Preparation method of MOF-based anode interface modification layer, product and application thereof

Abstract

This invention discloses a method for preparing a MOF-based anode interface modification layer, comprising the following steps: (1) synthesizing MIL-68 by heating an indium salt and terephthalic acid in a solvent; (2) mixing MIL-68, a conductive agent, and a binder, then adding a solvent to obtain a slurry, and coating the slurry onto the surface of a zinc foil to form a protective layer, thereby obtaining MIL-68@Zn. This invention also discloses the MOF-based anode interface modification layer obtained by the above preparation method and its application in zinc batteries. The simple and efficient synthesis method for preparing MIL-68@Zn effectively reduces the nucleation overpotential of zinc and significantly improves the cycle life of the battery, exhibiting excellent electrochemical performance when applied in zinc batteries.

Description

Technical Field

[0001] This invention relates to the field of electrochemical energy storage technology, specifically to a method for preparing a MOF-based anode interface modification layer, its products, and applications. Background Technology

[0002] With the escalating global energy crisis, the development of efficient, safe, and low-cost novel electrochemical energy storage systems has become a research hotspot. Zinc-based batteries possess unique advantages due to their significant safety, cost-effectiveness, and environmental friendliness. Among them, zinc anodes, with their low potential, price advantage, high specific capacity, high hydrogen evolution overpotential, chemical inertness, abundant resources, and ease of processing, have become a highly promising material in the field of aqueous zinc batteries. However, problems such as uncontrolled zinc dendrite growth, electrolyte erosion, significant volume changes, and interfacial instability still hinder their commercialization process and pose obstacles to further development.

[0003] To address these issues, researchers have proposed various strategies, including electrolyte modification, three-dimensional host structure design, and anolyte interface engineering (artificial SEI films). Among these, constructing an artificial protective layer is considered one of the most direct and effective methods. Existing protective layer materials mainly include polymers (such as Nafion, PVDF, etc.), inorganic materials (such as CaCO3, TiO2, etc.), and their composites. For example, Chinese patent CN121172274A discloses a weakly solvated non-aqueous electrolyte, its preparation method, and its applications. The weakly solvated non-aqueous electrolyte uses 1-methylimidazole as a solvent and zinc bis(trifluoromethanesulfonyl)imide as the soluble salt. 2+ Zn(EMI) was formed in this electrolyte. 4.99 (TFSI) 1.01 The solvation structure. As the electrochemical reaction proceeds, TFSI... - Anions preferentially reduce and decompose, forming a zinc anode surface rich in ZnF2, ZnS, and ZnN. x Organic-inorganic hybrid double-layer SEI membrane with inorganic components.

[0004] However, existing interface protection layer technologies still have the following shortcomings: Limited ion transport regulation capability: Many traditional coatings lack a uniform pore structure, making it difficult to achieve a uniform flux distribution of zinc ions and fundamentally suppress dendrite nucleation. Poor mechanical stability: Some polymer coatings are prone to swelling or cracking during long-term cycling, while inorganic coatings are prone to brittleness, leading to failure of the protective effect. Insufficient ability to block water molecules: Existing materials cannot effectively block the contact between water molecules and the zinc surface while allowing zinc ions to pass through rapidly, resulting in the inability to completely eliminate side reactions. Untunable structure: The microstructure of traditional materials is difficult to precisely control, making it impossible to adapt to the ion transport requirements under different operating conditions.

[0005] In recent years, the unique properties of MOFs, including their ability to promote zinc ion transport, large specific surface area, and highly tunable pore structure, have attracted increasing attention for their application in zinc-ion batteries. The high surface area and porous nature of MOFs facilitate the diffusion of ion species, ensuring that ions can effectively reach active sites. Customized pore sizes optimize ion transport while providing ample space for the interaction of reactant molecules with active sites. Strong coordination bonds between the metal center and ligands enhance the stability of the MOF framework. Thermal and chemical stability ensure that MOFs can withstand operating conditions without significant degradation. Chinese patent CN119798700A discloses a method for preparing VMOF nanomaterials, including the following steps: dissolving vanadium salt in anhydrous ethanol to form solution A; dissolving the organic ligand 2-bromoterephthalic acid and dilute hydrochloric acid in anhydrous ethanol to form organic ligand solution B; mixing solution A and organic ligand solution B and stirring to obtain mixed solution C; reacting mixed solution C under ultrasonic conditions to obtain mixed solution D; subjecting mixed solution D to a isothermal hydrothermal reaction; and washing the product after the hydrothermal reaction to obtain VMOF nanomaterials. The application of the VMOF nanomaterials disclosed in this invention in aqueous zinc batteries involves coating the VMOF nanomaterials as an electrode slurry onto the surface of titanium foil, drying it, and using it as an electrode sheet for the aqueous zinc battery. The vanadium-based nanomaterials prepared by this invention exhibit high conductivity and cycle stability.

