A method for preparing and applying a high-bonding-strength zinc anodic coating

Abstract

This invention discloses a method for preparing and applying a high-bonding-strength zinc anode coating. The aim is to address problems such as zinc dendrite formation on the zinc anode surface, hydrogen evolution reaction at the anode interface, and insufficient coating bonding strength. The preparation method includes: 1. Grinding the zinc foil; 2. Installing the substrate in a vacuum chamber and evacuating the vacuum; 3. Introducing argon gas for ion source cleaning, followed by bias cleaning; 4. Pre-deposition using a bias power supply and a DC pulse power supply; 5. First, depositing a transition layer by magnetron sputtering, then introducing reactive gas and depositing a functional layer by magnetron sputtering; 6. Performing in-situ heat treatment on the composite coating. The zinc anode coating prepared by this invention achieves uniform zinc ion deposition, significantly improving the cycle stability and electrochemical performance of aqueous zinc-ion batteries. The assembled Ti / TiN@Zn symmetric battery achieves a cycle life of 720 hours at high current density, and the assembled full cell retains a capacity of up to 96.6% after 1500 cycles at high current density.

Description

Technical Field

[0001] This invention belongs to the field of functional coatings and aqueous zinc-ion batteries, and in particular relates to a method for preparing a zinc anode coating with high bonding strength and its application in aqueous zinc-ion batteries. Background Technology

[0002] With the increasing scarcity of lithium resources and growing safety concerns, aqueous zinc-ion batteries have become increasingly popular due to the high theoretical capacity (820 mAh g) of their zinc anodes. -1 Or 5855 mAh cm -3 With its advantages of high safety and low cost, zinc-ion batteries are widely considered one of the most promising next-generation energy storage devices. However, zinc anodes themselves suffer from limited nucleation sites and uneven zinc ion deposition, leading to uncontrolled dendrite growth and exacerbating side reactions at the electrode / electrolyte interface. These problems severely limit the cycle stability and lifespan of aqueous zinc-ion batteries. Therefore, there is an urgent need to develop effective strategies to control the interfacial behavior between the zinc anode and the electrolyte to achieve dendrite-free, highly stable, and controllable zinc deposition.

[0003] Constructing a protective coating is considered a particularly effective approach. A stable protective coating can act as a physical barrier, reducing direct contact between the zinc anode and water molecules in the electrolyte, thereby effectively suppressing side reactions. Simultaneously, it can homogenize the surface electric field and modulate the Zn content. 2+ The concentration distribution and the optimized interfacial electrochemical environment provide more nucleation sites while guiding uniform zinc deposition. This mitigates the degradation in cycling performance caused by dendrite growth and interfacial side reactions.

[0004] In recent years, with the deepening research on suppressing zinc dendrites and hydrogen evolution reaction, various coating materials and coating preparation technologies have been applied to the surface modification of zinc anodes. However, the zinc anode undergoes drastic volume changes during charge and discharge, and coatings with insufficient bonding strength are prone to cracking and peeling, leading to rapid performance degradation and even safety hazards. Therefore, constructing a robust coating with strong interfacial bonding is crucial for achieving long-term stable cycling of aqueous zinc-ion batteries. Magnetron sputtering technology has been widely used in recent years due to its advantages of high controllability, low deposition temperature, wide range of plating substrates, and good mechanical and tribological properties. Studies have shown that the coating structure has a significant impact on the bonding strength, and controlling the coating structure through magnetron sputtering technology can effectively improve its bonding strength. This provides a new and effective approach to solving the interfacial stability and electric field uniformity of zinc anodes. Summary of the Invention

[0005] The present invention aims to solve the problems of short cycle life and insufficient coating bonding strength caused by zinc dendrites on the zinc anode surface and hydrogen evolution reaction at the anode interface, and provides a method for preparing and applying a zinc anode coating with high bonding strength.

[0006] The method for preparing the high-bonding-strength zinc anolyte coating of the present invention is carried out according to the following steps:

[0007] Step 1: Sand the zinc foil with sandpaper, cut the sanded zinc foil into zinc discs using a cutting machine, and obtain the substrate after ultrasonic cleaning and drying.

[0008] Step 2: Install the substrate in the vacuum chamber of the magnetron sputtering apparatus and evacuate to 1.0 × 10⁻⁶. -2 Below Pa, heat the vacuum chamber to 200 ~ 400℃;

[0009] Step 3: Introduce argon gas into the vacuum chamber after evacuation, turn on the ion source power supply to perform ion source cleaning, and then turn on the bias power supply to perform bias cleaning.

