Method for electrophoretic cellulose surface modification of a zinc metal negative electrode and applications thereof

Abstract

This invention relates to a method for electrophoretic modification of the cellulose surface of a zinc metal anode and its application, belonging to the field of electrochemical energy storage technology. The modified zinc metal anode comprises zinc metal, a cellulose layer and a basic zinc chloride layer coating the zinc metal; wherein the cellulose layer is the outer layer and the basic zinc chloride layer is the inner layer. The invention also provides a method for electrophoretic modification of the cellulose surface of a zinc metal anode. This invention regulates the surface of the zinc metal anode by electrophoretically constructing the cellulose layer and the basic zinc chloride layer. The method is simple and efficient, providing a promising candidate anode for dendrite-free aqueous zinc-ion batteries.

Description

Technical Field

[0001] This invention belongs to the field of electrochemical energy storage technology, specifically relating to a method for electrophoretic cellulose surface modification of a zinc metal anode and its application. Background Technology

[0002] Traditional energy sources such as coal and oil generate significant pollution, and their reserves are dwindling. With increasing global attention to environmental issues and growing public awareness, the demand for renewable energy is rising. The use of renewable energy can reduce dependence on traditional energy sources, lower energy costs, improve economic efficiency, and promote sustainable economic development. Therefore, the search for cleaner and more sustainable energy sources has become a major focus, and the development of renewable energy sources such as solar, wind, and geothermal energy has become an urgent priority. Zinc, with its abundant energy resources, high theoretical specific capacity, low toxicity, and ease of processing, along with its environmentally friendly, safe, and economical advantages, makes aqueous zinc-ion batteries a promising energy storage device for future large-scale energy storage systems.

[0003] Interface control of zinc anodes significantly impacts battery performance and cycle life. However, zinc anodes are prone to dendrite growth, corrosion, and hydrogen evolution reaction (HEP) during cycling. During zinc deposition / stripping, uneven electric field forces and irreversible 2D diffusion cause zinc to accumulate on the anode surface. Zinc ions are attracted to the dendrite tips, nucleating and growing, inducing a "tip effect" that accelerates dendrite growth. These dendrites can puncture the separator, leading to a short circuit. HEP reduces coulombic efficiency, and continuous HEP can cause battery bulging. Corrosion roughens the zinc anode surface, further exacerbating dendrite growth. Dendrite growth, corrosion, and HEP are interconnected and limit the further development of zinc-ion batteries. Therefore, there is an urgent need to develop satisfactory strategies to stabilize zinc anodes in aqueous environments. Summary of the Invention

[0004] To address the problems existing in the prior art, the present invention aims to provide a method for electrophoretic cellulose surface modification of a zinc anode. To suppress dendrite growth and hydrogen evolution corrosion in zinc-ion battery anodes, the present invention utilizes a ruthenium-iridium-titanium cathode and an electrophoretic solution containing cellulose and polyacrylamide to form a smooth, uniform, and dense BC / ZHC coating layer on the zinc anode surface. The BC / ZHC@Zn electrode material consists of two coating layers: an upper bacterial cellulose layer, denoted as the BC layer, and a lower basic zinc chloride layer, denoted as the ZHC layer. In symmetrical battery rate performance tests, the polarization voltage of the coated zinc foil electrode was lower than that of the pure zinc electrode at different current densities. During long-cycle testing, the coated zinc electrode maintained stable cycling for 1000 hours while also exhibiting a low polarization voltage. In a Cu / Zn asymmetrical battery, the coated zinc electrode achieved a coulombic efficiency of 99.05% after 400 stable cycles. The method of this invention can significantly improve the cycle stability of zinc-ion batteries, and the preparation method is simple.

[0005] To achieve the above objectives, the present invention adopts the following technical solution: On one hand, the present invention provides a zinc metal anode modified by electrophoretic cellulose surface, wherein the modified zinc metal anode comprises zinc metal, a cellulose layer and a basic zinc chloride layer coated on the outside of the zinc metal; The cellulose layer is the outer layer, and the basic zinc chloride layer is the inner layer.

