Preparation method of polyoxovanadate-based hydrophobic two-dimensional superstructure and application thereof in water-based zinc ion battery positive electrode
By preparing a hydrophobic two-dimensional superstructure based on vanadium-oxygen clusters, the problems of vanadium dissolution, poor reversibility, and short cycle life of aqueous zinc-ion battery cathode materials were solved, and the specific capacity and cycle stability were significantly improved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- JILIN UNIVERSITY
- Filing Date
- 2024-01-12
- Publication Date
- 2026-06-23
AI Technical Summary
Existing vanadium-oxygen cluster cathode materials suffer from problems such as vanadium dissolution, poor reversibility, low specific capacity, and short cycle life in aqueous zinc-ion batteries.
A method for preparing a hydrophobic two-dimensional superstructure based on vanadium-oxygen clusters was adopted. TPA was protonated and then combined with (V10O28)6- through electrostatic interaction to form a yellow flocculent precipitate. After drying, the composite material was obtained and used as the positive electrode of an aqueous zinc-ion battery.
The specific capacity and cycling stability of the material were significantly improved. After one cycle at 0.1 A/g, the specific capacity of TPA-V10 reached 448 mAh/g, and it remained above 300 mAh/g after 100 cycles. In addition, the material has hydrophobic properties, which prevents vanadium dissolution.
Smart Images
Figure CN117894944B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of aqueous zinc-ion battery technology. Background Technology
[0002] Aqueous zinc-ion batteries are a novel type of multivalent ion battery based on aqueous electrolytes. They possess advantages such as reliable safety, low cost, environmental friendliness, high theoretical capacity (820 mAh / g), and low redox potential (-0.76 V compared to the standard hydrogen electrode), making them highly valuable and promising for applications in emerging large-scale energy storage fields such as energy storage grids. However, the cathode materials for aqueous zinc-ion batteries still face challenges such as irreversible phase transitions, metal ion dissolution, and poor cycle stability. Therefore, one of the challenges in developing aqueous zinc-ion batteries is designing cathode materials with superior performance.
[0003] Vanadium-based compounds, as commonly used cathode materials for aqueous zinc-ion batteries, exhibit high specific capacity and high cycle rate, making them promising representatives among aqueous zinc-ion battery cathode materials. Multivanadium oxide clusters (POVs) offer the following advantages as cathode materials: (1) their flexible valence states (+2 to +5) allow for the construction of various cluster structures; (2) they possess strong redox capabilities; (3) they maintain a stable framework structure even after undergoing reversible redox reactions; and (4) the cluster structures have a larger specific surface area, providing more ion migration and storage sites. However, the application of known multivanadium oxide cluster cathode materials in aqueous zinc-ion batteries still faces challenges such as insufficient capacity, short cycle life, poor reversibility, and vanadium cluster dissolution. Therefore, developing an aqueous zinc-ion battery cathode material that can leverage the inherent advantages of multivanadium oxide clusters is of great significance. Summary of the Invention
[0004] This invention aims to address the problems of poor reversibility, low specific capacity, and short cycle life caused by vanadium dissolution in existing vanadium-based compounds used as cathode materials in aqueous zinc-ion batteries. It provides a method for preparing a hydrophobic two-dimensional superstructure based on vanadium-oxygen clusters and its application in the cathode of aqueous zinc-ion batteries.
[0005] A method for preparing a hydrophobic two-dimensional superstructure based on a vanadium-oxygen cluster comprises the following steps:
[0006] 1. Add hydrochloric acid solution to 4-amino-p-terphenyl and seal the reactor. React at room temperature for 15 min to 20 min. Then, sonicate at room temperature and power of 100 W to 120 W for 5 min to 10 min to obtain protonated TPA. Dissolve the protonated TPA in methanol solution and then add water to obtain a protonated TPA solution.
[0007] 2. At room temperature, (NH4)6V 10 O28 ·6H2O dissolves in water, then methanol solution is added to obtain V 10 Solution;
[0008] 3. At room temperature, the protonated TPA solution is reacted with V 10 The solutions were mixed to obtain a yellow flocculent precipitate. The yellow flocculent precipitate was allowed to stand, filtered, and dried to obtain a hydrophobic two-dimensional superstructure based on vanadium-oxygen clusters.