[0010] Step 4: Adjust the argon flow rate to 100 ~ 120 sccm, control the deposition pressure to 0.8 ~ 1.0 Pa, and turn on the bias power supply and DC pulse power supply for pre-deposition;

[0011] Step 5: After pre-deposition, keep the DC pulse power supply on, first deposit the transition layer by magnetron sputtering, then control the argon flow rate to 100 ~ 110 sccm, the reactive gas flow rate to 2 ~ 20 sccm, and maintain the deposition gas pressure at 0.8 ~ 1.0 Pa, then deposit the functional layer by magnetron sputtering to obtain the composite coating.

[0012] Step 6: Perform in-situ heat treatment on the composite coating at a temperature of 200 ~ 400℃ to deposit a high-bonding-strength zinc anode coating on the substrate.

[0013] In step five, the transition layer is an Al layer, a Cr layer, or a Ti layer; the functional layer is an aluminum nitride layer, a chromium nitride layer, a titanium nitride layer, an aluminum carbide layer, a chromium carbide layer, or a titanium carbide layer.

[0014] The application of the high-bonding-strength zinc anode coating of this invention is to deposit a high-bonding-strength zinc anode coating on zinc foil using a magnetron sputtering process as the anode, and to apply it to aqueous zinc-ion batteries.

[0015] This invention uses zinc foil with a high-bonding-strength zinc anolyte coating as the anode, and employs ammonium vanadate (NH4V4O) 10 The cathode, glass fiber diaphragm, and ZnSO4 electrolyte are assembled to form an aqueous zinc-ion battery.

[0016] The high bonding strength zinc anode coating of the present invention is formed by magnetron sputtering deposition of a metal target. The coating is a composite coating consisting of a transition layer and a functional layer, wherein the transition layer is an Al layer, a Cr layer or a Ti layer, and the functional layer is an aluminum nitride layer, a chromium nitride layer, a titanium nitride layer, an aluminum carbide layer, a chromium carbide layer or a titanium carbide layer.

[0017] In the preparation method of the high-bonding-strength zinc anode coating of this invention, the flow rate of reactive gas needs to be controlled during the coating deposition process to achieve the composition of the composite coating. The metal layer, as a transition coating, effectively enhances the bonding strength between the coating and the zinc substrate, thereby improving the cycle stability of the anode during battery cycling. The nitride or carbide functional layer, due to its excellent conductivity and columnar crystal structure, effectively regulates the surface electric field of the zinc anode, thereby controlling the zinc deposition behavior and achieving uniform zinc deposition. Simultaneously, this composite coating isolates the zinc anode from direct contact with the electrolyte, effectively suppressing the hydrogen evolution reaction at the zinc anode.

[0018] The method for preparing the high-bonding-strength zinc anolyte coating of the present invention has the following beneficial technical effects:

[0019] 1. The present invention provides a zinc anode coating with high bonding strength. The coating is a composite coating consisting of a transition layer and a functional layer. This composite structure is beneficial to improving the bonding strength of the coating and improving the performance of the zinc anode.

[0020] 2. This zinc anode coating with high bonding strength not only enhances the bonding strength between the coating and the substrate but also unifies the surface electric field and regulates the deposition behavior of zinc ions. This effectively suppresses the formation of zinc dendrites and the hydrogen evolution reaction, significantly improving the cycle stability and electrochemical performance of aqueous zinc-ion batteries. The assembled Ti / TiN@Zn symmetric battery achieved a cycle stability of 10 mA / cm². -2 A cycle life of 720 h can be achieved at high current densities; using Ti / TiN@Zn as the anode, NH4V4O 10 Ti / TiN@Zn||NVO full cells assembled with (NVO) as the cathode at a current density of 5 A g -1 After 1500 cycles, the capacity retention rate remained as high as 96.6%. Furthermore, the rate performance and corrosion resistance of the aqueous zinc-ion battery were also improved. This provides a feasible strategy for the design of highly stable zinc anodes and has broad prospects for practical applications. Attached Figure Description

[0021] Figure 1 Micro-scratches are shown in the images of the TiN and Ti / TiN coatings prepared in Examples 1 and 2.

[0022] Figure 2 This is a scanning electron microscope image of the Ti / TiN coating prepared in Example 2;

[0023] Figure 3 The GIXRD patterns of the TiN and Ti / TiN coatings prepared in Examples 1 and 2 are shown.