[0006] The zinc metal anode modified by electrophoretic cellulose has a total thickness of 5~15 μm for the cellulose layer and the basic zinc chloride layer.

[0007] Secondly, the present invention provides a method for modifying the electrophoretic cellulose surface of the zinc metal anode, comprising the following steps: (1) Weigh out cellulose (BC), add deionized water, stir at room temperature to form a homogeneous cellulose solution; (2) Weigh out polyacrylamide (PAM), dissolve it in deionized water, stir at room temperature to form a homogeneous polyacrylamide solution; (3) Mix the cellulose solution and the polyacrylamide solution and stir at room temperature to obtain a uniform cellulose-polyacrylamide mixed electrophoresis solution (BC-PAM). (4) Weigh zinc foil, sand the surface of zinc foil with sandpaper until zinc metal luster is exposed, set up counter electrode, place in electrophoresis tank, add cellulose-polyacrylamide mixed electrophoresis solution, turn on power and perform electrophoresis; (5) Remove the zinc foil that has undergone electrophoresis from the electrophoresis tank and dry it in a vacuum oven to obtain a zinc electrode ((BC / ZHC@Zn)) with a cellulose coating layer and a polyacrylamide coating layer.

[0008] A method for electrophoretic cellulose surface modification of the zinc metal anode, wherein the stirring conditions in step (1) are: rotation speed 300~600 r / min, time 10 min; The cellulose is selected from one of bacterial nanocellulose, microfibrillated cellulose, nanofibrillated cellulose, carboxymethyl cellulose, and carboxylated cellulose nanofibers.

[0009] A method for electrophoretic cellulose surface modification of the zinc metal anode, wherein the stirring conditions in step (2) are: rotation speed 300~600 r / min, time 60min; The polyacrylamide is an anionic polymer with a molecular weight of 5 million to 12 million.

[0010] A method for electrophoretic cellulose surface modification of the zinc metal anode, wherein the stirring conditions in step (3) are: rotation speed 300~600 r / min, time 30 min; The concentration of cellulose in the cellulose-polyacrylamide mixed electrophoresis solution is 1~3 g / L, and the concentration of polyacrylamide is 1~5 g / L.

[0011] A method for electrophoretic cellulose surface modification of the zinc anode, wherein the thickness of the zinc foil in step (4) is 50~100 μm; The sandpaper is of a grit size of 800-3000. The electrophoresis conditions are: pressure 5~20 V, electrophoresis time 0.5~2 min; The counter electrode is selected from one of ruthenium-iridium-titanium electrode, platinum sheet electrode, tin-antimony electrode or graphite electrode; The distance between the two electrodes in the electrophoresis is 1 to 5 cm.

[0012] A method for surface modification of cellulose by electrophoresis of zinc metal anode, wherein the drying time in the vacuum oven in step (5) is 6-8 h and the temperature is 50-70 ℃.

[0013] Thirdly, this invention provides the application of the electrophoretic cellulose surface-modified metallic zinc anode as a negative electrode in an aqueous zinc-ion battery. The BC / ZHC@Zn electrode material can be cut into pieces with a diameter of 1.2 cm and an area of ​​1.13 cm². 2 The disc is used as the negative electrode of the battery.

[0014] Fourthly, the present invention provides an aqueous zinc-ion battery comprising a metallic zinc negative electrode, a positive electrode material, and an electrolyte as described in claim 1 or 2. Preferably, the cathode material is selected from MnO2 and Zn. 0.25 V₂O₅nH₂O, HNaV₆O16 One of MZHCFs; Preferably, the electrolyte is selected from one of zinc sulfate solution, zinc trifluoromethanesulfonate solution, or zinc trifluoromethanesulfonylimide solution. Compared with the prior art, the present invention has the following beneficial effects: (1) The present invention uses an electrophoresis process to deposit a zinc anode material with two coating layers onto the surface of metallic zinc using a mixed solution of cellulose and polyacrylamide as the electrophoresis solution.

