Zinc powder negative electrode for aqueous zinc ion battery

Abstract

The invention discloses a zinc powder negative electrode for an aqueous zinc ion battery, which is characterized in that a metal zinc powder negative electrode is used as a substrate, and at least one of a polyacrylic resin side chain grafted organic silicon group or organic fluorine group and a polyurethane resin side chain grafted organic silicon group or organic fluorine group is constructed on the surface of the zinc powder negative electrode. And a thin and uniform polymer protective coating is formed. Compared with the prior art, the thickness of the prepared zinc powder negative electrode protective coating is only 0.1-2 microns, the coating can reduce the contact between the zinc powder negative electrode and electrolyte, and the surface of the zinc powder is protected from being corroded by water; meanwhile, a macromolecular chain structure and functional groups of the coating endow the coating with good flexibility, hydrophobicity and compactness, so that the coating has very high elasticity and mechanical strength; after the polymer protective coating is constructed on the surface of the zinc powder negative electrode, a relatively good protection effect on structure collapse caused by deintercalation of zinc powder can be achieved, and meanwhile, an effect of uniformizing an electric field can be achieved.

Description

Technical Field

[0001] The present invention belongs to the technical field of new energy materials, and particularly relates to a zinc powder negative electrode for aqueous zinc ion batteries. Background Art

[0002] Aqueous zinc ion batteries have received extensive attention due to their characteristics of low cost, high safety, and high capacity; in addition, the metal zinc negative electrode has advantages such as a high theoretical specific capacity (820 mAh / g) and a low redox potential (-0.762 V, relative to the standard hydrogen electrode), etc., and has become one of the focuses of attention in the field of new secondary batteries at present, and is considered to be the most promising electrochemical energy storage device in the future.

[0003] However, similar to the metal lithium negative electrode, the metal zinc negative electrode of aqueous zinc ion batteries also has problems such as dendrites, hydrogen evolution, and corrosion. When these problems are serious, they will affect the deposition and dissolution efficiency and stability of the metal zinc negative electrode, thereby causing the overall performance of aqueous zinc batteries to decline.

[0004] Currently, the protection strategies for metal zinc negative electrodes mainly include zinc negative electrode interface modification, three-dimensional electrode structure design, and electrolyte optimization. These methods can significantly improve the reversibility and stability of metal zinc negative electrodes; currently, the main zinc negative electrodes are zinc foil negative electrodes and zinc powder negative electrodes. Compared with zinc foil negative electrodes, zinc powder negative electrodes can be fully wetted with the electrolyte, have higher electrochemical activity and higher capacity, and are the trend of the industrialization of negative electrode materials for future aqueous zinc ion batteries; however, during the charge and discharge process of zinc powder negative electrodes, there are problems such as the collapse of zinc powder particle structures due to deintercalation.

[0005] In view of this, the present invention aims to provide a zinc powder negative electrode for aqueous zinc ion batteries. After introducing a micron-level polymer ultra-thin coating on the surface of the zinc powder negative electrode through interface modification, it can effectively prevent the collapse of zinc powder particle structures, and can also maximize the high electrochemical activity of zinc powder; the silicon hydroxyl group (Si-OH) in the organosilicon group grafted on the side chain of polyacrylic resin or polyurethane can form a strong Si-O-M bond with the metal substrate, which can enhance the adhesion and hydrophobicity of the coating. After grafting organic fluorine groups on polyacrylic resin or polyurethane, the flexibility and corrosion resistance of the coating can be improved. At the same time, the insulating property of the polymer coating enables zinc ions to be reduced and deposited under the coating, thereby more effectively improving the utilization rate of the negative electrode, prolonging the cycle life, and improving the performance. Summary of the Invention

[0006] Aiming at the deficiencies of the prior art, a zinc powder negative electrode for aqueous zinc ion batteries is provided, which can solve the problem that the collapse of zinc powder particle structures during the charge and discharge process of zinc powder negative electrodes limits the stability of zinc powder negative electrodes during long-term cycling.