[0024] Figure 4The symmetric cell assembled with the Ti / TiN@Zn electrode prepared in Example 2 was tested at 10 mA cm⁻¹. -2 Comparison of cycling performance at current density;

[0025] Figure 5 Comparison of electrochemical impedance spectroscopy (EIS) of the full cell assembled with the Ti / TiN@Zn anode prepared in Example 2;

[0026] Figure 6 The full cell assembled with the Ti / TiN@Zn anode prepared in Example 2 was tested at 10 A g. -1 The graph shows the test performance of charge-discharge cycle under the specified current density. Detailed Implementation

[0027] Specific Implementation Method 1: The preparation method of the high-bonding-strength zinc anolyte coating in this implementation method is carried out according to the following steps:

[0028] Step 1: Sand the zinc foil with sandpaper, cut the sanded zinc foil into zinc discs using a cutting machine, and obtain the substrate after ultrasonic cleaning and drying.

[0029] Step 2: Install the substrate in the vacuum chamber of the magnetron sputtering apparatus and evacuate to 1.0 × 10⁻⁶. -2 Below Pa, heat the vacuum chamber to 200 ~ 400℃;

[0030] Step 3: Introduce argon gas into the vacuum chamber after evacuation, turn on the ion source power supply to perform ion source cleaning, and then turn on the bias power supply to perform bias cleaning.

[0031] Step 4: Adjust the argon flow rate to 100 ~ 120 sccm, control the deposition pressure to 0.8 ~ 1.0 Pa, and turn on the bias power supply and DC pulse power supply for pre-deposition;

[0032] Step 5: After pre-deposition, keep the DC pulse power supply on, first deposit the transition layer by magnetron sputtering, then control the argon flow rate to 100 ~ 110 sccm, the reactive gas flow rate to 2 ~ 20 sccm, and maintain the deposition gas pressure at 0.8 ~ 1.0 Pa, then deposit the functional layer by magnetron sputtering to obtain the composite coating.

[0033] Step 6: Perform in-situ heat treatment on the composite coating at a temperature of 200 ~ 400℃ to deposit a high-bonding-strength zinc anode coating on the substrate.

[0034] In step five, the transition layer is an Al layer, a Cr layer, or a Ti layer; the functional layer is an aluminum nitride layer, a chromium nitride layer, a titanium nitride layer, an aluminum carbide layer, a chromium carbide layer, or a titanium carbide layer.

[0035] In step five of this embodiment, the transition layer is preferably a Ti layer, the functional layer is preferably a titanium nitride layer, and the reactive gas used for magnetron sputtering deposition of the titanium nitride layer is nitrogen.

[0036] In this embodiment, a transition layer and a functional layer are sequentially prepared on a zinc anode substrate using magnetron sputtering technology to form a composite coating. The reactive gas used in the magnetron sputtering deposition of the functional layer is nitrogen or methane. In the vacuum chamber of magnetron sputtering, the deposited composite coating is subjected to in-situ heat treatment to obtain a zinc anode coating with high bonding strength.

[0037] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that in step one, anhydrous ethanol and acetone are used sequentially to ultrasonically clean the zinc discs for 10 to 15 minutes respectively.

[0038] Specific Implementation Method Three: This implementation method differs from Specific Implementation Method One or Two in that step two involves evacuating the vacuum to 3 × 10⁻⁶. -3 Pa, heating the vacuum chamber to 200 ℃.

[0039] Specific Implementation Method Four: This implementation method differs from Specific Implementation Methods One to Three in that in step three, the current of the ion source power supply is controlled to be 0.3 A with a duty cycle of 70%; and the voltage of the bias power supply is controlled to be 800 V with a duty cycle of 50%.

[0040] Specific Implementation Method 5: This implementation method differs from Specific Implementation Methods 1 to 4 in that the ion source cleaning time in step 3 is controlled to be 10 to 15 minutes; the bias cleaning time is 10 to 15 minutes.

[0041] Specific Implementation Method Six: This implementation method differs from Specific Implementation Methods One to Five in that the voltage of the bias power supply in step four is 200 V, the power supply power is 1000 W, and the pre-deposition time is 3 to 5 min.

[0042] Specific Implementation Method Seven: This implementation method differs from Specific Implementation Methods One to Six in that the thickness of the transition layer deposited in step five is 10 to 100 nm.

[0043] Specific Implementation Method Eight: This implementation method differs from Specific Implementation Methods One to Seven in that the thickness of the functional layer in step five is 400 ~ 600 nm.