[0015] (2) The preparation method of the present invention is simple to operate, the reaction conditions are mild, and the selected reagents have many advantages such as low cost, environmental friendliness and abundant sources, and have good application prospects.

[0016] (3) The BC / ZHC@Zn obtained in this invention can inhibit the formation and growth of zinc dendrites in zinc-ion batteries, and its corrosion resistance and ability to inhibit hydrogen evolution reaction are improved, thus promoting the growth of Zn. 2+ Uniform deposition. Experiments have shown that the BC / ZHC coating layer possesses high mechanical flexibility, exhibits excellent rate performance at different current densities, and can cycle stably. The zinc anode with the BC / ZHC coating layer demonstrates excellent cycling performance in long-cycle tests of zinc-ion symmetric batteries and maintains a low polarization voltage. In Zn / / Cu asymmetric battery tests, the zinc anode with the BC / ZHC coating layer obtained by this invention exhibits superior cycle life and high coulombic efficiency compared to blank zinc. When assembled into a full cell with a cathode material, the rate performance of the zinc anode with the BC / ZHC coating layer is significantly better than that of the blank zinc anode, and after 1000 cycles, the capacity retention rate of the zinc anode with the BC / ZHC coating layer is much higher than that of the blank zinc anode. Attached Figure Description

[0017] Figure 1 The X-ray diffraction (XRD) patterns of the BC / ZHC@Zn electrode material prepared in Example 1 are shown, where (a) is the XRD broad spectrum of BC / ZHC@Zn and (b) is a magnified view of the low-angle region of the XRD of BC / ZHC@Zn. Figure 2 Fourier transform infrared spectrum of the BC / ZHC coating prepared in Example 1; Figure 3 The images are scanning electron microscope (SEM) images of the BC / ZHC@Zn electrode material prepared in Example 1, where (a) is a scanning electron microscope image of BC / ZHC@Zn SEM; and (b) is a scanning electron microscope image of ZHC@Zn SEM. Figure 4The rate performance of button cells assembled with the BC / ZHC@Zn electrode prepared in Example 1 and the blank zinc electrode at different current densities is shown in the graph. Figure 5 The long-cycle performance of the BC / ZHC@Zn electrode and the blank zinc electrode prepared in Example 2 after being assembled into button cells is shown in the following figures: (a) long-cycle charge-discharge curve; (b) charge-discharge curve for the 96th-100th cycle; (c) charge-discharge curve for the 996th-1000th cycle. Figure 6 The BC / ZHC@Zn negative electrode and the blank zinc negative electrode prepared in Example 3 were assembled with copper foil positive electrodes to form button cells, and the coulombic efficiency was tested. (a) is the coulombic efficiency graph; (b) is the capacity-voltage graph after 50 cycles. Figure 7 The BC / ZHC@Zn negative electrode and the blank zinc negative electrode prepared in Example 4 were respectively reacted with HNaV6O 16 The positive electrode assembly of a button cell was subjected to rate and long-cycle performance tests. (a) shows the rate performance graph; (b) shows the performance at 5 A g. -1 Long-cycle performance test at current density. Detailed Implementation

[0018] The present invention will be described below with reference to specific embodiments, but the present invention is not limited thereto.

[0019] Example 1: 1. Prepare a 4 g / L bacterial cellulose solution; take 0.12 g of polyacrylamide, add it to 60 mL of deionized water, stir evenly at room temperature, and mix it evenly with an equal volume of the 4 g / L bacterial cellulose solution to obtain a homogeneous BC-PAM electrophoresis buffer. Place a 50 μm thick zinc foil on a glass slide, and polish the surface of the zinc foil with 2000-grit sandpaper until a zinc metallic luster appears. Then place it in an electrophoresis tank; using ruthenium-iridium-titanium as the counter electrode, transfer the BC-PAM electrophoresis buffer into the electrophoresis tank, turn on the power, set the voltage to 15 V, and the electrophoresis time to 1 min. After electrophoresis, remove the zinc foil from the electrophoresis tank and dry it in a vacuum oven at 60 ℃ for about 6 h to obtain a zinc foil with a BC / ZHC coating.