[0007] To solve the above problems, the technical solution of the present invention is as follows:

[0008] A zinc powder negative electrode for an aqueous zinc-ion battery, comprising a zinc negative electrode prepared from metallic zinc powder and a protective coating provided on the surface of the zinc negative electrode, wherein the protective coating comprises at least one of a polyacrylic resin side chain grafted with an organosilicon group or an organofluorine group, and a polyurethane resin side chain grafted with an organosilicon group or an organofluorine group.

[0009] As an improvement to the zinc powder negative electrode for an aqueous zinc-ion battery of the present invention, its preparation method at least includes the following steps:

[0010] S1. Add at least one solution of a polyacrylic resin side chain grafted with an organosilicon group or an organofluorine group, and a polyurethane resin side chain grafted with an organosilicon group or an organofluorine group synthesized in the laboratory to deionized water and dilute evenly to obtain a slurry;

[0011] S2. Pre-bake the zinc powder negative electrode in an oven;

[0012] S3. Build the slurry obtained in step S1 onto the surface of the zinc powder negative electrode, and after drying, obtain a zinc powder negative electrode with a protective coating.

[0013] As an improvement to the zinc powder negative electrode for an aqueous zinc-ion battery of the present invention, the mass fraction of the solute of the slurry obtained in step S1 is 1-80%.

[0014] As an improvement to the zinc powder negative electrode for an aqueous zinc-ion battery of the present invention, in step S2, the pre-baking temperature of the zinc powder negative electrode of the coating substrate is 50-150°C, and the baking time is 0.1-10 min.

[0015] As an improvement to the zinc powder negative electrode for an aqueous zinc-ion battery of the present invention, in step S3, the building methods include spraying, brushing, and roll coating.

[0016] As an improvement to the zinc powder negative electrode for an aqueous zinc-ion battery of the present invention, the drying method in step S3 is air drying or infrared drying, the drying temperature is 80-150°C, the drying time is 0.1-10 min, and the thickness of the zinc negative electrode protective coating is 0.1-2 μm.

[0017] As an improvement to the zinc powder negative electrode for an aqueous zinc-ion battery of the present invention, the organosilicon group is specifically -R n SiX 4-n , where R is an organic group, X is an alkyl group or an aromatic hydrocarbon group, and 1≤n≤3; the organofluorine group is specifically -(CF 2 ) n -CF 3 , where 1≤n≤3. Preferably, the organosilicon group is specifically -O-CH 2 -CH2 -CH 2 -Si(OCH 3 ) 3 ; The organic fluorine group is specifically -O-CH 2 -CH 2 -CF 3 .

[0018] The present invention provides a preparation method for a zinc powder negative electrode protection coating of an aqueous zinc ion battery. By constructing a micron-level polymer ultra-thin coating on the surface of the zinc powder negative electrode, the cycle stability of the zinc powder negative electrode is improved. It can not only prevent the collapse of the zinc powder particle structure, but also maximize the high electrochemically active characteristics of the zinc powder; the insulating property of the polymer coating enables zinc ions to be reduced and deposited under the coating.

[0019] During use, the positive electrode sheet, negative electrode sheet, separator and electrolyte are assembled into a button battery. Of course, the present invention uses the prepared protection coating to modify the zinc powder negative electrode. The rechargeable aqueous zinc ion battery can be made into not only button type, but also column type, sheet type and soft package and other structures.