[0044] Specific Implementation Method Nine: This implementation method differs from Specific Implementation Methods One to Eight in that the in-situ heat treatment time in step six is ​​1 to 2 hours.

[0045] Example 1: The preparation method of the TiN coating on the zinc anode by magnetron sputtering in this example is carried out according to the following steps:

[0046] Step 1: Polish the 0.2 mm thick commercial zinc foil with 3000 grit sandpaper to remove the surface oxide layer, cut it into 16 mm diameter round pieces, and ultrasonically clean the zinc foil electrode with anhydrous ethanol and acetone for 15 min respectively. After drying, the substrate is obtained.

[0047] Step 2: Install the substrate in the vacuum chamber of the magnetron sputtering apparatus and evacuate to 5 × 10⁻⁶. -3 Pa, then the vacuum chamber was heated to 200°C, and evacuated again to 3 × 10 Pa. -3 Pa;

[0048] Step 3: Introduce argon gas into the vacuum chamber after evacuation, control the argon gas flow rate to 20 sccm, turn on the ion source power supply (current 0.3 A, duty cycle 70%) to perform ion source cleaning for 10 min, then turn off the ion source power supply, and then turn on the bias power supply (voltage 800 V, duty cycle 50%) to perform bias cleaning for 10 min.

[0049] Step 4: Adjust the argon flow rate to 110 sccm, control the deposition pressure to 1.0 Pa, turn on the bias power supply and DC pulse power supply, set the bias power supply voltage to 200 V and the power supply power to 1000 W, and perform pre-deposition for 3 min.

[0050] Step 5: After pre-deposition, keep the DC pulse power supply on, gradually reduce the argon flow rate and increase the nitrogen flow rate, then control the argon flow rate to 110 sccm and the nitrogen flow rate to 15 sccm, keep the deposition pressure at 1.0 Pa, and use magnetron sputtering to deposit the TiN layer to obtain a TiN coating with a thickness of about 500 nm.

[0051] Step 6: Perform in-situ heat treatment on the TiN coating at 300℃ for 2 hours to deposit a zinc anode coating on the substrate.

[0052] Example 2: The preparation method of the high bonding strength zinc anode Ti / TiN coating in this example is carried out according to the following steps:

[0053] Step 1: Polish the 0.2 mm thick commercial zinc foil with 3000 grit sandpaper to remove the surface oxide layer, cut it into 16 mm diameter round pieces, and ultrasonically clean the zinc foil electrode with anhydrous ethanol and acetone for 15 min respectively. After drying, the substrate is obtained.

[0054] Step 2: Install the substrate in the vacuum chamber of the magnetron sputtering apparatus and evacuate to 5 × 10⁻⁶. -3 Pa, then the vacuum chamber was heated to 200°C, and evacuated again to 3 × 10 Pa. -3 Pa;

[0055] Step 3: Introduce argon gas into the vacuum chamber after evacuation, control the argon gas flow rate to 20 sccm, turn on the ion source power supply (current 0.3 A, duty cycle 70%) to perform ion source cleaning for 10 min, then turn off the ion source power supply, and then turn on the bias power supply (voltage 800 V, duty cycle 50%) to perform bias cleaning for 10 min.

[0056] Step 4: Adjust the argon flow rate to 110 sccm, control the deposition pressure to 1.0 Pa, turn on the bias power supply and DC pulse power supply, set the bias power supply voltage to 200 V and the power supply power to 1000 W, and perform pre-deposition for 3 min.

[0057] Step 5: After the pre-deposition is completed, keep the DC pulse power supply on and first deposit a Ti transition layer with a thickness of about 50 nm by magnetron sputtering. Then, control the argon flow rate to 110 sccm, control the nitrogen flow rate to 15 sccm, keep the deposition pressure at 1.0 Pa, and then deposit a TiN layer by magnetron sputtering to obtain a Ti / TiN coating with a thickness of about 500 nm.

[0058] Step 6: Perform in-situ heat treatment on the Ti / TiN coating at 300℃ for 2 h to deposit a high-bonding-strength zinc anode coating (Ti / TiN coating) on ​​the substrate.