[0009] Application: The hydrophobic two-dimensional superstructure based on vanadium-oxygen clusters is used to prepare the cathode of an aqueous zinc-ion battery.
[0010] The beneficial effects of this invention are:
[0011] This invention discloses a method for preparing a hydrophobic two-dimensional superstructure based on a multivanadium-oxygen cluster. The method first protonates TPA to give it a positive charge, and then reacts it with (NH4)6V... 10 O 28 ·6H2O (abbreviated as V) 10 The negatively charged [V] 10 O 28 ] 6- The composite material, formed by electrostatic interactions, binds together to form a yellow flocculent precipitate. Characterization of the dried product reveals that it is composed of two-dimensional nanoscale sheets, thus possessing a large specific surface area and numerous zinc ion migration and storage sites, enhancing its electrochemical energy storage performance. Furthermore, as a composite of organic and inorganic materials, the material exhibits hydrophobic properties, preventing vanadium dissolution and significantly improving its stability in aqueous electrolyte environments. The aforementioned preparation method is simple, easy to operate and repeat, and possesses broad applicability, making it suitable for large-scale production and demonstrating promising application prospects.
[0012] This invention also discloses the application of the aforementioned hydrophobic two-dimensional superstructure based on vanadium-oxygen clusters in the cathode of aqueous zinc-ion batteries. Due to the material's hydrophobic properties and large specific surface area, when used as a cathode material in aqueous zinc-ion batteries, this material significantly improves the specific capacity and cycle stability (TPA-V) of the battery system. 10 It is fully activated after one cycle at 0.1 A / g, with a fully activated specific capacity of 448 mAh / g. After 100 cycles, its capacity remains above 300 mAh / g. (TPA-V) 10 The composite of vanadium-oxygen clusters and organic materials not only possesses the advantages of vanadium-oxygen clusters, such as abundant valence, large specific surface area, and numerous active sites, but also the hydrophobicity of organic materials. In summary, the hydrophobic two-dimensional superstructure based on vanadium-oxygen clusters—TPA-V 10 The electrochemical performance of aqueous zinc-ion batteries, including specific capacity and cycle stability, has been significantly improved.
[0013] Instruction manual illustrations
[0014] Figure 1 TPA-V prepared in Example 1 10 Images under a scanning electron microscope (SEM);
[0015] Figure 2 TPA-V prepared according to Example 1 10 The graph shows the cycle performance of a coin cell with positive electrode active material, after 100 cycles at a current density of 0.1 A / g. 1 is the coulombic efficiency curve and 2 is the discharge specific capacity curve.
[0016] Figure 3 TPA-V prepared according to Example 1 10 The graph shows the cycle performance of a coin cell with positive electrode active material, after 600 cycles at a current density of 2A / g. 1 is the coulombic efficiency curve, and 2 is the discharge specific capacity curve.
[0017] Figure 4 TPA-V prepared in Example 1 10 X-ray diffraction images, a is the XRD pattern in the small-angle region of 2-10 degrees, and b is the XRD pattern in the 5-40 degree region.
[0018] Figure 5 For V 10 Protonated TPA prepared in step one of Example 1 and TPA-V prepared in Example 1 10 Fourier transform infrared spectrum;
[0019] Figure 6 The protonated TPA prepared in step one of Example 1 and the TPA-V prepared in Example 1. 10 The hydrogen nuclear magnetic spectrum image;
[0020] Figure 7 TPA-V prepared in Example 1 10 Images under a transmission electron microscope (TEM);
[0021] Figure 8 TPA-V prepared in Example 1 10 High-resolution images under a transmission electron microscope (TEM);
[0022] Figure 9 The results are the contact angle test results for the positive electrode, where a represents the TPA-V prepared using Example 1. 10 The prepared positive electrode, b is the value of V 10 The prepared positive electrode sheet;
[0023] Figure 10 For V 10 and TPA-V prepared in Example 110 The BET test results. Detailed Implementation
[0024] Specific Implementation Method 1: This implementation method is a method for preparing a multivanadium-oxygen cluster-based hydrophobic two-dimensional superstructure, which is carried out according to the following steps:
[0025] 1. Add hydrochloric acid solution to 4-amino-p-terphenyl and seal the reactor. React at room temperature for 15 min to 20 min. Then, sonicate at room temperature and power of 100 W to 120 W for 5 min to 10 min to obtain protonated TPA. Dissolve the protonated TPA in methanol solution and then add water to obtain a protonated TPA solution.
