Preparation and application of a zinc anode electrode material with a heterometallic interface

Abstract

This invention relates to the field of zinc-ion battery technology, and in particular to the preparation and application of a zinc anode electrode material with a heterogeneous metal interface. The method includes: S1: preparation of the precursor metal-organic framework Bio-MOF-100; S2: annealing Bio-MOF-100 powder at high temperature under inert gas protection; S3: mixing the annealed Bio-MOF-100 powder with a conductive agent and a binder, and pressing it onto a current collector; S4: assembling the pressed sample with a zinc sheet into a battery, and performing electrodeposition to prepare samples with different zinc deposition amounts; S5: immersing the electrodeposited zinc sample in a displacement solution for a displacement reaction, followed by washing and vacuum drying to finally obtain the desired electrode material. The electrode material obtained by the above method exhibits high performance at a current density of 2 mA cm⁻¹. ‑2 The capacity density is 1 mAh cm⁻¹ ‑2 Under these conditions, after 700 hours of cyclic testing, its polarization voltage was only 16 mV.

Description

Technical Field

[0001] This invention relates to the field of zinc-ion battery technology, and in particular to the preparation and application of a zinc anode electrode material with a heterogeneous metal interface. Background Technology

[0002] The continued exploitation of fossil fuels has exacerbated the energy crisis and ecological damage, posing a severe challenge to the sustainable development of human society. Against this backdrop, the development and utilization of clean and renewable energy sources such as solar, tidal, and wind power have become crucial. However, the supply of these energy sources is intermittent and geographically limited, making the development of efficient, large-scale energy storage technologies an urgent priority. Among numerous energy storage options, rechargeable battery technology has garnered significant attention due to its flexibility and efficiency. Lithium-ion batteries, in particular, have been widely used in various fields, from small electronic devices to large electric vehicles, due to their excellent energy density and cycle performance. However, with their widespread application, lithium-ion batteries have also encountered several challenges. First, large-scale deployment may pose safety hazards. Second, due to the scarcity of lithium resources, the production cost of lithium-ion batteries remains high. These factors not only significantly hinder the application of lithium-ion batteries in large-scale energy storage but also constitute a considerable obstacle to the long-term development of renewable energy.

[0003] Against this backdrop, developing a new type of battery system that is safe, economical, environmentally friendly, and has high energy density has become an urgent need for industry development. In recent years, multivalent metal-ion batteries, including aqueous zinc-ion batteries, have attracted widespread attention from the scientific community due to their unique advantages. Zinc-ion batteries, with their low redox potential (-0.763 V relative to the standard hydrogen electrode), high theoretical capacity (820 mAh / g and 5855 mAh / cm³), wide operating voltage window (0-2.0 V), economical cost, excellent safety, and environmental friendliness, have attracted widespread attention from the global academic and industrial communities.

