Flexible thin film interface modified zinc negative electrode based on pressure-induced permeation bonding as well as preparation method and application of flexible thin film interface modified zinc negative electrode

Abstract

The invention relates to the technical field of aqueous zinc ion batteries, and particularly discloses a flexible film interface modified zinc negative electrode based on pressure-induced permeation bonding and a preparation method and application thereof, and the preparation method comprises the following steps: preparing a composite flexible film formed by mixing bacterial cellulose and a carbon material; the polished zinc substrate is coated with 10-20 [mu] L cm <-2 > PVA as an interface cross-linking agent; then covering the PVA with the composite flexible film, and applying a pressure of 5-20 MPa to form a BC / C-PVA-Zn three-layer integrated structure; and then carrying out heat treatment under a vacuum condition to obtain the modified zinc negative electrode with high bonding strength. According to the invention, an integrated protection structure method of flexible buffering, high conductivity, strong interface bonding and green process is constructed, dendritic crystal growth and side reaction are effectively inhibited, the cycle life of the aqueous zinc ion battery is remarkably prolonged, and the electrochemical performance of the aqueous zinc ion battery is remarkably improved.

Description

Technical Field

[0001] This invention relates to the field of aqueous zinc-ion battery anode material technology, specifically to a flexible thin-film interface-modified zinc anode based on pressure-induced permeation bonding, its preparation method, and its application. Background Technology

[0002] Aqueous zinc-ion batteries, as an emerging electrochemical energy storage technology, have attracted widespread attention due to their advantages such as high safety, low cost, and high theoretical capacity. Compared with traditional organic batteries, aqueous electrolytes are non-flammable, fundamentally solving safety hazards; zinc resources are abundant and inexpensive, and the battery manufacturing process is simple, significantly reducing production costs; the zinc anode has a high theoretical capacity (820 mAh g⁻¹). -1 This makes it possible to construct high-energy-density batteries. These advantages enable aqueous zinc-ion batteries to show broad application prospects in large-scale energy storage fields such as smart grid energy storage and wearable electronic devices.

[0003] However, zinc anodes still face severe challenges in practical applications: dendrite formation, corrosion, and hydrogen evolution. The most pressing issue is zinc dendrite formation: during cycling, uneven deposition of zinc ions forms dendrites, which can puncture the separator, causing short circuits, battery failure, and even thermal runaway. Current mainstream technologies involve introducing inorganic / organic coatings onto the zinc anode surface, which can improve interface issues to some extent. However, these coatings typically suffer from high rigidity and poor local conductivity, leading to cracking and detachment after volume expansion / contraction during cycling, as well as localized current density concentration, causing dendrite growth. While 3D / porous current collector structures can alleviate localized current concentration, they face challenges such as interface instability, complex fabrication, and high cost, hindering scalability. Existing technologies generally lack an integrated protective structure that combines flexible buffering, high conductivity, strong interfacial adhesion, and environmentally friendly processes. Summary of the Invention

[0004] The purpose of this invention is to address the aforementioned problems by providing a flexible thin-film interface-modified zinc anode based on pressure-induced permeation bonding, its preparation method, and its application. This method is an integrated protective structure method that combines "flexible buffering + good conductivity + strong interface bonding + green process." When applied to aqueous zinc-ion batteries, it achieves high performance at 1 mA cm⁻¹. -2 1mAh cm -2 Under these conditions, the symmetric cell can cycle stably for more than 2000 hours; the vanadium-based full cell still has a coulombic efficiency of more than 99% and a capacity retention of more than 88% after 2000 cycles. Therefore, the modified zinc anode prepared by this method significantly improves the cycle life and electrochemical performance of aqueous zinc-ion batteries.

[0005] To achieve the above objectives, the first aspect of the present invention provides a method for preparing a flexible thin-film interface-modified zinc anode based on pressure-induced permeation bonding, comprising the following steps:

[0006] (1) Preparation of composite flexible film: After fully fusing bacterial cellulose (BC) with carbon material (C), a composite flexible film with a three-dimensional porous network structure is prepared by vacuum filtration.

[0007] (2) Pre-positioning of interfacial crosslinking agent: Polyvinyl alcohol (PVA) is introduced as an interfacial crosslinking agent on the surface of the zinc substrate;

[0008] (3) Pressure-induced in-situ anchoring: The composite flexible film is covered on PVA and pressure is applied so that PVA can penetrate and fill the pores of the composite flexible film and the microstructure of the zinc substrate under the action of pressure, forming a “BC / C-PVA-Zn” three-layer integrated structure.