[0026] 2. At room temperature, (NH4)6V 10 O 28 ·6H2O dissolves in water, then methanol solution is added to obtain V 10 Solution;
[0027] 3. At room temperature, the protonated TPA solution is reacted with V 10 The solutions were mixed to obtain a yellow flocculent precipitate. The yellow flocculent precipitate was allowed to stand, filtered, and dried to obtain a hydrophobic two-dimensional superstructure based on vanadium-oxygen clusters.
[0028] The beneficial effects of this embodiment are:
[0029] This embodiment discloses a method for preparing a hydrophobic two-dimensional superstructure based on a multivanadium-oxygen cluster. The method first protonates TPA to give it a positive charge, and then reacts it with (NH4)6V... 10 O 28 ·6H2O (abbreviated as V) 10 The negatively charged [V] 10 O 28 ] 6- The composite material, formed by electrostatic interactions, binds together to form a yellow flocculent precipitate. Characterization of the dried product reveals that it is composed of two-dimensional nanoscale sheets, thus possessing a large specific surface area and numerous zinc ion migration and storage sites, enhancing its electrochemical energy storage performance. Furthermore, as a composite of organic and inorganic materials, the material exhibits hydrophobic properties, preventing vanadium dissolution and significantly improving its stability in aqueous electrolyte environments. The aforementioned preparation method is simple, easy to operate and repeat, and possesses broad applicability, making it suitable for large-scale production and demonstrating promising application prospects.
[0030] This embodiment also discloses the application of the above-mentioned hydrophobic two-dimensional superstructure based on vanadium-oxygen clusters in the cathode of an aqueous zinc-ion battery. Due to the hydrophobic properties and large specific surface area of the material, when used as a cathode material in an aqueous zinc-ion battery, it significantly improves the specific capacity and cycle stability (TPA-V) of the battery system. 10 It is fully activated after one cycle at 0.1 A / g, with a fully activated specific capacity of 448 mAh / g. After 100 cycles, its capacity remains above 300 mAh / g. (TPA-V) 10 The composite of vanadium-oxygen clusters and organic materials not only possesses the advantages of vanadium-oxygen clusters, such as abundant valence, large specific surface area, and numerous active sites, but also the hydrophobicity of organic materials. In summary, the hydrophobic two-dimensional superstructure based on vanadium-oxygen clusters—TPA-V 10 The electrochemical performance of aqueous zinc-ion batteries, including specific capacity and cycle stability, has been significantly improved.
[0031] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that the concentration of the hydrochloric acid solution mentioned in step one is 10 mol / L to 14 mol / L. Everything else is the same as in Specific Implementation Method One.
[0032] Specific Implementation Method 3: This implementation method differs from Specific Implementation Method 1 or 2 in that: the molar ratio of 4-amino-p-terphenyl to the volume of hydrochloric acid solution in step 1 is 6 mmol:(1-3) mL; the molar ratio of 4-amino-p-terphenyl to the total volume of methanol and water in step 1 is 6 mmol:(200-300) mL. Everything else is the same as in Specific Implementation Method 1 or 2.
[0033] Specific Implementation Method Four: This implementation method differs from Specific Implementation Methods One to Three in that: the (NH4)6V mentioned in step two... 10 O 28 The molar ratio of 6H2O to the total volume of methanol and water is 1 mmol:(90-300) mL. Other aspects are the same as in embodiments one through three.
[0034] Specific Implementation Method Five: This implementation method differs from Specific Implementation Methods One to Four in that the volume ratio of methanol to water in steps one and two is (2-3):1. Everything else is the same as in Specific Implementation Methods One to Four.
[0035] Specific Implementation Method Six: This implementation method differs from Specific Implementation Methods One through Five in that: in step three, the protonated TPA solution contains protonated TPA and V... 10 (NH4)6V in solution 10 O 28The molar ratio of ·6H2O is 6:(1-3). Other aspects are the same as in embodiments one through five.