[0020] In summary, due to the adoption of the above technical solutions, the beneficial effects of the present invention are:

[0021] 1. In the present invention, the surface of the zinc powder negative electrode of the aqueous zinc ion battery is covered with a polymer protection coating that has both a relatively high tensile strength and elastic modulus and a hydrophobic desolvation function. The elastic modulus of the polymer coating in the present invention is between 0.1 - 4.0 GPa, and the elastic elongation rate is between 50% - 400%. This enables the coating to effectively prevent the structural collapse of the zinc powder particles during charge and discharge, and can maximize the high electrochemically active characteristics of the zinc powder; the side-chain grafted organosilicon group can improve the hydrophobicity of the coating, and has a certain desolvation effect. At the same time, the insulating property of the polymer coating enables zinc ions to be reduced and deposited under the coating, thereby extending the cycle life of the aqueous zinc ion battery.

[0022] 2. In the present invention, the preparation process of the polymer negative electrode protection coating is simple, fast, environmentally friendly, and low in cost, which is convenient for developing high-performance zinc ion batteries.

[0023] 3. After introducing a micron-level polymer ultra-thin coating on the surface of the zinc powder anode through interface modification, the collapse of the zinc powder particle structure can be effectively prevented, and the high electrochemical activity of the zinc powder can be maximally exerted. The silicon hydroxyl group (Si-OH) in the organosilicon group grafted on the side chain of polyacrylic resin or polyurethane can form a strong Si-O-M bond with the metal substrate, which can enhance the adhesion and hydrophobicity of the coating. After grafting the organofluoro group on the side chain of polyacrylic resin or polyurethane, the flexibility and corrosion resistance of the coating can be improved. At the same time, the insulating property of the polymer coating enables zinc ions to be reduced and deposited under the coating, thereby more effectively improving the anode utilization rate, extending the cycle life, and enhancing the performance.

[0024] 4. The thickness of the zinc powder anode protection coating prepared by the present invention is only 0.1 - 2 μm. This coating can reduce the contact between the zinc powder anode and the electrolyte and protect the surface of the zinc powder from being corroded by water. At the same time, the polymer chain structure and functional groups of the coating endow the coating with good flexibility, hydrophobicity, and compactness, making the coating have high elasticity and mechanical strength. After constructing this polymer protection coating on the surface of the zinc powder anode, it can have a good protective effect on the structural collapse caused by the insertion and extraction of zinc ions, and at the same time can play a role in uniforming the electric field. In addition, the insulating property of the coating can prevent zinc ions from depositing outside the coating, ensure that zinc ions are reduced under the coating, and reduce the formation of dendrites. These three protective effects can greatly improve the cycle performance of the aqueous zinc-ion battery.

[0025] 5. In the prior art, the anode coatings of aqueous zinc-ion batteries are all for the protection of the zinc foil anode system. This application is for the protection of the zinc powder anode system with more industrialization value, which has more practical application value. In addition, the materials used in this technology have low cost and can be prepared on a large scale. Description of the Drawings

[0026] Figure 1a The physical diagram of the zinc powder anode prepared in the comparative example of the present invention;

[0027] Figure 1b The physical diagram of the cut zinc powder anode prepared in the comparative example of the present invention;

[0028] Figure 1c The physical diagram of the optically magnified zinc powder anode prepared in the comparative example of the present invention;

[0029] Figure 2a The physical diagram of the zinc powder anode prepared with the protective layer in Example 1 of the present invention;

[0030] Figure 2b The physical diagram of the cut zinc powder anode prepared with the protective layer in Example 1 of the present invention;

[0031] Figure 2cPhotomicrograph of the zinc powder anode with the protective layer prepared in Example 1 of the present invention after optical magnification;

[0032] Figure 3a Photomicrograph of the zinc powder anode with the protective layer prepared in Example 2 of the present invention;

[0033] Figure 3b Photomicrograph of the cut zinc powder anode with the protective layer prepared in Example 2 of the present invention;

[0034] Figure 3c Photomicrograph of the zinc powder anode with the protective layer prepared in Example 2 of the present invention after optical magnification;

[0035] Figure 4 Charge-discharge curve of the symmetric cells prepared in Example 1 and Comparative Example 1 at a current density of 0.5 mA·cm -2 and an areal capacity of 1.5 mAh·cm -2 ;