[0020] 2. XRD analysis was performed on the BC / ZHC@Zn prepared in this embodiment, and the results are as follows: Figure 1As shown, characteristic peaks of BC are observed at 14.5°, 16.9°, and 22.7°. Peaks at 11.2°, 24.9°, 28°, 30.4°, 31°, 32.8°, 33.5°, and 34.5° correspond to the (003), (015), (110), (113), (107), (021), (202), and (018) crystal planes of basic zinc chloride, respectively. This confirms that the coating layer consists of BC and basic zinc chloride. 3. SEM analysis was performed on the surface morphology of the BC / ZHC@Zn prepared in this embodiment. Due to the poor conductivity of the bacterial cellulose layer, we performed gold sputtering treatment on it, and the results are as follows. Figure 3 As shown in (a), the fiber bands with a diameter of approximately 30–200 μm are interwoven with hydrogen bonds to form a three-dimensional network structure. Because of its three-dimensional network structure, bacterial cellulose has good mechanical properties. Figure 3 (b) is a SEM of the basic zinc chloride layer. Basic zinc chloride is a nano-thin powder with a thickness of about 200 to 500 nm. Due to its high diameter and thickness, the two-dimensional material can form a "maze effect" in the coating matrix, which greatly prolongs the diffusion path of the corrosive medium.

[0021] 4. The upper and lower coating layers prepared in this embodiment were removed from the zinc foil and subjected to infrared spectroscopy testing. The results are as follows: Figure 2 As shown, layer BC is located at 3345, 2908, and 1050 cm. -1 A strong absorption peak is observed at 3345 cm⁻¹. -1 The absorption peak at 2908 cm⁻¹ is due to the intermolecular hydrogen bond stretching vibration caused by the OH bond in BC. -1 The absorption peak at 1050 cm⁻¹ is due to the stretching vibration of CH₂-CH in BC; -1 The absorption peak at 1630 cm⁻¹ is due to CO stretching vibration. Therefore, this further confirms that the upper coating layer is a BC layer. The ZHC coating layer at 1630 cm⁻¹... -1 The peak at 800–1000 cm⁻¹ is the Zn-Cl peak. -1 The strong absorption peaks in the range belong to Zn-OH; 500–600 cm⁻¹ -1 The peak at this point is Zn-O. This further confirms that the lower coating layer is a basic zinc chloride layer.

[0022] 5. Using BC / ZHC@Zn as the negative electrode and unprotected zinc metal as the positive electrode, and a 2 mol / L ZnSO4 aqueous solution as the electrolyte, along with a separator, gasket, and spring, assemble a BC / ZHC@Zn / / Zn button cell. Use blank zinc foil as the negative electrode to assemble a Zn / / Zn button cell as a control experiment.

[0023] After assembling the blank zinc electrode and the BC / ZHC@Zn electrode into button cells, rate performance tests were conducted at different current densities. The results are as follows: Figure 4 As shown. Figure 4 This indicates that at a constant capacity of 1 mAh cm⁻¹ -2 Under these conditions, the current density is 0.25 mA cm⁻¹. -2 0.5 mA cm -2 1 mA cm -2 2 mA cm -2 5 mA cm -2 10 mA cm -2 BC / ZHC@Zn / / Zn batteries operate at 0.25~10 mA cm⁻¹ -2 The polarization voltage at different current densities ranges from 47 to 155 mV, exhibiting high reversibility. In contrast, the Zn / / Zn battery shows higher polarization voltages (66–365 mV) at different current densities, and a short circuit occurs after approximately 93 hours of cycling. At all current densities, the polarization voltage of the BC / ZHC@Zn / / Zn battery is significantly lower than that of the Zn / / Zn battery, indicating that the presence of the BC / ZHC coating reduces the interfacial resistance, and the BC / ZHC@Zn zinc anode exhibits good stability.