[0004] Although aqueous zinc batteries based on zinc anodes offer advantages such as high theoretical energy density, intrinsic safety, and low cost, the zinc anode in aqueous solutions faces challenges related to thermodynamic stability and electrochemical kinetics, severely hindering their practical application. In recent years, various strategies have emerged to address the problems of zinc anodes, including constructing interfacial protective layers, electrode structure design, electrolyte regulation, and separator optimization. While the performance of zinc anodes has improved, it remains difficult to continuously regulate zinc deposition behavior during long-term and high-rate charge-discharge cycles. Specifically, functional physical protective coatings, including inorganic non-metallic materials, organic polymers, metallic materials or alloy solid solutions, and other composite materials, are only effective on the zinc anode surface. During long-term cycling (especially at high current densities), the interfacial protective layer struggles to suppress crack formation due to the drastic volume changes of the zinc anode, thus rendering its protective function ineffective. The introduction of additives typically reduces the ionic conductivity of the electrolyte, leading to severe performance degradation at high current densities. Furthermore, the uneven growth of zinc metal is difficult to regulate within the internal space of a 3D electrode structure. Therefore, to address the inherent problems of zinc metal anodes in constructing high-performance aqueous zinc-ion batteries, it is urgent to optimize zinc metal nucleation and suppress dendrite formation and side reactions, fundamentally solving the kinetic and thermodynamic problems of zinc anodes. In 2023, Qi et al. studied the electrochemical performance of Zn-Al heteroalloys in aqueous zinc-ion batteries (Qi, Zichen, et al. Suppressing zinc dendrite growth in aqueous battery via Zn-Al alloying with spatially confined zinc reservoirs[J]. Journal of Power Sources558 (2023): 232628.). The test results showed that the fabricated symmetrical battery achieved a current density of 0.5 mA cm⁻¹. -2 0.25mAh capacity -2Under certain conditions, its cycle time can reach 300 hours, exhibiting good cycle stability. The inert alumina layer constructed in this invention can effectively reduce the side reactions between zinc metal and electrolyte, achieving a high degree of reversibility of the zinc anode. However, it still suffers from problems such as high internal resistance, large nucleation barrier, and low cycle life. Therefore, how to reduce the nucleation barrier of zinc ions at the anode interface, reduce the polarization voltage, and improve the cycle life of the battery has become a key problem that urgently needs to be solved. Metal-organic frameworks (MOFs) are crystalline porous materials with a periodic network structure formed by the self-assembly of transition metal ions and organic ligands. They possess advantages such as precise pore structure, ultra-high porosity, and diverse morphologies. In recent years, composite materials prepared based on MOFs as supports or precursors have shown excellent performance in the field of electrochemical energy storage. Due to its porosity and tunable structure, we selected Bio-MOF-100 as a precursor-derived carbon material as a deposition support to construct a stable zinc anode interface. Due to its ZnO nucleation sites and inherent porosity, the zinc electrode can effectively guide the deposition path of zinc ions, resulting in a smooth and uniform zinc deposition layer. However, a single nucleation site may lead to problems such as low nucleation density and high nucleation barriers. Therefore, developing heterometallic interfaces with multiple nucleation sites is expected to effectively reduce the zinc nucleation barrier and increase the zinc nucleation density, thereby promoting the uniform deposition of zinc ions on the electrode surface and improving the overall performance of aqueous zinc-ion batteries. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention aims to develop a zinc anode electrode material with a heterometallic interface, solving problems such as zinc dendrite growth and the formation of inert byproducts on the zinc anode surface. The innovation of this invention lies in first using a carbon material derived from Bio-MOF-100 as a matrix, then electrochemically depositing zinc onto this material to form a zinc anode; subsequently, immersing this zinc anode in a salt solution containing indium, tin, antimony, and bismuth to conduct a displacement reaction, successfully preparing a zinc anode electrode material with a heterometallic interface. This material exhibits high cycle stability and low polarization potential. Through these steps, a novel aqueous zinc-ion battery anode material with excellent performance is obtained, completing this invention.

[0006] Therefore, in a first aspect, the present invention provides a zinc negative electrode material with a heterometallic interface, the method comprising:

[0007] S1: First, adenine was dissolved in N,N-dimethylformamide (DMF) and stirred thoroughly to prepare solution A. Next, 4,4'-biphenyl dicarboxylic acid was also dissolved in DMF and stirred until completely dissolved to form solution B. Then, polyvinylpyrrolidone (PVP) was dissolved in DMF, and after complete dissolution, zinc acetate was added, and stirring continued to form solution C. Finally, solutions A, B, and C were sequentially added to a mixed solution containing DMF, methanol, and deionized water, and stirring continued until the mixture was homogeneous. After stirring, the mixture was washed three times with DMF, and then dried at 80 °C for 10 h to obtain Bio-MOF-100 powder.

[0008] S2: Anneal the Bio-MOF-100 powder under high temperature and inert atmosphere conditions.

[0009] S3: After annealing, Bio-MOF-100 powder is mixed with Ketjen black and PTFE, rolled into a film, and pressed onto a titanium mesh using a tablet press.

[0010] S4: The pressed sample is combined with a zinc sheet to assemble a battery. The electrodeposition process is performed by setting a specific current density, and the amount of zinc deposited is precisely controlled by adjusting the electrodeposition time.

[0011] S5: The electrodeposited sample is immersed in an indium trichloride (InCl3) solution to carry out a displacement reaction. After the reaction is complete, the sample is rinsed and dried in an oven to finally obtain the desired electrode material.

[0012] In a preferred embodiment, in S1, the mass of adenine is 0.02~0.2 g, the mass of 4,4'-biphenyldicarboxylic acid is 0.05~0.5 g, the mass of PVP is 0.5~2 g, and the mass of zinc acetate is 0.2~0.5 g.

[0013] In a preferred embodiment, in S1, the amounts of solutions A, B, C and the DMF in the mixed solution are all 10-20 mL, the amount of methanol is 1-5 mL, and the amount of deionized water is 1-5 mL.