[0009] (4) Curing and shaping: Heat treatment is carried out under vacuum conditions to remove the solvent and obtain a modified zinc anode with high bonding strength.

[0010] Preferably, the bacterial cellulose solution in step (1) is prepared by placing bacterial cellulose in a beaker, adding a certain amount of deionized water, and stirring or ultrasonically dispersing for 1-1.5 hours to make the bacterial cellulose evenly dispersed. The carbon material solution is prepared by placing carbon material in a beaker, adding a certain amount of ethanol, and stirring or ultrasonically dispersing for 0.5-1 hours.

[0011] More preferably, the mass ratio of bacterial cellulose to carbon material is (5-15):1.

[0012] Preferably, the carbon material is carbon nanotube, graphene, or carbon fiber.

[0013] Preferably, the polyvinyl alcohol in step (2) is obtained by dissolving solid polyvinyl alcohol in a water bath at 90°C.

[0014] Preferably, step (3) of introducing polyvinyl alcohol onto the zinc substrate surface specifically involves dropwise addition of 5-15 wt% polyvinyl alcohol onto the zinc substrate, with a coating amount of 10-20 μL / cm³. -2 .

[0015] Preferably, the pressure applied in step (3) is applied by pressing with a tablet press at a pressure of 5-20 MPa.

[0016] Preferably, the heat treatment in step (4) is performed at a heating temperature of 50-80℃ for a heating time of 0.5-5h.

[0017] In another aspect, the present invention provides a flexible thin-film interface-modified zinc anode based on pressure-induced permeation bonding prepared according to the above preparation method.

[0018] The present invention also provides an application of a flexible thin-film interface-modified zinc anode based on pressure-induced permeation bonding in an aqueous zinc-ion battery.

[0019] By adopting the above technical solution, the present invention has at least the following beneficial effects:

[0020] In this invention, BC acts as an "ion flux regulator." Its hydrophilicity and porous structure homogenize the zinc ion flow. Furthermore, the green material BC, as the substrate material of the composite flexible film, possesses high mechanical strength, effectively alleviating expansion stress during cycling and acting as a buffer. Meanwhile, the carbon material acts as an "electric field homogenizer," eliminating tip reactions and inducing uniform zinc ion deposition, resulting in excellent conductivity of the BC / C flexible film interface-modified zinc anode. This invention utilizes pressure-induced permeation technology to create a "rivet-like" effect between PVA in the nanopores of the composite flexible film and the microstructure on the zinc substrate surface, achieving physical interlocking and improving interfacial adhesion strength.

[0021] Furthermore, by applying the flexible thin-film interface-modified zinc anode based on pressure-induced permeation bonding to aqueous zinc-ion batteries, the modified zinc anode of the present invention exhibits significant advantages under the same electrolyte and testing conditions compared to the unmodified pure zinc anode:

[0022] (1) At 1mA cm -2 1mAh cm -2 Under these conditions, the symmetrical battery can cycle stably for more than 2000 hours, which is 30 times longer than that of the unmodified pure zinc anode.

[0023] (2) In (0.5, 1, 2, 3, 5, 8, 0.5mA cm) -2 ), 1mAh cm -2 Under these conditions, it exhibits excellent rate performance, and the current density returns to 0.5 mA cm⁻¹. -2 It can still cycle stably for more than 2000 hours; compared with the unmodified pure zinc anode, the performance improvement is huge.

[0024] (3) In 2A g -1 Under current density conditions, the full cell (positive electrode NH4V4O) 10 After 2000 cycles, the coulombic efficiency is still greater than 99%, and the capacity retention rate is higher than 88%, which is much higher than that of pure zinc anode.

[0025] Therefore, this invention achieves effective suppression of zinc dendrites and slows down corrosion and hydrogen evolution side reactions by modifying the zinc anode with a flexible thin film interface based on pressure-induced permeation bonding, thereby significantly improving the lifespan and performance of aqueous zinc-ion batteries. This provides a new approach that combines with the field of membrane science for the subsequent research and application of aqueous zinc-ion battery anodes. Attached Figure Description

[0026] Figure 1 This is a planar optical photograph of the flexible thin film interface-modified zinc anode based on pressure-induced permeation bonding in this invention.