[0036] Figure 5 Charge-discharge curve of the symmetric cells prepared in Example 2 and Comparative Example 1 at a current density of 0.5 mA·cm -2 and an areal capacity of 1.5 mAh·cm -2 ;

[0037] Figure 6 Cycling performance comparison chart of the full cells prepared in Examples 1-2 and Comparative Example 1 at a current density of 0.1 A·g -1 ;

[0038] Figure 7 Rate performance chart of the full cells prepared in Examples 1-2 and Comparative Example 1. Detailed implementation manners

[0039] To make the objectives, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below. Apparently, the described embodiments are some, but not all, of the embodiments of the present application. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present application without creative efforts shall fall within the scope of protection of the present application.

[0040] The experimental methods used in the embodiments of the present application are all conventional methods unless otherwise specified.

[0041] In the following embodiments and comparative examples, unless otherwise specified, all raw materials can be prepared and synthesized by conventional methods or obtained commercially.

[0042] Example 1

[0043] This embodiment provides a zinc powder anode for an aqueous zinc-ion battery, which includes a zinc anode prepared from metallic zinc powder and a protective coating provided on the surface of the zinc anode. The protective coating contains a polyacrylic acid resin side chain grafted with an organosilicon group (-O-CH 2 -CH 2 -CH 2 -Si(OCH 3 ) 3 )

[0044] Its preparation method includes the following steps:

[0045] 1. Weigh the polyacrylate side chain grafted with an organosilicon group solution synthesized in the laboratory and deionized water according to a mass ratio of 7:3; add the polyacrylate side chain grafted with an organosilicon group solution to the deionized water, stir and mix at a speed of 400 r / min, and ultrasonicate for 20 min to obtain a uniform polyacrylate side chain grafted with an organosilicon group slurry;

[0046] 2. Bake the zinc powder anode in an oven at 110 °C for 1 min;

[0047] 3) Spray the slurry obtained in step 1 onto the surface of the zinc powder anode through a spray gun, with a spraying amount of 100 mL / min. After drying in a blast dryer at 80 °C for 2 min, cut it to obtain a zinc powder anode coated with a polyacrylate side chain grafted with an organosilicon group coating, and the coating thickness is 0.1 - 2 μm.

[0048] 4. Prepare an electrolyte with a certain concentration of ZnSO 4 electrolyte;

[0049] 5. Assemble the positive electrode plate, negative electrode plate, separator and electrolyte into a button battery.

[0050] The physical diagram of the zinc powder anode for an aqueous zinc-ion battery prepared in this embodiment is as shown in Figure 2a ; the physical diagram after cutting is as shown in Figure 2b ; the physical diagram after optical magnification is as shown in Figure 2c described.

[0051] Example 2

[0052] This embodiment provides a zinc powder anode for an aqueous zinc-ion battery, which includes a zinc anode prepared from metallic zinc powder and a protective coating provided on the surface of the zinc anode. The protective coating contains a polyurethane side chain grafted with an organosilicon group (-O-CH 2 -CH 2 -CH 2 -Si(OCH 3 ) 3 )

[0053] Its preparation method includes the following steps:

[0054] 1. Weigh the polyurethane side-chain grafted silicone group solution and deionized water according to a mass ratio of 6:4; add the polyurethane side-chain grafted silicone group solution to deionized water, stir and mix at a speed of 400 r / min, and ultrasonicate for 20 min to obtain a uniform polyurethane side-chain grafted silicone group slurry.

[0055] 2. Bake the zinc powder negative electrode in an oven at 100 °C for 1 min.

[0056] 3. Spray the slurry obtained in step 1 onto the surface of the zinc powder negative electrode through a spray gun at a spraying rate of 50 mL / min. After drying in a blast oven at 80 °C for 2 min, cut it to obtain a zinc powder negative electrode coated with a polyurethane side-chain grafted silicone group coating, and the coating thickness is 0.1 - 2 μm.