[0024] Example 2: 1. Prepare a homogeneous 4 g / L bacterial cellulose solution; take 0.24 g of polyacrylamide, add it to 60 mL of deionized water, stir evenly at room temperature, and mix it evenly with an equal volume of the 4 g / L bacterial cellulose solution to obtain a homogeneous BC-PAM electrophoresis buffer. Place a 50 μm thick zinc foil on a glass slide, and polish the oxide layer on the surface of the zinc foil with 2000-grit sandpaper until a zinc metallic luster appears. Then place it in an electrophoresis tank; using ruthenium-iridium-titanium as the counter electrode, transfer the BC-PAM electrophoresis buffer into the electrophoresis tank, turn on the power, set the voltage to 10 V, and the electrophoresis time to 1 min. Remove the zinc foil from the electrophoresis tank and dry it in a vacuum oven at 60 ℃ for about 7 h. A zinc foil with a BC / ZHC coating is obtained.

[0025] 2. Using the BC / ZHC@Zn prepared in Example 2 as the negative electrode and zinc metal without a protective layer as the positive electrode, the electrolyte was a 2 mol / L ZnSO4 aqueous solution. Other components included were a separator, gaskets, and springs. A BC / ZHC@Zn / / Zn button cell was assembled using these materials. A Zn / / Zn button cell was assembled using blank zinc as the negative electrode as a control experiment.

[0026] After assembling the blank zinc electrode and the BC / ZHC@Zn electrode into button cells, long-cycle performance tests were conducted, and the results are as follows: Figure 5 As shown. Figure 5 This indicates that at a current density of 1 mA cm⁻¹ -2 , with a capacity of 1 mAh cm -2 Under the given conditions, the BC / ZHC@Zn / / Zn battery has a lower polarization voltage (60 mV) and a cycle life exceeding 1000 h, while the Zn / / Zn battery has a higher polarization voltage (75 mV) and short-circuit after about 100 h of cycling. This indicates that the presence of the BC / ZHC coating layer greatly improves the cycle life of zinc-ion batteries.

[0027] Example 3: 1. Prepare a 4 g / L bacterial cellulose solution; add 0.36 g of polyacrylamide to 60 mL of deionized water, stir evenly at room temperature, and mix evenly with an equal volume of the 4 g / L bacterial cellulose solution to obtain a homogeneous BC-PAM electrophoresis buffer. Place a 50 μm thick zinc foil on a glass slide, and use 2000-grit sandpaper to remove the oxide layer from the zinc foil surface until a zinc metallic luster appears. Then place it in an electrophoresis tank; using ruthenium-iridium-titanium as the counter electrode, transfer the BC-PAM electrophoresis buffer into the electrophoresis tank, turn on the power, set the voltage to 10 V, and the electrophoresis time to 1 min. Remove the zinc foil from the electrophoresis tank and dry it in a vacuum oven at 60 ℃ for about 6 h. Finally, a zinc foil with a BC / ZHC coating is obtained.

[0028] 2. Using BC / ZHC@Zn as the negative electrode, copper foil as the positive electrode, and a 2 mol / L ZnSO4 aqueous solution as the electrolyte, along with a separator, gasket, and spring, assemble a BC / ZHC@Zn / / Cu asymmetric button cell. Use blank zinc as the negative electrode to assemble a Zn / / Cu asymmetric button cell as a control experiment.