[0014] In a preferred embodiment, in S2, the annealing temperature is 400~800 ℃, the inert gas is argon, the heating rate is 3~5 ℃ / min, and the holding time is 5~10 h.

[0015] In a preferred embodiment, in S3, the Bio-MOF-100 powder is mixed with Ketjen Black and PTFE in a ratio of 8:1:1 or 7:2:1.

[0016] In a preferred embodiment, in S4, the battery uses the sample prepared in S3 as the working electrode and a zinc sheet as the counter electrode, with a current density of 2~5 mA cm⁻¹. -2 Under these conditions, the zinc deposition amounts after deposition for 10, 15, 20, 25, and 30 h were 20, 30, 40, 50, and 60 mAh cm⁻¹, respectively. -2 .

[0017] In a preferred embodiment, in step S5, the concentrations of the indium trichloride (InCl3), antimony trichloride (SbCl3), bismuth trifluoromethanesulfonate (Bi(CF3SO3)3), and tin trichloride (SnCl3) solutions are 0.1~2 mol / L.

[0018] In a preferred embodiment, in step S5, the sample prepared in step S4 is immersed in a 0.1-2 mol / L solution of indium trichloride (InCl3), antimony trichloride (SbCl3), bismuth trifluoromethanesulfonate (Bi(CF3SO3)3), and tin trichloride (SnCl3) for 1-10 minutes.

[0019] In a preferred embodiment, in step S5, the drying process is carried out in a constant temperature oven at 60 °C for a duration of 1 to 10 minutes.

[0020] In a second aspect, the present invention provides a zinc anode electrode material with a heterogeneous metal interface obtained by the above preparation method.

[0021] In a preferred embodiment, the zinc negative electrode material with a heterogeneous metal interface achieves elemental substitution between zinc and indium through a simple and efficient immersion process, thereby obtaining a pebble-like structure.

[0022] In a third aspect, the present invention provides the application of the zinc anode electrode material with a heterogeneous metal interface in an aqueous zinc-ion battery.

[0023] In a preferred embodiment, in an aqueous zinc-ion battery, after the electrode materials are assembled into the battery, at a current density of 2 mA cm⁻¹ -2 Surface capacity is 1 mAh cm -2 Under these conditions, after 700 hours of cyclic testing, its polarization voltage was only 16 mV.

[0024] Technical effect

[0025] This invention uses annealed Bio-MOF-100 as a substrate, on which zinc is deposited. On one hand, Bio-MOF-100 possesses a large specific surface area and a rich variety of organic ligands, releasing a large number of gaseous small molecules during calcination, thus resulting in a sample with a large specific surface area. On the other hand, the uniform distribution of metal elements in Bio-MOF-100 allows for uniform encapsulation within the porous carbon.

[0026] In this invention, Bio-MOF-100 is a MOF with a good porous structure. During electrodeposition, it can effectively guide the deposition path of zinc ions, resulting in a smooth and uniform zinc deposition layer. Furthermore, by controlling the deposition time at a rated current density, zinc deposition layers with different deposition amounts can be obtained, thereby achieving a zinc anode with superior performance.

[0027] This invention involves immersing a prepared zinc anode in an aqueous solution of indium trichloride. Through a simple displacement reaction, an indium metal layer is grown on the surface of the zinc anode to modify it. The indium metal forms a uniform and dense metal interface phase on the zinc anode surface. This interface acts as a barrier, effectively isolating the zinc anode from direct contact with the electrolyte, reducing the reaction between water and oxygen in the electrolyte and the zinc anode, thereby suppressing side reactions and improving battery stability. Indium metal has a high affinity for zinc, inducing uniform deposition of zinc ions on the zinc anode surface and reducing dendrite formation. The indium metal interface promotes smooth zinc deposition by lowering the nucleation barrier of zinc ions and providing a uniform ion concentration field, significantly improving battery safety and cycle stability. The presence of the indium metal interface improves the transport kinetics of zinc ions on the anode surface, enhancing zinc ion transport efficiency by reducing interfacial resistance during deposition, thereby improving the battery's rate performance.