[0057] 4. Prepare an electrolyte with a certain concentration of ZnSO 4 electrolyte;

[0058] 5. Assemble the positive electrode plate, negative electrode plate, separator and electrolyte into a button battery.

[0059] The physical diagram of the zinc powder negative electrode for aqueous zinc-ion batteries prepared in this example is as shown in Figure 3a shown; the physical diagram after cutting is as shown in Figure 3b shown; the physical diagram after optical magnification is as shown in Figure 3c described.

[0060] Comparative Example 1

[0061] The preparation method of the zinc powder negative electrode in this comparative example includes the following steps:

[0062] 1. Cut the zinc powder negative electrode plate prepared in the laboratory into a negative electrode plate for button battery use.

[0063] 2. Prepare an electrolyte with a certain concentration of ZnSO 4 electrolyte;

[0064] 3. Assemble the positive electrode plate, negative electrode plate, separator and electrolyte into a button battery.

[0065] The physical diagram of the zinc powder negative electrode for aqueous zinc-ion batteries prepared in this comparative example is as shown in Figure 1a shown; the physical diagram after cutting is as shown in Figure 1b shown; the physical diagram after optical magnification is as shown in Figure 1c described.

[0066] The symmetric batteries prepared in Example 1 and Comparative Example 1 were subjected to charge-discharge tests at a current density of 0.5 mA·cm -2 , and a areal capacity of 1.5 mAh·cm -2 to obtain the charge-discharge curve graphs as shown inFigure 4 as shown;

[0067] The symmetric cells prepared in Example 2 and Comparative Example 1 were subjected to charge-discharge tests at a current density of 0.5 mA·cm -2 , and a areal capacity of 1.5 mAh·cm -2 , and the charge-discharge curves obtained are as shown in Figure 5 as shown;

[0068] The full cells prepared in Example 1, Example 2 and Comparative Example 1 were subjected to cyclic performance tests at a current density of 0.1 A·g -1 , and the cyclic test results obtained are as shown in Figure 6 as shown;

[0069] The full cells prepared in Example 1, Example 2 and Comparative Example 1 were subjected to rate performance tests, and the results obtained are as shown in Figure 7 as shown.

[0070] It can be seen from FIGS. 1-3 that the zinc powder anodes of Example 1 and Example 2 with protective coatings and the zinc powder anode of the comparative example without a protective coating are relatively similar in macroscopic and microscopic surface morphologies, but the spraying traces can be slightly seen.

[0071] From Figures 4 - 6 it can be seen that under the same conditions, compared with the comparative example, the symmetric cells of Example 1 and Example 2 with protective coatings have a cycle life of more than 600 h at a current density of 0.5 mA·cm -2 (1.5 mAh·cm -2 ); and the full cells of Example 1 and Example 2 with protective coatings can maintain 500 cycles and the capacity retention rates are as high as 79.1% and 78.6% respectively (calculated based on the highest and end points of the capacity) at a current density of 0.1 A·g -1 ; meanwhile, at a rate from 0.1C to 2C, the reversible discharge capacities of the full cells of Example 1 and Example 2 with protective coatings are significantly better than those of the full cells of the comparative example without a protective coating.

[0072] Example 3

[0073] This example provides a zinc powder anode for an aqueous zinc-ion battery, including a zinc anode prepared from metallic zinc powder and a protective coating provided on the surface of the zinc anode, and the protective coating contains polyacrylic resin side chains grafted with organic fluorine groups (-O-CH 2 -CH 2 -CF 3 ).

[0074] Its preparation method includes the following steps:

[0075] 1. Weigh the solution of polyacrylate side-chain grafted with organic fluorine groups synthesized in the laboratory and deionized water according to a mass ratio of 5:5; add the solution of polyacrylate side-chain grafted with organic silicon groups to deionized water, stir and mix at a speed of 500 r / min, and ultrasonicate for 30 min to obtain a uniform slurry of polyacrylate side-chain grafted with organic fluorine groups.