[0027] Figure 2 This is a cross-sectional optical photograph of the flexible thin film interface-modified zinc anode based on pressure-induced permeation bonding in this invention, wherein the inset is a schematic diagram of the cross-sectional structure;

[0028] Figure 3 The symmetrical battery assembled in Example 1 and Comparative Example 1 of this invention is at 1 mA cm -2 1mAh cm -2 Cyclic performance under charge-discharge conditions;

[0029] Figure 4 These are XRD comparison images of Example 1 and Comparative Example 1 before and after cycling in this invention;

[0030] Figure 5 These are rate performance diagrams of the symmetrical batteries assembled in Example 2 and Comparative Example 2 of this invention at different current densities;

[0031] Figure 6 This is the rate performance of the symmetrical batteries assembled in Example 2 and Comparative Example 2 of this invention under different current densities for the first 150 hours.

[0032] Figure 7 These are vanadium-based full cells assembled in Embodiment 3 and Comparative Example 3 of the present invention, with a yield of 2A g. -1 Long-cycle performance diagram of constant current charge and discharge at current density. Detailed Implementation

[0033] The technical effects of the present invention will be further illustrated below with reference to the accompanying drawings and specific embodiments and comparative examples, but the scope of protection of the present invention is not limited to these embodiments.

[0034] The electrolyte used in the examples and comparative examples consisted of 7.27 g of zinc trifluoromethanesulfonate and 10 mL of deionized water. The preparation method was as follows: zinc trifluoromethanesulfonate was dissolved in deionized water and stirred until homogeneous.

[0035] Example 1

[0036] A method for preparing a flexible thin-film interface-modified zinc anode based on pressure-induced permeation bonding includes the following steps:

[0037] 1. Preparation of the composite flexible film: 25 mg of bacterial cellulose was weighed into a beaker, 30 ml of deionized water was added, and the mixture was stirred for 1 h to disperse the bacterial cellulose evenly. Simultaneously, 2 mg of carbon nanotubes was weighed into a beaker, 10 ml of ethanol was added, and the mixture was ultrasonically dispersed for 0.5 h. The ultrasonically dispersed carbon nanotube solution was then added to the bacterial cellulose solution and stirred for 1 h to obtain a homogeneous mixed solution. The mixed solution was then poured into a vacuum filtration apparatus for film formation, yielding a composite flexible film with a diameter of 4.5 cm.

[0038] 2. Preparation of interfacial crosslinking agent: Add 9 ml of deionized water to a beaker and heat it in a water bath at 90°C. Weigh 1 g of polyvinyl alcohol (PVA, type 1799) and add it to the beaker in three portions, stirring for 1 hour until completely dissolved. Turn off the water bath heating switch and allow the PVA solution to cool naturally to remove air bubbles.

[0039] 3. Pressure-induced in-situ anchoring: Cut zinc metal sheets with a thickness of 150μm and a length and width of 6cm, and polish them with 600-mesh and 2000-mesh sandpaper respectively to obtain zinc substrate; drop 250μL of 10wt% PVA obtained in step (2) onto the center of zinc substrate, cover the PVA with composite flexible film, and apply a pressure of 10MPa using a tablet press, so that PVA permeates and fills the pores of composite flexible film and the microstructure of zinc substrate surface under pressure, forming a “BC / CNT-PVA-Zn” three-layer integrated structure, and obtain the modified zinc anode.

[0040] 4. Curing and shaping: The modified zinc anode is vacuum dried. The vacuum drying oven is set at -0.1 MPa, the heating temperature is 60℃, and the temperature is maintained for 1 hour. After drying, a modified zinc anode with high bonding strength is obtained.

[0041] Figure 1 This is a planar optical photograph of the modified zinc anode. Figure 2 This is an optical photograph of the cross-section of the modified zinc anode, with the inset showing a schematic diagram of the structure. (Combined with...) Figure 1 and Figure 2 As can be seen, the modified zinc anode prepared in this embodiment exhibits a three-layer integrated structure, namely, a PVA gel buffer layer with adjustable thickness is formed between the zinc substrate and the BC / CNT film. The PVA acts as a binder and is physically interlocked in the microstructure of the BC / CNT network and the zinc substrate surface, so that the modified zinc anode has good structural stability.

[0042] Battery assembly: The modified zinc negative electrode is cut into electrode sheets with a diameter of 12mm, and then assembled into a symmetrical battery under a pressure of 500psi in the order of positive electrode shell, modified zinc negative electrode, separator, electrolyte, modified zinc negative electrode, gasket, spring sheet and negative electrode shell.