[0028] This invention proposes a zinc anode electrode material with a heterometallic interface. The surface layer of the indium-based component has numerous nucleation sites to induce zinc ion deposition. Furthermore, the indium metal effectively isolates the electrolyte from direct contact with the zinc anode surface, thereby inhibiting surface corrosion of the zinc anode. The electrode material obtained through this method exhibits good performance at a current density of 2 mAcm⁻¹. -2 Surface capacity is 1 mAh cm -2 Under these conditions, the stable cycling time can reach over 700 hours, and it has a low polarization voltage. Attached Figure Description

[0029] Figure 1 These are scanning electron microscope images of Zn / In-40 prepared in Example 1;

[0030] Figure 2 The Zn / In-40 obtained in Example 1 was used as the electrode material at 2 mA cm⁻¹-2 1 mAh cm -2 Under normal cyclic performance;

[0031] Figure 3 These are scanning electron microscope images of Zn / In-30 obtained in Example 2;

[0032] Figure 4 The Zn / In-30 obtained in Example 2 was used as the electrode material at 2 mA cm⁻¹ -2 1 mAh cm -2 Under normal cyclic performance;

[0033] Figure 5 These are scanning electron microscope images of Zn / In-50 obtained in Example 2;

[0034] Figure 6 The Zn / In-50 obtained in Example 2 was used as the electrode material at 2 mA cm⁻¹ -2 1 mAh cm -2 Under normal cyclic performance;

[0035] Figure 7 These are scanning electron microscope images of zinc deposited on the MOF substrate material prepared in Comparative Example 1;

[0036] Figure 8 Zinc was deposited as an electrode material on the MOF substrate prepared in Comparative Example 1 at 2 mA cm⁻¹ -2 1 mAh cm -2 Under normal cyclic performance; Detailed Implementation

[0037] The following description, with reference to the accompanying drawings, illustrates several preferred embodiments of the present invention to make its technical content clearer and easier to understand. The present invention can be embodied in many different forms, and the scope of protection of the present invention is not limited to the embodiments mentioned herein.

[0038] Example 1

[0039] A zinc anode electrode material with a heterogeneous metal interface:

[0040] First, 0.135 g of adenine was dissolved in 20 mL of N,N-dimethylformamide (DMF) and stirred thoroughly to prepare solution A. Next, 0.485 g of 4,4'-biphenyl dicarboxylic acid was also dissolved in 20 mL of DMF and stirred until completely dissolved to form solution B. Then, 2 g of polyvinylpyrrolidone (PVP) was dissolved in 40 mL of DMF. After complete dissolution, 0.42 g of zinc acetate was added, and stirring continued to form solution C. Finally, solutions A, B, and C were sequentially added to a mixed solution containing 20 mL of DMF, 4 mL of methanol, and 2 mL of deionized water, and stirring continued until the mixture was homogeneous. After stirring, the mixture was washed three times with DMF and then dried at 80 °C for 10 h to obtain Bio-MOF-100 powder.

[0041] Bio-MOF-100 powder was annealed at 600 °C under an inert atmosphere. The annealed powder was then mixed with Ketjen Black and PTFE in an 8:1:1 ratio, and finally pressed onto a titanium mesh using a tablet press.

[0042] The pressed sample was combined with a zinc sheet to assemble a battery. (At 2 mA cm⁻¹) -2 Electrodeposition was performed at a current density of 40 mAh / cm³ for 20 h, with a deposition amount of 40 mAh / cm³. -2 The electrodeposited sample was immersed in a 0.2 M or 0.5 M indium trichloride aqueous solution for a displacement reaction for 5 min. After the reaction, the sample was rinsed with deionized water and dried in a 60 °C oven for 10 min to obtain the desired electrode material. The prepared sample was assembled into a symmetrical cell with a glass fiber separator and a 2 M ZnSO4 solution or a 2 M Zn(OTF)2 electrolyte.

[0043] The scanning electron microscope images of the prepared Zn / In-40 are as follows: Figure 1 As shown.

[0044] The materials prepared in this embodiment, when assembled into a symmetrical battery, exhibit the following cycle performance: Figure 2 As shown, at 2 mA cm -2 At a current density, the areal capacity is 1 mAh cm⁻¹ -2 Under these conditions, the cycle time can reach 700 h, and the polarization voltage is only 16 mV.