[0006] Therefore, designing a MOF-based modified material that can be easily synthesized and can significantly improve the cycle life of zinc-ion batteries is currently a research hotspot in this field. Summary of the Invention

[0007] The purpose of this invention is to provide a method for preparing a MOF-based anode interface modification layer. MIL-68@Zn is prepared by a simple and efficient synthesis method, which effectively reduces the nucleation overpotential of zinc and significantly improves the cycle life of the battery. When applied to zinc batteries, it exhibits excellent electrochemical performance.

[0008] To achieve the above-mentioned objectives, the present invention provides the following technical solution: A method for preparing a MOF-based anode interface modification layer includes the following steps: (1) MIL-68 was synthesized by heating a solvent using indium salt and terephthalic acid as reactants; (2) Mix MIL-68, conductive agent and binder and add solvent to obtain slurry. Coat the slurry on the zinc foil surface to form a protective layer to obtain MIL-68@Zn.

[0009] The preparation method provided by this invention is an anode interface engineering strategy based on MOFs. By selecting In metal centers and specific organic ligands, MOF materials with tunable pore size and charge density are synthesized for stabilizing zinc-ion batteries. This MOF layer, with its regular morphology, ordered pore structure, and high specific surface area, can achieve uniform Zn content. 2+ Flux distribution; its framework acts as an ordered ion channel, guiding Zn 2+ Directional deposition; simultaneously, suitable pore environment and charge density can optimize Zn deposition. 2+ The solvation structure effectively suppresses hydrogen evolution side reactions and promotes Zn 2+ Rapid migration. This design significantly reduces nucleation overpotential and imparts excellent cycle stability to the battery.

[0010] The indium salt is indium nitrate pentahydrate, and the mass ratio of indium nitrate pentahydrate to terephthalic acid is 1-3:1-3. Indium nitrate pentahydrate has extremely high solubility in polar organic solvents, rapidly forming a clear, homogeneous solution, providing a good foundation for subsequent coordination reactions; nitrate ions (NO3) - The ion is a weakly coordinating anion, which does not compete with organic ligands for metal ions, thus ensuring the smooth progress of the coordination reaction. The water of crystallization helps to achieve a slow and uniform coordination reaction, making MOF crystal growth more controllable, resulting in products with good crystallinity and regular morphology. Its chemical properties are stable and controllable, reacting according to the expected pathway. It is a stable crystalline solid, easy to weigh, and not prone to deliquescence. By limiting the mass ratio to achieve coordination equilibrium, unreacted metal ions or organic ligands are avoided in the product, ensuring the structural integrity and high purity of the final product.

[0011] In steps (1) and (2), the heating reaction temperature is 120~180℃. Firstly, in this invention, MIL-68 is synthesized using a solvothermal method, i.e., the reactants are heated in a closed system. The increased temperature provides the activation energy required for the reaction, allowing In... 3+ The reaction can overcome the energy barrier with the ligand and undergo coordination reaction; secondly, if the temperature is too low, the reaction rate will be slow, and crystals may not be formed or the product may have poor crystallinity. If the temperature is too high, the reaction may be too violent, producing a large number of crystal nuclei, forming crystals that are too small or irregular in size, or even causing the framework structure to collapse or generate impurity phases; moreover, the properties of DMF as a solvent will undergo subtle changes at high temperatures, which is more conducive to dissolving reactants and promoting coordination reaction.

[0012] In step (1), the length of the synthesized MIL-68 is 4-20 μm.

[0013] In step (2), the mass ratio of MIL-68, superconducting carbon black, and PVDF is 6-8:1-3:1.