[0059] Bond strength analysis: The bonding strength of the coatings was determined using a micro-scratch test. Micro-scratch test images of the TiN and Ti / TiN coatings prepared in Examples 1 and 2 are shown below. Figure 1 As shown, by critering the coating surface with a continuously increasing load while monitoring friction and acoustic emission signals, the critical load at which the coating fails (such as cracking or peeling) is precisely determined, thus quantifying the coating's bonding strength. The TiN@Zn anode coating exhibited numerous cracks and significant peeling shortly after contact with the indenter, indicating low bonding strength. In contrast, the Ti / TiN@Zn anode coating demonstrated higher bonding strength, with critical load values ​​(Lc2 and Lc3) of 6048 mN and 7947 mN, respectively. This is attributed to the addition of the Ti layer, which resulted in a better match between the coating and the substrate's coefficients of thermal expansion, leading to lower internal stress and reducing the risk of coating peeling. These results confirm that the composite structure can significantly improve the bonding strength between the coating and the substrate, thereby enhancing the coating's protective ability for the zinc anode.

[0060] Scanning electron microscopy analysis: The surface morphology of the Ti / TiN coating was studied using a field emission scanning electron microscope (FE-SEM, Zeiss Gemini SEM 360). The composite Ti / TiN coating was observed using scanning electron microscopy (SEM), such as... Figure 2As shown, the coating surface morphology consists of dense and uniform columnar crystal clusters. To determine the coating thickness, Figure 2 (Right) shows a scanning electron microscope image of the cross-section of the coating. The Ti / TiN coating is 526 nm thick, demonstrating that the coating has a columnar structure and a smooth bond with the substrate. This is an ideal interfacial bond with good adhesion strength. Furthermore, the porous structure composed of these columnar clusters allows Zn... 2+ Ions diffuse freely through the coating, thereby modulating the Zn content. 2+ Uniform deposition.

[0061] Crystal phase analysis: The crystal phase of the Ti / TiN coating was analyzed using grazing incidence X-ray diffraction (GIXRD, Rigaku-Smart Lab), and Cu Kα radiation was performed. The 2θ range was 5°–90°, the scan rate was 5° / min, and the incident angle was 1°. The GIXRD patterns of the TiN and Ti / TiN coatings prepared in Examples 1 and 2 are shown below. Figure 3 As shown. The composition of TiN and Ti / TiN coatings was characterized using grazing incidence X-ray diffraction (GIXRD), as follows. Figure 3 As shown, the diffraction peaks at 61.775° and 74.021° in the spectrum are consistent with the TiN standard card face (TiN#87-0628), corresponding to the (220) and (311) crystal planes of TiN, respectively, proving that the TiN and Ti / TiN coatings are mainly composed of TiN.

[0062] Electrochemical Measurement:

[0063] Electrochemical performance tests in this work were all conducted using CR2032 coin cells. In the symmetrical cell tests, the working electrode and counter electrode were both Zn and Ti / TiN@Zn, respectively, with a 2 M ZnSO4 aqueous solution as the electrolyte and glass fiber (Whatman, UK) as the separator. The electrochemical performance was measured at 10 mA cm⁻¹. -2 The current density was used to test the cycle performance of the battery. The cycle performance of the symmetrical battery was as follows: Figure 4 As shown, the Ti / TiN@Zn anode exhibits excellent stable cycle life (720 h). This indicates that the Ti / TiN coating can continuously maintain the cycle stability of the zinc anode during high-speed electroplating / stripping.

[0064] To evaluate the practical applicability of magnetron sputtering high-bonding-strength Ti / TiN coatings, a full-cell test was conducted using Zn and Ti / TiN@Zn as anodes, NVO as cathode, 2 M ZnSO4 aqueous solution as electrolyte, and glass fiber (Whatman, UK) as separator. Electrochemical impedance spectroscopy (EIS) was performed on the full cells, and the reaction kinetics were further investigated using EIS. Figure 5), Figure 5 The Nyquist plots from 0.01 Hz to 100 kHz are displayed. At high frequencies, the intercept on the Z' axis represents the internal resistance (Rs) of the electrode material, composed of the electrolyte resistance and intrinsic resistance. As shown in the magnified image, the Rs for Ti / TiN@Zn||NVO is 1.28 Ω, slightly lower than the 3.52 Ω for Bare Zn||NVO. In the high-to-mid-frequency region, the diameter of the semicircle represents the charge transport resistance (Rct), which is a combination of the electrolyte, electrode, and series resistance. Figure 5 It can be seen that the charge transfer resistance of Ti / TiN@Zn||NVO is 7.15 Ω, which is much lower than that of Bare Zn||NVO (259.2 Ω). This indicates that the reaction kinetics are faster and the electrochemical activity is higher due to the effect of the Ti / TiN layer.