[0029] The blank zinc negative electrode and the BC / ZHC@Zn negative electrode were respectively assembled into button cells with copper foil positive electrodes, and their electrochemical performance was tested. The results are as follows: Figure 6 As shown. Figure 6 (a) indicates that at a current density of 0.5 mA cm⁻¹ -2 The capacity is 0.5 mAh cm⁻¹ -2Under the specified conditions, in the Zn / / Cu cell, the coulombic efficiency increased from 60.74% to 94% in the first 20 cycles, fluctuated between 94% and 97% in the subsequent 80 cycles, and finally dropped to almost zero after the 100th cycle. The initial low coulombic efficiency and the fluctuations in coulombic efficiency during cycling are likely caused by side reactions and dendrite growth on the blank zinc foil. In the BC / ZHC@Zn / / Cu cell, the coulombic efficiency increased from 65.78% to 95.2% in the first 20 cycles, and continued to increase in the subsequent 380 cycles, still reaching 99.05% at the 400th cycle. This indicates that the presence of the BC / ZHC coating layer effectively suppressed interfacial side reactions. Figure 6 (b) The capacity-voltage curves of the Zn / / Cu battery and the BC / ZHC@Zn / / Cu battery at the 50th cycle show that the BC / ZHC@Zn / / Cu battery has a lower nucleation overpotential. These results indicate that the presence of the BC / ZHC coating layer effectively suppresses interfacial side reactions, improves the reversibility of the zinc anode, and achieves uniform zinc deposition during the stripping / electroplating process.

[0030] Example 4: 1. Prepare a 4 g / L bacterial cellulose solution; take 0.12 g of polyacrylamide, add it to 60 mL of deionized water, stir well, and mix it with an equal volume of the 4 g / L bacterial cellulose solution to obtain a homogeneous BC-PAM electrophoresis buffer. Place a 50 μm thick zinc foil on a glass slide, and polish the oxide layer on the surface of the zinc foil with 2000-grit sandpaper until a zinc metallic luster appears. Then place it in an electrophoresis tank; using ruthenium-iridium-titanium as the counter electrode, transfer the BC-PAM electrophoresis buffer into the electrophoresis tank, turn on the power, set the voltage to 15 V, and the electrophoresis time to 1 min. Remove the zinc foil from the electrophoresis tank and dry it in a vacuum oven at 60 ℃ for about 6 h. A zinc foil with a BC / ZHC coating is obtained.

[0031] 2. Using BC / ZHC@Zn as the negative electrode and HNaV6O as the positive electrode in a zinc-ion battery. 16 The electrolyte is a 2.5 mol / L zinc trifluoromethanesulfonate solution. Other components include a diaphragm, gaskets, and springs. The above materials are assembled into BC / ZHC@Zn / / HNaV6O. 16 Full cell. Using blank zinc foil as the negative electrode, assemble Zn / / HNaV6O. 16 A full cell was used as a control.

[0032] The Zn / / HNaV6O 16 ,BC / ZHC@Zn / / HNaV6O 16 Electrochemical performance tests were performed separately, and the results are as follows: Figure 7As shown in the figure. Rate performance tests were conducted on the two different zinc anode-assembled full cells described above, and the results are as follows. Figure 7 As shown in (a), the current densities are 0.1~5.0 A g. -1 Under the conditions, BC / ZHC@Zn / / HNaV6O 16 The capacities are 403.4, 354.2, 325.8, 308, 304.2, 288.5, and 247.6 mAh g, respectively. -1 All are much higher than Zn / / HNaV6O 16 After the rate test was completed, long-cycle stability tests were conducted on the two different zinc anode-assembled full cells, and the results are as follows. Figure 7 As shown in (b), at 5 A g -1 After 1000 charge-discharge cycles at current density, Zn / / HNaV6O 16 ,BC / ZHC@Zn / / HNaV6O 16 The initial reversible capacities were 220 and 241 mAh g, respectively. -1 After 1000 cycles, the reversible capacities were 190.4 and 240 mAh g, respectively. -1 The BC / ZHC@Zn electrode exhibits higher rate performance and more stable cycle performance in full cells, indicating its potential application in rechargeable zinc-ion batteries.