[0014] In step (2), the conductive agent is selected from superconducting carbon black (high conductivity, high purity, branched structure, extremely low addition amount, and superior performance), and the binder is selected from PVDF (possessing extremely strong electrochemical corrosion resistance and a wide electrochemical window, good mechanical strength, flexibility and thermal stability, can be dissolved in organic solvents such as N-methylpyrrolidone (NMP) to form a uniform slurry, which is easy to coat and has highly stable chemical properties).

[0015] Preferably, the preparation method includes: (1) Dissolve indium nitrate pentahydrate and terephthalic acid in 20-60 mL of N,N-dimethylformamide. Then transfer the mixture to a high-pressure reactor with a 50-100 mL polytetrafluoroethylene liner, seal and heat for 5-7 h, cool to room temperature, filter and wash three times with ethanol to obtain a white solid product, and vacuum dry for 8-12 h to obtain the MIL-68 sample.

[0016] (2) MIL-68, superconducting carbon black, and PVDF were mixed in mass ratios of 8:1:1, 7:2:1, and 6:3:1, respectively, and thoroughly ground / stirred to ensure uniform mixing. An appropriate amount of NMP solvent was added, and the mixture was ground again to obtain a uniform slurry. The slurry was then uniformly coated onto the polished zinc foil surface using a spin coater to form a protective layer. The coated sample was then placed in a vacuum drying oven and dried at 60-80 ℃ for 6-24 h to finally obtain MIL-68@Zn.

[0017] Preferably, the amount of N,N-dimethylformamide is 20-40 mL, and the drying time is 6-8 h.

[0018] This invention also provides a method for preparing the aforementioned MOF-based anode interface modification layer. This invention provides a MOF-based anode interface modification layer for reducing zinc nucleation overpotential and improving the cycle life of zinc-ion batteries.

[0019] The present invention also provides an application of the above-mentioned MOF-based anode interface modification layer in zinc batteries.

[0020] Preferably, the zinc battery is a symmetrical zinc battery, an asymmetrical copper-zinc battery, or a full battery.

[0021] A symmetrical zinc battery device is constructed using the aforementioned MIL-68@Zn; the symmetrical zinc battery device includes a single MIL-68@Zn electrode, a zinc foil, a separator, and a 2M zinc sulfate electrolyte. An asymmetric copper-zinc battery device is constructed using the aforementioned MIL-68@Zn; the asymmetric copper-zinc battery device includes a single MIL-68@Zn electrode, a copper foil, a separator, and a 2M zinc sulfate electrolyte. A full battery device is constructed using the aforementioned MIL-68@Zn; the full battery device includes a PEDOT-V₂O₅ positive electrode, a MIL-68@Zn negative electrode, a separator, and a 2M zinc sulfate electrolyte.

[0022] The MIL-68@Zn preparation method provided by this invention has significant advantages such as simple process, low cost, easy control, and high reproducibility. Electrochemical performance evaluation by assembling zinc-ion symmetric cells, half-cells, and full cells demonstrates the excellent performance of MIL-68@Zn.

[0023] Compared with existing technologies, this invention has the following superior effects: This invention provides an interface modification layer based on an indium-based metal-organic framework (MIL-68) on the zinc anode surface, which effectively reduces the nucleation overpotential of zinc and significantly improves the cycle life of the battery. MIL-68 has a smaller pore size (and a higher specific surface area), which can homogenize Zn. 2+ Flux, promotes [Zn(H2O)6] 2+ Desolvation accelerates ion migration and suppresses hydrogen evolution side reactions: for example, the MIL-68@Zn symmetric cell achieved stable deposition / stripping for over 5800 hours during long-term cycling, exhibiting extremely low overpotential; its desolvation energy is only 19.0 kJ mol. -1 ; such as the Zn / / Cu asymmetric cell based on MIL-68@Zn at 5 mA cm⁻¹ -2 After nearly 2000 cycles, the coulombic efficiency reached 99.7%, and the nucleation overpotential was as low as 71 mV. For example, in full-cell testing, the MIL-68@Zn battery with a PEDOT-V2O5 cathode achieved a performance of 5 A g. -1 After 1000 cycles at high current density, the capacity retention rate reached 84.1%, demonstrating excellent comprehensive electrochemical performance. Attached Figure Description