[0036] Specific Implementation Method Seven: This implementation method is the application of a multivanadium-oxygen cluster-based hydrophobic two-dimensional superstructure in the positive electrode of an aqueous zinc-ion battery. The positive electrode of an aqueous zinc-ion battery is prepared using a multivanadium-oxygen cluster-based hydrophobic two-dimensional superstructure.
[0037] Specific Implementation Method Eight: This implementation method differs from Specific Implementation Method Seven in that it utilizes a vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure to prepare an aqueous zinc-ion battery cathode. The preparation process involves the following steps: mixing the vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure, a conductive agent, a binder, and N-methylpyrrolidone to obtain a slurry; coating the slurry onto a current collector, or pressing the dried slurry onto the current collector to obtain the aqueous zinc-ion battery cathode. Everything else is the same as in Specific Implementation Method Seven.
[0038] Specific Implementation Method Nine: This implementation method differs from Specific Implementation Method Seven or Eight in that: the mass ratio of the vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure to the binder is (6-8):1; the mass ratio of the conductive agent to the binder is (3-1):1; and the loading of the vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure in the aqueous zinc-ion battery cathode is 0.8 mg / cm³. 2 ~2mg / cm 2 The rest is the same as in specific implementation methods seven or eight.
[0039] Specific Embodiment Ten: This embodiment differs from Specific Embodiments Seven to Nine in that: the current collector is titanium foil, stainless steel foil, titanium mesh, or stainless steel mesh; the conductive agent is one or a mixture of several of Super P, carbon nanotubes, Ketjen Black, acetylene black, and graphene; and the binder is one or a mixture of several of polyvinylidene fluoride, sodium carboxymethyl cellulose, and polyvinyl alcohol. Everything else is the same as in Specific Embodiments Seven to Nine.
[0040] The beneficial effects of the present invention are verified using the following embodiments:
[0041] Example 1:
[0042] A method for preparing a hydrophobic two-dimensional superstructure based on a vanadium-oxygen cluster comprises the following steps:
[0043] 1. Add 1 mL of hydrochloric acid solution to 6 mmol of 4-amino-p-terphenyl and seal the reactor. React at room temperature for 20 min. Then, sonicate at room temperature and 120 W for 5 min to obtain protonated TPA. Dissolve the protonated TPA in 200 mL of methanol solution and then add 100 mL of water to obtain the protonated TPA solution.
[0044] II. At room temperature, 1 mmol (NH4)6V 10 O 28 ·6H2O is dissolved in 30mL of water, then 60mL of methanol solution is added to obtain V 10 Solution;
[0045] 3. At room temperature, the protonated TPA solution is reacted with V 10 The solutions were mixed to obtain a yellow flocculent precipitate. The yellow flocculent precipitate was allowed to stand for 1 hour, filtered, and dried to obtain a hydrophobic two-dimensional superstructure with a vanadium-oxygen cluster group, named TPA-V. 10 .
[0046] The concentration of the hydrochloric acid solution mentioned in step one is 12 mol / L.
[0047] The above-prepared vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure is used in the positive electrode of an aqueous zinc-ion battery. The preparation of the positive electrode of an aqueous zinc-ion battery using the vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure is carried out in the following steps: the vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure, conductive agent, binder and N-methylpyrrolidone are mixed to obtain a slurry, the slurry is coated on a current collector, or the dried slurry is pressed onto the current collector to obtain the positive electrode of an aqueous zinc-ion battery.
[0048] The mass ratio of the vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure to the binder is 7:1; the mass ratio of the conductive agent to the binder is 2:1; and the loading of the vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure in the aqueous zinc-ion battery cathode is 1 mg / cm³. 2 .
[0049] The current collector is titanium foil; the conductive agent is Super P; and the binder is polyvinylidene fluoride.
[0050] Assembly of the coin cell: In an air atmosphere, the battery casing, positive electrode, separator, electrolyte, and negative electrode are assembled sequentially to obtain an aqueous zinc-ion coin cell. The positive electrode is the aqueous zinc-ion battery positive electrode prepared in Example 1, the separator is a glass fiber separator, the electrolyte is 3M Zn(CF3SO3)2, and the negative electrode is a zinc sheet.