[0043] Comparative Example 1

[0044] The difference from Example 1 is that the preparation method of the zinc anode was changed, and the zinc anode was not modified. The specific method is as follows:

[0045] Zinc metal sheets with a thickness of 150 micrometers and a length and width of 6 cm were cut and polished with 600-grit and 2000-grit sandpaper respectively to obtain pure zinc negative electrodes. The zinc negative electrodes, which are not protected by the thin film, were cut into electrode sheets with a diameter of 12 mm. The positive electrode shell, pure zinc negative electrode, separator, electrolyte, pure zinc negative electrode, gasket, spring sheet and negative electrode shell were assembled into a symmetrical cell under a pressure of 500 psi.

[0046] The test schemes and analysis results of Example 1 and Comparative Example 1 are as follows:

[0047] For the symmetrical cells assembled in Example 1 and Comparative Example 1, at 1 mA cm -2 1mAh cm -2 Under constant current charge-discharge conditions, Figure 3 This illustrates a symmetrical cell at 1 mA cm⁻¹ -2 1mAh cm -2 The charge-discharge cycle performance diagram under the given conditions is derived from... Figure 3 It can be seen that the stable cycle time of Example 1 exceeds 2000h; while the stable cycle time of Comparative Example 1 only reaches 65h, with a maximum improvement of 3000%. Figure 4 The XRD comparison diagrams of Example 1 and Comparative Example 1 before and after cycling are shown. It can be clearly seen that the by-products of Example 1 after cycling are much less than those of Comparative Example 1 after cycling. This indicates that the flexible thin film interface modified zinc anode based on pressure-induced infiltration bonding has a stable composite interface layer structure. The conductive network constructed by BC+CNT is conducive to the uniform distribution of current and can effectively suppress dendrite growth and the generation of by-products.

[0048] Example 2

[0049] A method for preparing a flexible thin-film interface-modified zinc anode based on pressure-induced permeation bonding includes the following steps:

[0050] 1. Preparation of the composite flexible film: 20 mg of bacterial cellulose was weighed into a beaker, 30 ml of deionized water was added, and the mixture was stirred for 1 h to disperse the bacterial cellulose evenly. Simultaneously, 2 mg of graphene was weighed into a beaker, 10 ml of ethanol was added, and the mixture was sonicated in an ultrasonic machine for 0.5 h. The sonicated graphene solution was then added to the bacterial cellulose solution, and the mixture was stirred for 1 h to obtain a homogeneous mixed solution. The mixed solution was then poured into a vacuum filtration apparatus for film formation, yielding a composite flexible film with a diameter of 4.5 cm.

[0051] 2. Preparation of interfacial crosslinking agent: Add 9 ml of deionized water to a beaker and heat it in a water bath at 90°C. Weigh 1 g of polyvinyl alcohol (PVA, type 1799) and add it to the beaker in three portions, stirring for 1 hour until completely dissolved. Turn off the water bath heating switch and allow the PVA solution to cool naturally to remove air bubbles.

[0052] 3. Pressure-induced in-situ anchoring: A zinc metal sheet with a thickness of 150μm and a length and width of 6cm is cut and polished with 600-grit and 2000-grit sandpaper to obtain a zinc substrate; 250μL of 10wt% PVA is dropped into the center of the zinc substrate, and a composite flexible film is covered on the PVA. A pressure of 10MPa is applied using a tablet press, so that the PVA permeates and fills the pores of the composite flexible film and the microstructure of the zinc substrate surface under pressure, forming a three-layer integrated structure of "BC / C-PVA-Zn".

[0053] 4. Curing and shaping: The modified zinc anode is vacuum dried. The conditions of the vacuum drying oven are -0.1MPa, heating to 60℃, and holding for 1 hour. After drying, a modified zinc anode with high bonding strength is obtained.

[0054] Battery assembly: The modified zinc negative electrode is cut into electrode sheets with a diameter of 12mm, and then assembled into a symmetrical battery under a pressure of 500psi in the order of positive electrode shell, modified zinc negative electrode, separator, electrolyte, modified zinc negative electrode, gasket, spring sheet and negative electrode shell.

[0055] Comparative Example 2

[0056] The difference from Example 2 is that the preparation method of the zinc anode was changed, and the zinc anode was not modified. The specific method is as follows:

[0057] Zinc metal sheets with a thickness of 150 micrometers and a length and width of 6 cm were cut and polished with 600-grit and 2000-grit sandpaper respectively to obtain pure zinc negative electrodes. The zinc negative electrodes, which are not protected by the thin film, were cut into electrode sheets with a diameter of 12 mm. The positive electrode shell, pure zinc negative electrode, separator, electrolyte, pure zinc negative electrode, gasket, spring sheet and negative electrode shell were assembled into a symmetrical cell under a pressure of 500 psi.