[0024] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0025] Figure 1Morphology image of MIL-68 prepared in Example 1; Figure 2 Morphology image of MIL-68(PTA) prepared in Example 1; Figure 3 The pore size distribution curve of MIL-68 prepared in Example 1; Figure 4 The pore size distribution curve of MIL-68(PTA) prepared in Example 1; Figure 5 XRD images of the surfaces of MIL-68@Zn, MIL-68(PTA)@Zn, and Zn anodes prepared for Example 1 after immersion in 2 M ZnSO4 electrolyte for 30 days; where: the x-axis is the diffraction angle (2θ), and the y-axis is the relative diffraction intensity; Figure 6 Morphology images of the MIL-68@Zn, MIL-68(PTA)@Zn, and Zn anodes prepared in Example 1 after 100 electroplating / stripping cycles; Figure 7 Time-voltage curves and partial magnified views of the symmetrical cells assembled with MIL-68@Zn, MIL-68(PTA)@Zn, and Zn anodes prepared in Example 1; Figure 8 Electrochemical impedance spectroscopy (EIS) of symmetrical cells assembled with MIL-68@Zn, MIL-68(PTA)@Zn, and Zn anodes prepared in Example 1 at different temperatures, and calculation of the desolvation energy of zinc ions in different zinc anode protection systems; Figure 9 Voltage-capacity curves of asymmetric batteries assembled with MIL-68@Zn, MIL-68(PTA)@Zn, and Zn anodes prepared in Example 1 after 500 cycles.

[0026] Figure 10 Charge-discharge curves of asymmetric batteries prepared in Example 1, namely MIL-68@Zn, MIL-68(PTA)@Zn, and Zn anode assembly; Figure 11 The full cell assembled from MIL-68@Zn, Zn anode, and PEDOT-V2O5 cathode prepared in Example 1 was used at 5 Ag. -1 Long cycle diagram at current density. Detailed Implementation

[0027] The X-ray diffractometer used in the embodiments of the present invention is a Bruker D8 X-ray diffractometer from the United States, the scanning electron microscope is a Zeiss GeminiSEM 300 field emission scanning electron microscope (FE-SEM) from Germany, the physical adsorption instrument is a Belsopr series physical adsorption instrument from Japan, and the electrochemical workstation is a CT3001A electrochemical workstation from Wuhan Landian Company.

[0028] The following examples further illustrate the method for preparing MOF interface modification layers with low nucleation overpotential and long cycle life in this invention.

[0029] Example 1 Step (1): First, indium nitrate pentahydrate and terephthalic acid were dissolved in DMF (20 mL) at a mass ratio of 3:1. The mixture was then transferred to a high-pressure reactor lined with 50 mL of polytetrafluoroethylene, sealed, and heated at 125 °C for 5 hours. After cooling to room temperature, the mixture was filtered and washed three times with ethanol to obtain a white solid product. Finally, the product was vacuum dried at 80 °C for 12 hours to obtain the MIL-68 sample. Step (2): MIL-68, superconducting carbon black, and PVDF were mixed at a mass ratio of 8:1:1, and an appropriate amount of NMP solvent was added. The mixture was then ground to obtain a uniform slurry. Subsequently, the slurry was uniformly coated onto the polished zinc foil surface using a spin coater to form a protective layer. The coated sample was then dried in a vacuum drying oven at 60 °C for 6 hours to finally obtain MIL-68@Zn and MIL-68(PTA)@Zn.

[0030] Comparative Example 1 Step (1): First, indium nitrate pentahydrate and biphenyl dicarboxylic acid were dissolved in DMF (20 mL) at a mass ratio of 3:1. The mixture was then transferred to a high-pressure reactor lined with 50 mL of polytetrafluoroethylene, sealed, and heated at 125 °C for 5 hours. After cooling to room temperature, the mixture was filtered and washed three times with ethanol to obtain a white solid product. Finally, the product was vacuum dried at 80 °C for 12 hours to obtain the MIL-68(PTA) sample. The SEM image of the obtained product is shown below. Figure 2 .

[0031] MIL-68 (PTA), superconducting carbon black and PVDF are mixed according to... After mixing in a mass ratio of 8:1:1, an appropriate amount of NMP solvent was added, and the mixture was ground to obtain a uniform slurry. Subsequently, the slurry was uniformly coated onto the polished zinc foil surface using a spin coater to form a protective layer. The coated sample was then placed in a vacuum drying oven and dried at 60°C for 6 hours to finally obtain MIL-68(PTA)@Zn.

[0032] Example 2 The difference from Example 1 is that MIL-68 was prepared at 180°C and 150°C, respectively, and at 2:2 and 1:3 conditions, respectively.