Claims

1. An electrophoretically cellulose surface-modified metal zinc negative electrode, characterized by, The modified zinc anode comprises zinc, a cellulose layer and a basic zinc chloride layer coated on the outside of the zinc. The cellulose layer is the outer layer, and the basic zinc chloride layer is the inner layer.

2. A metal zinc negative electrode surface-modified with electrophoretic cellulose according to claim 1, characterized in that, The total thickness of the cellulose layer and the basic zinc chloride layer is 5~15 μm.

3. A method for surface modification of electrophoretic cellulose of a metal zinc negative electrode as claimed in claim 1 or 2, characterized by, Includes the following steps: (1) Weigh out cellulose, add deionized water, stir at room temperature to form a homogeneous cellulose solution; (2) Weigh out polyacrylamide, dissolve it in deionized water, stir at room temperature to form a homogeneous polyacrylamide solution; (3) Mix the cellulose solution and the polyacrylamide solution and stir at room temperature to obtain a uniform cellulose-polyacrylamide mixed electrophoresis solution; (4) Weigh out zinc foil, sand the surface of zinc foil with sandpaper until zinc metal luster is exposed, place it in an electrophoresis tank, set up the counter electrode, add cellulose-polyacrylamide mixed electrophoresis solution, turn on the power and perform electrophoresis; (5) Take out the zinc foil that has undergone electrophoresis in the electrophoresis tank and dry it in a vacuum oven to obtain a zinc electrode with a cellulose coating layer and a polyacrylamide coating layer.

4. A method for modifying the surface of electrophoretic cellulose on a zinc metal anode as described in claim 3, characterized in that, The stirring conditions in step (1) are: rotation speed 300~600 r / min, time 10 min; The cellulose is selected from any one of bacterial nanocellulose, microfibrillated cellulose, nanofibrillated cellulose, carboxymethyl cellulose, and carboxylated cellulose nanofibers.

5. A method for surface modification of electrophoretic cellulose on a zinc metal anode as described in claim 3, characterized in that, The stirring conditions in step (2) are: rotation speed 300~600 r / min, time 60min; The polyacrylamide is an anionic polymer with a molecular weight of 5 million to 12 million.

6. A method for modifying the surface of electrophoretic cellulose on a zinc metal anode as described in claim 3, characterized in that, The stirring conditions in step (3) are: rotation speed 300~600 r / min, time 30 min; The concentration of cellulose in the cellulose-polyacrylamide mixed electrophoresis solution is 1~3 g / L, and the concentration of polyacrylamide is 1~5 g / L.

7. A method for electrophoretic cellulose surface modification of a zinc metal anode as described in claim 3, characterized in that, In step (4), the thickness of the zinc foil is 50~100 μm; The sandpaper is of a grit size of 800-3000. The electrophoresis conditions are: pressure 5~20 V, electrophoresis time 0.5~2 min; The counter electrode is selected from one of ruthenium-iridium-titanium electrode, platinum sheet electrode, tin-antimony electrode or graphite electrode; The distance between the two electrodes in the electrophoresis is 1 to 5 cm.

8. A method for electrophoretic cellulose surface modification of a zinc metal anode as described in claim 3, characterized in that, In step (5), the drying time in the vacuum oven is 6-8 hours and the temperature is 50-70 ℃.

9. The application of the electrophoretic cellulose surface-modified metallic zinc anode as described in claim 1 or 2 as an anode in an aqueous zinc-ion battery.

10. An aqueous zinc-ion battery, characterized in that, It comprises a zinc anode, a cathode material, and an electrolyte as described in claim 1 or 2; Preferably, the cathode material is selected from the group consisting of MnO2, Zn 0.25 V2O5nH2O, HNaV6O 16 , one of the MZHCFs; Preferably, the electrolyte is selected from one of zinc sulfate solution, zinc trifluoromethanesulfonate solution, or zinc trifluoromethanesulfonamide solution.

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