[0051] Figure 1 TPA-V prepared in Example 1 10 The image is taken under a scanning electron microscope (SEM). As can be seen from the figure, it is composed of uniformly stacked two-dimensional nanosheets, which provides a larger specific surface area and active sites.
[0052] Figure 2 TPA-V prepared according to Example 1 10The graph shows the cycle performance of a coin cell using TPA-V as the positive electrode active material, after 100 cycles at a current density of 0.1 A / g. Figure 1 shows the coulombic efficiency curve, and figure 2 shows the discharge specific capacity curve. As can be seen from the graph, TPA-V... 10 It can be fully activated after one cycle under 0.1A / g conditions. The discharge capacity in the first cycle is only 148.1mAh / g, but the capacity quickly reaches the maximum capacity of 448mAh / g in the second cycle. After 100 cycles, its capacity still remains above 300mAh / g, which fully demonstrates that the material improves the specific capacity and cycle stability of the battery.
[0053] Figure 3 TPA-V prepared according to Example 1 10 The graph shows the cycle performance of a coin cell using a positive electrode active material, after 600 cycles at a current density of 2 A / g. Figure 1 shows the coulombic efficiency curve, and figure 2 shows the discharge specific capacity curve. It can be seen that TPA-V... 10 After activation, the capacity retention rate can reach 98.5% after 600 cycles, which fully demonstrates the material's superior cycling stability.
[0054] Figure 4 TPA-V prepared in Example 1 10 The X-ray diffraction images are shown in Figure a, where a is the XRD pattern in the small-angle region (2-10 degrees) and b is the XRD pattern in the 5-40 degree region. As can be seen from the figures, TPA-V... 10 It exhibits strong crystallinity and a layered structure, with an interlayer spacing of 2.16 nm corresponding to the (001) face. Furthermore, since Figure a represents the test results for the small-angle region, and Figure b was obtained using a different instrument and under different testing conditions, the intensity of the vertical axis differs.
[0055] Figure 5 For V 10 Protonated TPA prepared in step one of Example 1 and TPA-V prepared in Example 1 10 Fourier transform infrared spectra; as shown in the figure, from top to bottom, they are protonated TPA, TPA-V 10 and V 10 Comparing the three substances at 400-4000 cm -1 Within the range of stretching vibrations, TPA-V can be observed. 10 It not only possesses the same stretching vibrations as protonated TPA (e.g., located at 1484 cm⁻¹) -1 The stretching vibrations at the band (which can be attributed to the stretching vibrations of the benzene structure) also have similar characteristics to V. 10 Similar absorption peaks (e.g., 956 cm⁻¹) -1 The left and right bands are attributed to V=0), which strongly suggests TPA-V 10 It is a product of the uniform compounding of the two.
[0056] Figure 6 The protonated TPA prepared in step one of Example 1 and the TPA-V prepared in Example 1. 10 The 1H NMR spectrum image; upon comparison, TPA-V 10 It not only has peaks of several hydrogen atoms found in protonated TPA, but the peak positions of these peaks have also shifted, indicating that V 10 The protonated TPA and the protonated TPA were combined to form a composite material through electrostatic interaction.
[0057] Figure 7 TPA-V prepared in Example 1 10 Images under a transmission electron microscope (TEM); as shown in the figure, the TEM results show that the nanosheets have well-arranged lattice fringes when viewed from the side, which is consistent with the XRD results, indicating that they exist in a layered structure, and the thickness of the nanosheets is 18 nm.
[0058] Figure 8 TPA-V prepared in Example 1 10 High-resolution images under a transmission electron microscope (TEM); as shown in the figure, TPA-V 10 (001) The interlayer spacing of the crystal plane is 2.08 nm, which is basically consistent with the XRD test results, further proving that TPA-V 10 The two-dimensional nanosheets exhibit a layered structure inside.
[0059] Figure 9 The results are the contact angle test results for the positive electrode, where a represents the TPA-V prepared using Example 1. 10 The prepared positive electrode, b is the value of V 10 The prepared positive electrode sheet; as shown in the figure, the composite material TPA-V 10 (105°) compared to a single V 10 The hydrophobicity of the material (53.88°) has been greatly improved.