[0033] Material characterization The SEM image of the prepared MIL-68 in Example 1 is shown below. Figure 1 c in Figure 1 In the text, 'a' and 'b' represent MIL-68 prepared at 180℃ and 150℃, respectively. Figure 1 In the figures, d and e represent MIL-68 prepared under 2:2 and 1:3 conditions, respectively. When synthesized at temperatures of 180℃, 150℃, and 125℃, the lengths of MIL-68 were 9 μm, 6.57 μm, and 4.32 μm, respectively. When the mass ratio of indium nitrate pentahydrate to terephthalic acid was 3:1 and 2:2, the lengths of MIL-68 were 4.32 μm and 20.24 μm, respectively. Furthermore, when the mass ratio was 1:3, an irregular morphology was observed.

[0034] Nitrogen adsorption-desorption measurements of MIL-68 prepared in Example 1 and MIL-68(PTA) prepared in Comparative Example 1 confirmed the porous properties of the two prepared materials. Figure 3 and Figure 4 Due to differences in ligand structure, the average pore size of MIL-68 is only 1.87 nm, smaller than that of MIL-68(PTA) at 3.19 nm, resulting in a total pore volume of 0.48 cm³. 3 g -1 It is 0.08 cm larger than MIL-68(PTA). 3 g -1 These ordered pores can be Zn 2+ and [Zn(H2O)6] 2+ The smaller pore structure provides an efficient channel for transport, and the smaller pore structure promotes the transport of [Zn(H2O)6]. 2+ The water molecules in the solution are desoluble, which further accelerates ion migration.

[0035] Application examples The MIL-68@Zn prepared in Example 1, the MIL-68(PTA)@Zn prepared in Comparative Example 1, and the Zn anode were immersed in 2 M ZnSO4 electrolyte. After 30 days, the surface condition of the bare zinc anode under different conditions was investigated by XRD. Figure 5 MIL-68 has a smaller pore size and a larger specific surface area, which has a stronger inhibitory effect on the corrosion of active water molecules at the electrode / electrolyte interface. Therefore, even after long-term electrolyte immersion, zinc anodes coated with MIL-68 do not produce zinc dendrites or basic byproducts on their surface.

[0036] The MIL-68@Zn prepared in Example 1, the MIL-68(PTA)@Zn prepared in Comparative Example 1, and a Zn anode were assembled into a symmetrical battery. The effects of different anodes on the long-term cycling of the battery were investigated using SEM. Figure 6 The zinc anode in the MIL-68@Zn anode symmetric cell maintains a dense and flat surface without obvious dendrites after 100 cycles.

[0037] The MIL-68@Zn prepared in Example 1, the MIL-68(PTA)@Zn prepared in Comparative Example 1, and the Zn anode were assembled into a symmetrical cell, and deposition-stripping cycle performance was tested on a CT3001A electrochemical workstation. Figure 7 As shown, the MIL-68@Zn anode exhibits the best performance at 1 mA cm⁻¹. -2 Current density, 1 mAh cm -2 It exhibits remarkable long-term stability exceeding 5800 hours under the electroplating capacity. Notably, magnified voltage and time plots clearly show that the symmetrical cell assembled with the MIL-68@Zn anode achieves ultra-low overpotential during continuous electroplating / stripping. Subsequently, electrochemical impedance spectroscopy was performed on different zinc anode protection systems at different temperatures, and the desolvation energy of zinc ions in different zinc anode protection systems was calculated using the Arrhenius equation. Figure 8 As shown, the symmetric cell assembled with MIL-68@Zn anodes exhibits a lower interfacial resistance than the other two symmetric cells, corresponding to the fastest interfacial ion diffusion rate, and its desolvation energy is only 19.0 kJ / mol. -1 The energy is much smaller than that of the other two symmetrical batteries, which further illustrates that applying MIL-68 with smaller pore size and higher charge density to the zinc anode protective layer can make it easier for hexahydrate zinc ions to remove water molecules from their solvent shell, thereby bringing about higher ion transfer rate and faster reaction kinetics. This shows that the designed molecular-level MOF microstructure will have a great impact on the electrochemical performance of the battery.