[0076] 3. Bake the zinc powder negative electrode in an oven at 100 °C for 1.5 min.

[0077] 6. Coat the slurry obtained in step 1 onto the surface of the zinc powder negative electrode by roll coating. After drying in a blast oven at 100 °C for 3 min, cut it to obtain a zinc powder negative electrode coated with a polyacrylate side-chain grafted with organic fluorine group coating, and the coating thickness is 0.1 - 2 μm.

[0078] 4. Prepare a ZnSO 4 electrolyte solution.

[0079] 5. Assemble the positive electrode sheet, negative electrode sheet, separator and electrolyte into a button battery.

[0080] Example 4

[0081] This example provides a zinc powder negative electrode for an aqueous zinc-ion battery, which includes a zinc negative electrode prepared from metallic zinc powder and a protective coating provided on the surface of the zinc negative electrode. The protective coating contains polyurethane side-chain grafted with organic fluorine groups (-O-CH 2 -CH 2 -CF 3 ).

[0082] Its preparation method includes the following steps:

[0083] 1. Weigh the solution of polyurethane side-chain grafted with organic fluorine groups and deionized water according to a mass ratio of 3:7; add the solution of polyurethane side-chain grafted with organic silicon groups to deionized water, stir and mix at a speed of 400 r / min, and ultrasonicate for 40 min to obtain a uniform slurry of polyurethane side-chain grafted with organic fluorine groups.

[0084] 3. Bake the zinc powder negative electrode in an oven at 90 °C for 3 min.

[0085] 3. Coat the slurry obtained in step 1 onto the surface of the zinc powder negative electrode by brushing. After drying in a blast oven at 110 °C for 4 min, cut it to obtain a zinc powder negative electrode coated with a polyurethane side-chain grafted with organic fluorine group coating, and the coating thickness is 0.1 - 2 μm.

[0086] 4. Prepare a ZnSO 4 electrolyte solution.

[0087] 5. Assemble the positive electrode sheet, negative electrode sheet, separator and electrolyte into a button battery.

[0088] Example 5

[0089] This example provides a zinc powder negative electrode for an aqueous zinc ion battery, including a zinc negative electrode prepared from metallic zinc powder and a protective coating provided on the surface of the zinc negative electrode, where the protective coating contains a polyacrylic acid resin side chain grafted with an organosilicon group (-O-CH 2 -CH 2 -CH 2 -Si(OCH 3 ) 3 ).

[0090] Its preparation method includes the following steps:

[0091] 1. Weigh the polyacrylate side chain grafted with an organosilicon group solution synthesized in the laboratory and deionized water according to a mass ratio of 2:8; add the polyacrylate side chain grafted with an organosilicon group solution to the deionized water, stir and mix at a speed of 350 r / min, and ultrasonicate for 25 min to obtain a uniform polyacrylate side chain grafted with an organosilicon group slurry;

[0092] 2. Bake the zinc powder negative electrode in an oven at 80 °C for 6 min;

[0093] 3) Spray the slurry obtained in step 1 onto the surface of the zinc powder negative electrode through a spray gun at a spraying rate of 90 mL / min, dry it in a blast dryer at 120 °C for 5 min, and then cut it to obtain a zinc powder negative electrode coated with a polyacrylate side chain grafted with an organosilicon group coating, with a coating thickness of 0.1 - 2 μm.

[0094] 4. Prepare an electrolyte with a certain concentration of ZnSO 4 ;

[0095] 5. Assemble the positive electrode sheet, negative electrode sheet, separator and electrolyte into a button battery.