[0060] Figure 10 For V 10 and TPA-V prepared in Example 1 10 The BET test results; as shown in the figure, compared to V 10 (10.096m 2 / g), TPA-V 10 Specific surface area (30.577m²) 2 The ratio ( / g) has increased by more than two times, making it more conducive to ion storage and migration when used as a cathode material.
Claims
1. A method for preparing a hydrophobic two-dimensional superstructure based on a multivanadium-oxygen cluster, characterized in that... It is done in the following steps:
1. Add hydrochloric acid solution to 4-amino-p-terphenyl and seal the reactor. React at room temperature for 15 min to 20 min. Then, sonicate at room temperature and power of 100 W to 120 W for 5 min to 10 min to obtain protonated TPA. Dissolve the protonated TPA in methanol solution and then add water to obtain a protonated TPA solution.
2. At room temperature, (NH4)6V 10 O 28 ·6H2O dissolves in water, then methanol solution is added to obtain V 10 Solution; 3. At room temperature, the protonated TPA solution is reacted with V 10 The solutions were mixed to obtain a yellow flocculent precipitate. The yellow flocculent precipitate was allowed to stand, filtered, and dried to obtain a hydrophobic two-dimensional superstructure based on vanadium-oxygen clusters.
2. The method for preparing a multi-vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure according to claim 1, characterized in that... The concentration of the hydrochloric acid solution mentioned in step one is 10 mol / L to 14 mol / L.
3. The method for preparing a multi-vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure according to claim 1, characterized in that... The molar ratio of 4-amino-p-terphenyl to hydrochloric acid solution in step one is 6 mmol:(1-3) mL; the molar ratio of 4-amino-p-terphenyl to the total volume of methanol and water in step one is 6 mmol:(200-300) mL.
4. The method for preparing a multi-vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure according to claim 1, characterized in that... The (NH4)6V mentioned in step two 10 O 28 The molar ratio of ·6H2O to the total volume of methanol and water is 1 mmol:(90~300) mL.
5. The method for preparing a multi-vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure according to claim 1, characterized in that... The volume ratio of methanol to water mentioned in steps one and two is (2-3):
1.
6. The method for preparing a multivanadium-oxygen cluster-based hydrophobic two-dimensional superstructure according to claim 1, characterized in that... In step three, the protonated TPA solution contains protonated TPA and V. 10 (NH4)6V in solution 10 O 28 The molar ratio of ·6H2O is 6:(1~3).
7. The application of the multi-vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure prepared according to claim 1 in the cathode of an aqueous zinc-ion battery, characterized in that... Aqueous zinc-ion battery cathodes were prepared using a multivanadium-oxygen cluster-based hydrophobic two-dimensional superstructure.
8. The application of the multi-vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure according to claim 7 in the positive electrode of an aqueous zinc-ion battery, characterized in that... Aqueous zinc-ion battery cathodes are prepared using a vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure. The preparation process involves the following steps: mixing the vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure, a conductive agent, a binder, and N-methylpyrrolidone to obtain a slurry; coating the slurry onto a current collector, or pressing the dried slurry onto the current collector to obtain the aqueous zinc-ion battery cathode.
9. The application of the multi-vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure according to claim 8 in the positive electrode of an aqueous zinc-ion battery, characterized in that... The mass ratio of the vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure to the binder is (6-8):1; the mass ratio of the conductive agent to the binder is (1-3):1; and the loading of the vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure in the aqueous zinc-ion battery cathode is 0.8 mg / cm³. 2 ~2mg / cm 2 .
10. The application of the multi-vanadium-oxygen cluster-based hydrophobic two-dimensional superstructure according to claim 9 in the positive electrode of an aqueous zinc-ion battery, characterized in that... The current collector is titanium foil, stainless steel foil, titanium mesh, or stainless steel mesh; the conductive agent is one or a mixture of several of SuperP, carbon nanotubes, Ketjen black, acetylene black, and graphene; the binder is one or a mixture of several of polyvinylidene fluoride, sodium carboxymethyl cellulose, and polyvinyl alcohol.