[0038] The MIL-68@Zn prepared in Example 1, the MIL-68(PTA)@Zn prepared in Comparative Example 1, and a Zn anode were assembled into a Zn / / Cu asymmetric cell to measure its nucleation potential at 5 mA cm⁻¹. -2 Electrochemical studies were conducted on the nucleation behavior of zinc at specific current densities. For example... Figure 9 As shown, the MIL-68 layer can reduce the nucleation overpotential of zinc to 71 mV, while the nucleation overpotentials of the MIL-68 (PTA) layer and zinc are 80 mV and 244 mV, respectively. This indicates that MIL-68 effectively reduces the difficulty of nucleation and the activation of deposition, thereby improving deposition stability.

[0039] The MIL-68@Zn prepared in Example 1, the MIL-68(PTA)@Zn prepared in Comparative Example 1, and the Zn anode were assembled into a Zn / / Cu asymmetric cell to measure their coulombic efficiency (CE). Figure 10 As shown, an asymmetric cell using a MIL-68@Zn anode operates at 5 mA cm⁻¹. -2 It exhibits stable cycling for approximately 2000 cycles at higher current densities, with a coulombic efficiency as high as 99.7%. This indicates that In-based MOF as a zinc anode protective layer can effectively and uniformly suppress dendrite growth by increasing zinc ion flux, and the MIL-68 coating provides even more outstanding protection for the zinc anode.

[0040] The full cell assembled from the MIL-68@Zn obtained in Example 1, along with the Zn anode and PEDOT-V2O5 cathode, was subjected to long-cycle testing, such as... Figure 11 As shown, a full cell using a MIL-68@Zn anode and a PEDOT-V2O5 cathode was tested at 5 A g. -1 It exhibits 270 mAh g at high current density. -1 The initial capacity, and still retains 227 mAh g after 1000 cycles. -1 With a capacity retention rate as high as 84.1%, it has a certain degree of competitiveness.

[0041] In summary, the MIL-68@Zn anode prepared in this invention exhibits significant comprehensive performance advantages. Indium-based MOF materials were synthesized through ligand engineering strategies and applied to aqueous zinc-ion batteries. By regulating ligands, the electronic structure and charge distribution of MIL-68 were optimized, resulting in smaller pore size and higher charge density. The unique properties of MOF materials are utilized to promote Zn... 2+ Ordered, directional migration suppresses side reactions such as hydrogen evolution and corrosion, effectively improving the cycle stability of zinc-ion batteries. Thanks to this structural design, the MIL-68@Zn anode exhibits extremely low nucleation overpotential, guiding uniform zinc deposition; simultaneously, it maintains a stable low plateau overpotential throughout the cycle, endowing the battery with excellent long-term cycle stability. This strategy not only verifies the feasibility of using ligand engineering to modulate MOF structures to activate their potential in aqueous zinc-ion batteries, but also provides new ideas for the design of functional MOFs for energy storage applications, which is of great significance for promoting the development of aqueous zinc-based energy storage technology.

[0042] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A method for preparing a MOF-based anode interfacial modification layer, characterized in that, Includes the following steps: (1) MIL-68 was synthesized by heating a solvent using indium salt and terephthalic acid as reactants; (2) Mix MIL-68, conductive agent and binder and add solvent to obtain slurry. Coat the slurry on the zinc foil surface to form a protective layer to obtain MIL-68@Zn.

2. The method for preparing a MOF-based anode interfacial modification layer according to claim 1, characterized in that, In step (1), the indium salt is indium nitrate pentahydrate, and the mass ratio of indium nitrate pentahydrate to terephthalic acid is 1-3:1-3.

3. The method for preparing the MOF-based anode interface modification layer according to claim 1, characterized in that, In step (1), the temperature of the heating reaction is 120~180℃.

4. The method for preparing the MOF-based anode interface modification layer according to claim 1, characterized in that, In step (1), the length of the synthesized MIL-68 is 4-20 μm.

5. The method of claim 1, wherein the MOF-based anode interfacial modification layer is prepared by a method comprising: In step (2), the mass ratio of MIL-68, superconducting carbon black, and PVDF is 6-8:1-3:

1.

6. A MOF-based anode interface modification layer obtained by the preparation method according to any one of claims 1-5.

7. The application of the MOF-based anode interface modification layer as described in claim 6 in a zinc battery.

8. Use according to claim 7, characterized in that, The zinc battery is a symmetrical zinc battery, an asymmetrical copper-zinc battery, or a full battery.

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