[0065] The cathode is prepared by using ammonium vanadate (NH4V4O) 10 The powder was mixed with Super P and polyvinylidene fluoride (PVDF) in an N-methylpyrrolidone (NMP) at a mass ratio of 7:2:1, then cast onto a stainless steel mesh and dried overnight in a vacuum oven at 60°C. The mass loading of NVO was approximately 1.5 mg / cm³. -2 To test the cycle performance of a Bare Zn||NVO full cell, at 5 Ag... -1 The charge-discharge cycle performance of the full battery was tested at a current density, and the charge-discharge cycle comparison graph is shown below. Figure 6 As shown. BareZn||NVO full battery at 10 A g -1 After cycling at high current density for 1500 cycles, the capacity rapidly decreased to 71.8 mAhg. -1 The Ti / TiN@Zn||NVO full cell maintained a capacity of 205 mAh g. -1 It has a high capacity and a capacity retention rate of up to 96.6%, while the capacity retention rate of Bare Zn||NVO full battery is only 37.2%.

[0066] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a high-bonding-strength zinc anolyte coating, characterized in that... The method for preparing the high-bonding-strength zinc anolyte coating is carried out according to the following steps: Step 1: Sand the zinc foil with sandpaper, cut the sanded zinc foil into zinc discs using a cutting machine, and obtain the substrate after ultrasonic cleaning and drying. Step 2: Install the substrate in the vacuum chamber of the magnetron sputtering apparatus and evacuate to 1.0 × 10⁻⁶. -2 Below Pa, heat the vacuum chamber to 200 ~ 400℃; Step 3: Introduce argon gas into the vacuum chamber after evacuation, turn on the ion source power supply to perform ion source cleaning, and then turn on the bias power supply to perform bias cleaning. Step 4: Adjust the argon flow rate to 100 ~ 120 sccm, control the deposition pressure to 0.8 ~ 1.0 Pa, and turn on the bias power supply and DC pulse power supply for pre-deposition; Step 5: After pre-deposition, keep the DC pulse power supply on, first deposit the transition layer by magnetron sputtering, then control the argon flow rate to 100 ~ 110 sccm, the reactive gas flow rate to 2 ~ 20 sccm, and maintain the deposition pressure at 0.8 ~ 1.0 Pa, then deposit the functional layer by magnetron sputtering to obtain the composite coating. Step 6: Perform in-situ heat treatment on the composite coating at a temperature of 200 ~ 400℃ to deposit a high-bonding-strength zinc anode coating on the substrate. In step five, the transition layer is an Al layer, a Cr layer, or a Ti layer; the functional layer is an aluminum nitride layer, a chromium nitride layer, a titanium nitride layer, an aluminum carbide layer, a chromium carbide layer, or a titanium carbide layer.

2. The method for preparing a high-bonding-strength zinc anolyte coating according to claim 1, characterized in that... In step one, the zinc discs are ultrasonically cleaned for 10 to 15 minutes each using anhydrous ethanol and acetone, respectively.

3. The method for preparing a high-bonding-strength zinc anolyte coating according to claim 1, characterized in that... In step two, a vacuum is drawn to 3 × 10⁻⁶. -3 Pa, heating the vacuum chamber to 200 ℃.

4. The method for preparing a high-bonding-strength zinc anolyte coating according to claim 1, characterized in that... In step three, the current of the ion source power supply is controlled to be 0.3 A with a duty cycle of 70%; the voltage of the bias power supply is controlled to be 800 V with a duty cycle of 50%.

5. The method for preparing a high-bonding-strength zinc anolyte coating according to claim 1, characterized in that... In step three, the ion source cleaning time is controlled to be 10-15 min; the bias cleaning time is 10-15 min.

6. The method for preparing a high-bonding-strength zinc anolyte coating according to claim 1, characterized in that... In step four, the bias power supply voltage is controlled at 200 V, the power supply power is 1000 W, and the pre-deposition time is 3 to 5 minutes.

7. The method for preparing a high-bonding-strength zinc anolyte coating according to claim 1, characterized in that... The thickness of the transition layer deposited in step five is 10 ~ 100 nm.

8. The method for preparing a high-bonding-strength zinc anolyte coating according to claim 1, characterized in that... The thickness of the functional layer deposited in step five is 400 ~ 600 nm.

9. The method for preparing a high-bonding-strength zinc anolyte coating according to claim 1, characterized in that... The in-situ heat treatment time in step six is ​​1 to 2 hours.

10. The application of the high-bonding-strength zinc anolyte coating prepared according to claim 1, characterized in that... Zinc foil with a high bonding strength zinc anode coating is used as an anode in aqueous zinc-ion batteries.

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