface of the negative electrode. After 50 hours of cycling, the battery was disassembled, and there was no large area of ​​exposed current collector on the electrode, and the zinc deposition was uniform. However, the stability of PVDF material in the strong alkaline electrolyte system of nickel-zinc batteries is extremely poor. During charge-discharge cycles, the PVDF membrane will gradually hydrolyze and degrade, and the structural integrity and ion transport performance of the membrane will rapidly decline, resulting in a gradual increase in electrode polarization. The battery overpotential is 0.6V, and the battery cannot work normally after the membrane fails, with a cycle time of only 130 hours.

[0031] Comparative Example 4 Comparative Example 4 and Example 1 follow most of the same steps, except that the hydrophilic polypropylene membrane of the composite separator is replaced with a hydrophobic polyimide membrane.

[0032] Battery testing methods: (1) Cycle duration: The symmetrical battery assembled is charged and discharged for 1 hour each under 1C conditions as one cycle, and the cycle duration is recorded.

[0033] (2) Overpotential is the voltage difference between the battery voltage after 1 hour of charging / discharging and the voltage at 0 point, which is directly proportional to the battery polarization.

[0034] (3) Whether the deposit is uniform: After the battery has been cycled for 50 hours, disassemble and observe whether there is a large area of ​​exposed tin-plated copper mesh on the electrode.

[0035] The above-described embodiments and comparative examples were subjected to charge-discharge cycle tests, and the Zn deposition morphology was observed after disassembly of the batteries following the cycles. The results are as follows: Figure 2 - Figure 4 As shown: Of Examples 1-8, Example 1 has the best overall performance because graphene not only provides excellent conductivity, but also has zinc affinity, which induces zinc to be deposited preferentially on the electrode, thus avoiding battery short circuits caused by uneven deposition.

[0036] Although Examples 2-4 provide excellent conductivity, the materials themselves do not have zinc affinity, so zinc cannot be deposited uniformly, resulting in the inability to effectively improve cycle performance.

[0037] Although Examples 5-6 provide zinc-loving additives, the conductivity decreases, leading to increased electrode polarization during charging and discharging, which causes severe energy loss during battery charging and reduces charging efficiency.

[0038] Examples 7-8 used zinc-repellent additives, which resulted in more severe polarization and made it easier for zinc to deposit on the diaphragm, leading to a significant reduction in cycle life.

[0039] Comparative Example 2 features a two-layer separator design, with one side being a vinylon separator. This causes the fibers to intertwine with the deposited zinc, resulting in a severe polarization effect, a sharp increase in overpotential, and severe battery heating, which leads to the failure of the polypropylene separator due to high temperature.

[0040] Comparative Example 3 uses a sandwich hydrophilic PVDF membrane, but because PVDF is unstable in a strongly alkaline environment, the PVDF membrane gradually fails as the cycle time increases, causing the battery to malfunction.

[0041] Comparative Example 4 uses a hydrophobic polyimide separator, which is easily degraded in a strongly alkaline environment. The battery has high polarization, and the battery heats up during cycling, which accelerates its degradation and leads to its failure.

[0042] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or / or apparatus that includes the element.

Claims

1. A method for manufacturing a zinc-loving wound symmetrical battery, characterized in that, Includes the following steps: S1: Preparation of negative electrode sheet: The negative electrode active material, zinc-loving additive, auxiliary agent, dispersant, binder and deionized water are mixed to prepare negative electrode slurry. The negative electrode slurry is coated on the current collector, and after drying, rolling and cutting, a pre-made negative electrode sheet is obtained. S2: Preparation of sandwich membrane: The adhesive is coated on the surface of the water-retaining membrane, and then the hydrophilic side membranes are laminated on both sides of the water-retaining membrane. After drying and cutting, the prefabricated sandwich membrane is obtained. S3: Winded battery assembly: Pre-formed positive electrode sheet, pre-formed sandwich separator and pre-formed negative electrode sheet with the same formula as the pre-formed negative electrode sheet are stacked in sequence, and the cell is made by winding process. After injecting electrolyte into the cell, it is sealed to obtain zinc-loving wound symmetrical battery.

2. The method for manufacturing a zinc-loving wound symmetrical battery according to claim 1, characterized in that: The negative electrode active material in S1 is zinc oxide, the zinc-loving additive is graphene, and the mass ratio of the zinc-loving additive to the negative electrode active material is 80:(0.5-3).

3. The method for manufacturing a zinc-loving wound symmetrical battery according to claim 1, characterized in that: The additives in S1 include Bi2O3, In2O3, Al2O3 and KF, the current collector is a tin-plated copper mesh, and the binder is polyvinyl alcohol.

4. The method for manufacturing a zinc-loving wound symmetrical battery according to claim 1, characterized in that: The negative electrode slurry mentioned in S1 is prepared by mixing the raw materials at high speed until they are uniform. The drying temperature is 80-120℃. After rolling, the electrode sheet has uniform surface density and the cutting size is compatible with the battery assembly specifications.

5. The method for manufacturing a zinc-loving wound symmetrical battery according to claim 1, characterized in that: The binder in S2 is 0.5% polyvinyl alcohol by mass, the drying temperature is 60-90℃, and the size of the cut interlayer diaphragm matches the pre-fabricated negative electrode sheet.

6. The method for manufacturing a zinc-loving wound symmetrical battery according to claim 1, characterized in that: The hydrophilic treatment described in S2 is plasma hydrophilic treatment, which improves the hydrophilicity of the polypropylene membrane, making it suitable for the strong alkaline aqueous electrolyte system of nickel-zinc batteries.

7. The method for manufacturing a zinc-loving wound symmetrical battery according to claim 1, characterized in that: The preparation process of the pre-formed positive electrode sheet described in S3 is completely consistent with the preparation process of the pre-formed negative electrode sheet, which is obtained by slurry preparation, coating, drying, rolling and cutting.

8. The method for manufacturing a zinc-loving wound symmetrical battery according to claim 1, characterized in that: The winding process described in S3 is constant tension winding, and the battery cell has no interlayer offset or edge folds after winding; the electrolyte is a strong alkaline zinc-based aqueous electrolyte, and the sealing is a vacuum sealing process.

9. The method for manufacturing a zinc-loving wound symmetrical battery according to claim 1, characterized in that: The strong alkaline zinc-based aqueous electrolyte in S3 is a mixed electrolyte of KOH and Zn(OH)2, wherein the molar concentration of KOH is 6-8 mol / L, the amount of Zn(OH)2 added is 0.2-0.5 mol / L, and the ratio of electrolyte injection volume to cell volume is 1.2-1.5:1, ensuring that the cell is fully wetted and that there is no excessive electrolyte overflow.

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