[0058] The test schemes and analysis results of Example 2 and Comparative Example 2 are as follows:

[0059] The symmetrical cells assembled in Example 2 and Comparative Example 2, at (0.5, 1, 2, 3, 5, 8, 0.5 mA cm⁻¹) -2 ), 1mAh cm -2 Under constant current charge-discharge conditions, 20 cycles were performed at each current density, until the current density returned to 0.5 mA cm⁻¹. -2 No limit is set on the number of loops; Figure 5 The diagram illustrates the rate performance of a symmetrical battery at different current densities. Figure 6 The rate performance graph shows the results over the first 150 hours. It can be seen that Example 2 returned to 0.5 mA cm⁻¹ after cycling at different current densities. -2 It still maintains a stable polarization voltage and stable performance, with a cycle time exceeding 2000 hours; while Comparative Example 2 only achieved a stable cycle time of 66 hours at 2 mA cm⁻¹. -2 Under the conditions that have already been damaged, the performance of the zinc anode modified by the flexible film interface based on pressure-induced permeation bonding is greatly improved. The composite flexible film with strong adhesion of PVA and high mechanical strength ensures that the composite interface layer structure can maintain stable cycling under different current densities and can effectively protect the zinc electrode surface during rapid zinc deposition / stripping.

[0060] Example 3

[0061] A method for preparing a flexible thin-film interface-modified zinc anode based on pressure-induced permeation bonding includes the following steps:

[0062] 1. Preparation of the composite flexible film: 15 mg of bacterial cellulose was weighed into a beaker, 30 ml of deionized water was added, and the mixture was stirred for 1 h to disperse the bacterial cellulose evenly. Simultaneously, 2 mg of carbon nanotubes were weighed into a beaker, 10 ml of ethanol was added, and the mixture was sonicated in an ultrasonic machine for 0.5 h. The sonicated carbon nanotube solution was then added to the bacterial cellulose solution, and the mixture was stirred for 1 h to obtain a homogeneous mixed solution. The mixed solution was then poured into a vacuum filtration apparatus for film formation, yielding a composite flexible film with a diameter of 4.5 cm.

[0063] 2. Preparation of interfacial crosslinking agent: Add 9 ml of deionized water to a beaker and heat it in a water bath at 90°C. Weigh 1 g of polyvinyl alcohol (PVA, type 1799) and add it to the beaker in three portions, stirring for 1 hour until completely dissolved. Turn off the water bath heating switch and let the PVA solution cool naturally to remove air bubbles.

[0064] 3. Pressure-induced in-situ anchoring: A zinc metal sheet with a thickness of 150μm and a length and width of 6cm is cut and polished with 600-grit and 2000-grit sandpaper respectively to obtain a zinc substrate; 250μl of 10wt% PVA is dropped into the center of the zinc substrate, and a composite flexible film is covered on the PVA. A pressure of 10MPa is applied using a tablet press, so that the PVA permeates and fills the pores of the composite flexible film and the microstructure of the zinc substrate surface under the pressure, forming a three-layer integrated structure of "BC / CNT-PVA-Zn".

[0065] 4. Curing and shaping: The modified zinc anode is vacuum dried. The conditions of the vacuum drying oven are -0.1MPa, heating to 60℃, and holding for 1 hour. After drying, a modified zinc anode with high bonding strength is obtained.

[0066] Preparation of NH4V4O 10 Positive electrode: 2.106 g of NH4VO3 was dissolved in 90 mL of deionized water and stirred continuously at 80°C. Then, 3.4038 g of H2C2O4·2H2O was gradually added to the mixture, and stirring continued until the solution turned dark green. The resulting solution was placed in a polytetrafluoroethylene high-pressure reactor and reacted at 140°C for 48 hours. After the hydrothermal reaction, the precipitate was collected and thoroughly washed with deionized water, and finally dried at 60°C for 12 hours to obtain NVO powder. NVO powder, acetylene black, and PVDF were mixed at a mass ratio of 7:2:1 and dry-milled for 30 minutes, followed by the addition of NMP and milling for 10 minutes. The prepared slurry was uniformly coated onto a stainless steel mesh current collector and dried in a 90°C vacuum oven for 14 hours to obtain the NVO positive electrode.