[0096] Example 6

[0097] This example provides a zinc powder negative electrode for an aqueous zinc ion battery, including a zinc negative electrode prepared from metallic zinc powder and a protective coating provided on the surface of the zinc negative electrode, where the protective coating contains a polyurethane side chain grafted with an organosilicon group (-O-CH 2 -CH 2 -CH 2 -Si(OCH 3 ) 3 ).

[0098] Its preparation method includes the following steps:

[0099] 1. Weigh the polyurethane side-chain grafted silicone group solution and deionized water according to a mass ratio of 8:2; add the polyurethane side-chain grafted silicone group solution to deionized water, stir and mix at a speed of 200 r / min, and ultrasonicate for 50 min to obtain a uniform polyurethane side-chain grafted silicone group slurry.

[0100] 2. Bake the zinc powder negative electrode in an oven at 105 °C for 3 min.

[0101] 3. Spray the slurry obtained in step 1 onto the surface of the zinc powder negative electrode through a spray gun at a spraying rate of 70 mL / min. After drying in a blast oven at 125 °C for 5 min, cut it to obtain a zinc powder negative electrode coated with a polyurethane side-chain grafted silicone group coating, and the coating thickness is 0.1 - 2 μm.

[0102] 4. Prepare an electrolyte with a certain concentration of ZnSO 4 electrolyte;

[0103] 5. Assemble the positive electrode sheet, negative electrode sheet, separator and electrolyte into a button battery.

[0104] According to the disclosure and teaching of the above specification, those skilled in the art to which the present invention pertains can also make changes and modifications to the above embodiments. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and changes to the present invention should also fall within the protection scope of the claims of the present invention. In addition, although some specific terms are used in this specification, these terms are only for convenience of description and do not constitute any limitation to the present invention.

Claims

1. A zinc powder negative electrode for an aqueous zinc ion battery, characterized in that: The invention comprises a zinc negative electrode prepared from metal zinc powder and a protective coating arranged on the surface of the zinc negative electrode, wherein the protective coating comprises at least one of a polyacrylic resin side chain grafted with an organic silicon group or an organic fluorine group, and a polyurethane resin side chain grafted with an organic silicon group or an organic fluorine group.

2. The zinc powder negative electrode for aqueous zinc ion battery according to claim 1, characterized in that: The preparation method thereof at least comprises the following steps: S1, adding at least one solution of polyacrylic acid resin side chain grafted with organosilicon group or organofluorine group, polyurethane resin side chain grafted with organosilicon group or organofluorine group synthesized in the laboratory into deionized water and diluting the solution evenly to obtain a slurry; S2, pre-baking the zinc powder negative electrode in an oven; S3, constructing the slurry obtained in step S1 onto the surface of the zinc powder negative electrode, and obtaining the zinc powder negative electrode with a protective coating after drying.

3. The zinc powder negative electrode for aqueous zinc ion battery according to claim 2, characterized in that: The solute mass fraction of the slurry obtained in step S1 is 1 to 80%.

4. The zinc powder negative electrode for aqueous zinc ion battery according to claim 2, characterized in that: In step S2, the pre-baking temperature of the coating substrate zinc powder negative electrode is 50-150° C., and the baking time is 0.1-10 min.

5. The zinc powder negative electrode for aqueous zinc ion battery according to claim 2, characterized in that: The construction methods in step S3 include spraying, brushing and roller coating.

6. The zinc powder negative electrode for aqueous zinc ion battery according to claim 2, characterized in that: The drying method in step S3 is air drying or infrared drying, the drying temperature is 80-150° C., the drying time is 0.1-10 min, and the thickness of the zinc negative electrode protective coating is 0.1-2 μm.

7. The zinc powder negative electrode for aqueous zinc ion battery according to claim 1, characterized in that: The organosilicon group is specifically -R n SiX 4-n , wherein R is an organic group, X is an alkyl group or an aromatic hydrocarbon group, 1≤n≤3; The organic fluorine group is specifically -(CF2) n -CF3, where 1≤n≤3.

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