[0067] Battery assembly: combining the modified zinc anode with NH4V4O 10 The positive electrode is cut into electrode sheets with a diameter of 12mm, according to the positive electrode shell, NH4V4O 10 The positive electrode, separator, electrolyte, modified zinc negative electrode, gasket, spring sheet, and negative electrode shell are assembled in sequence under a pressure of 500 psi to form a vanadium-based full cell.

[0068] Comparative Example 3

[0069] The positive electrode uses the same NH4V4O as in Example 3. 10 Positive electrode; the difference from Example 3 is that the preparation method of the zinc negative electrode was changed, and the zinc negative electrode was not modified. The specific method is as follows:

[0070] Zinc metal sheets with a thickness of 150μm and a length and width of 6cm were cut and polished with 600-grit and 2000-grit sandpaper respectively to obtain pure zinc negative electrodes; the zinc negative electrodes without thin film protection were cut into electrode sheets with a diameter of 12mm, and then processed according to the positive electrode shell, NH4V4O 10The positive electrode, separator, electrolyte, pure zinc negative electrode, gasket, spring sheet, and negative electrode shell are assembled in sequence under a pressure of 500 psi to form a vanadium-based full cell.

[0071] The test schemes and analysis results of Example 3 and Comparative Example 3 are as follows:

[0072] The vanadium-based full cells assembled in Example 3 and Comparative Example 3, with a yield of 2A g -1 Long-cycle constant current charge-discharge testing was conducted using current density. Figure 7 The performance curves for long-cycle testing show that the battery in Example 3 retains a capacity of over 88% and a coulombic efficiency of over 99% after 2000 cycles; the battery assembled in Comparative Example 3 retains a much lower capacity than that in Example 3 after 2000 cycles.

[0073] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a flexible thin-film interface-modified zinc anode based on pressure-induced permeation bonding, characterized in that, Includes the following steps: (1) Preparation of composite flexible film: After the bacterial cellulose solution and carbon material solution are thoroughly mixed, a composite flexible film with a three-dimensional porous network structure is prepared by vacuum filtration. (2) Pre-positioning of interfacial crosslinking agent: Polyvinyl alcohol is introduced as an interfacial crosslinking agent on the surface of zinc substrate; (3) Pressure-induced in-situ anchoring: The composite flexible film is covered on polyvinyl alcohol, and pressure is applied so that the polyvinyl alcohol permeates and fills the pores of the composite flexible film and the microstructure of the zinc substrate under the action of pressure, forming a "BC / C-PVA-Zn" three-layer integrated structure. (4) Curing and shaping: Heat treatment is carried out under vacuum conditions to remove the solvent and obtain a modified zinc anode with high bonding strength.

2. The preparation method according to claim 1, characterized in that, The bacterial cellulose solution in step (1) is prepared by placing bacterial cellulose in a beaker, adding a certain amount of deionized water, and stirring or ultrasonically dispersing for 1-1.5 hours to ensure uniform dispersion of the bacterial cellulose. The carbon material solution is prepared by placing carbon material in a beaker, adding a certain amount of ethanol, and stirring or ultrasonically dispersing for 0.5-1 hours.

3. The preparation method according to claim 2, characterized in that, The mass ratio of bacterial cellulose to carbon material is (5-15):

1.

4. The preparation method according to any one of claims 1-3, characterized in that, The carbon material is carbon nanotube, graphene, or carbon fiber.

5. The preparation method according to claim 1, characterized in that, The polyvinyl alcohol mentioned in step (2) is obtained by dissolving solid polyvinyl alcohol in a water bath at 90°C.

6. The preparation method according to claim 1, characterized in that, Step (3) of introducing polyvinyl alcohol onto the zinc substrate specifically involves dropping 5-15 wt% polyvinyl alcohol onto the zinc substrate, with a coating amount of 10-20 μL / cm². -2 .

7. The preparation method according to claim 1, characterized in that, The pressure applied in step (3) is to use a tablet press to compress the tablet at a pressure of 5-20 MPa.

8. The preparation method according to claim 1, characterized in that, The heat treatment in step (4) is a heating temperature of 50-80℃ and a heating time of 0.5-5h.

9. A flexible thin-film interface-modified zinc anode based on pressure-induced permeation bonding prepared by the preparation method according to any one of claims 1-8.

10. The application of a flexible thin-film interface-modified zinc anode based on pressure-induced permeation bonding prepared by the preparation method according to any one of claims 1-8 in an aqueous zinc-ion battery.

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