[0045] Example 2

[0046] A zinc anode electrode material with a heterogeneous metal interface:

[0047] First, 0.135 g of adenine was dissolved in 20 mL of N,N-dimethylformamide (DMF) and stirred thoroughly to prepare solution A. Next, 0.485 g of 4,4'-biphenyl dicarboxylic acid was also dissolved in 20 mL of DMF and stirred until completely dissolved to form solution B. Then, 2 g of polyvinylpyrrolidone (PVP) was dissolved in 40 mL of DMF. After complete dissolution, 0.42 g of zinc acetate was added, and stirring continued to form solution C. Finally, solutions A, B, and C were sequentially added to a mixed solution containing 20 mL of DMF, 4 mL of methanol, and 2 mL of deionized water, and stirring continued until the mixture was homogeneous. After stirring, the mixture was washed three times with DMF and then dried at 80 °C for 10 h to obtain Bio-MOF-100 powder.

[0048] Bio-MOF-100 powder was annealed at 600 °C under an inert atmosphere. The annealed powder was then mixed with Ketjen Black and PTFE in an 8:1:1 ratio, and finally pressed onto a titanium mesh using a tablet press.

[0049] The pressed sample was combined with a zinc sheet to assemble a battery. (At 2 mA cm⁻¹) -2 Electrodeposition was performed at a current density of 30 mAh / cm³ for 15 h, with a deposition amount of 30 mAh / cm³. -2 The electrodeposited sample was immersed in a 0.5 M indium trichloride aqueous solution for a displacement reaction for 5 min. After the reaction, the sample was rinsed with deionized water and dried in a 60 °C oven for 10 min to obtain the desired electrode material. The prepared sample was assembled into a symmetrical cell with a glass fiber separator and a 2 M ZnSO4 solution as the electrolyte.

[0050] The scanning electron microscope images of the prepared Zn / In-30 are as follows: Figure 3 As shown.

[0051] The materials prepared in this embodiment, when assembled into a symmetrical battery, exhibit the following cycle performance: Figure 4 As shown, at 2 mA cm -2 At a current density, the areal capacity is 1 mAh cm⁻¹ -2 In this case, the cycle time is only 100 h and the polarization voltage is 17 mV.

[0052] Example 3

[0053] A zinc anode electrode material with a heterogeneous metal interface:

[0054] First, 0.135 g of adenine was dissolved in 20 mL of N,N-dimethylformamide (DMF) and stirred thoroughly to prepare solution A. Next, 0.485 g of 4,4'-biphenyl dicarboxylic acid was also dissolved in 20 mL of DMF and stirred until completely dissolved to form solution B. Then, 2 g of polyvinylpyrrolidone (PVP) was dissolved in 40 mL of DMF. After complete dissolution, 0.42 g of zinc acetate was added, and stirring continued to form solution C. Finally, solutions A, B, and C were sequentially added to a mixed solution containing 20 mL of DMF, 4 mL of methanol, and 2 mL of deionized water, and stirring continued until the mixture was homogeneous. After stirring, the mixture was washed three times with DMF and then dried at 80 °C for 10 h to obtain Bio-MOF-100 powder.

[0055] Bio-MOF-100 powder was annealed at 600°C under an inert atmosphere. The annealed powder was then mixed with Ketjen Black and PTFE in an 8:1:1 ratio, and finally pressed onto a titanium mesh using a tablet press.

[0056] The pressed sample was combined with a zinc sheet to assemble a battery. (At 2 mA cm⁻¹) -2 Electrodeposition was performed at a current density of 50 mAh / cm³ for 25 h, with a deposition amount of 50 mAh / cm³. -2 The electrodeposited sample was immersed in a 0.5 M indium trichloride aqueous solution for a displacement reaction for 5 min. After the reaction, the sample was rinsed with deionized water and dried in a 60 °C oven for 10 min to obtain the desired electrode material. The prepared sample was assembled into a symmetrical cell with a glass fiber separator and a 2 M ZnSO4 solution as the electrolyte.

[0057] The scanning electron microscope images of the prepared Zn / In-50 are as follows: Figure 5 As shown.

[0058] The materials prepared in this embodiment, when assembled into a symmetrical battery, exhibit the following cycle performance: Figure 6 As shown, at 2 mA cm -2 At a current density, the areal capacity is 1 mAh cm⁻¹ -2 In this case, the cycle time is 190 h, and the polarization voltage is 18 mV in the first 100 h, and the polarization voltage begins to increase significantly after 100 h.

[0059] Comparative Example 1

[0060] A zinc anode electrode material with a heterogeneous metal interface:

[0061] First, 0.135 g of adenine was dissolved in 20 mL of N,N-dimethylformamide (DMF) and stirred thoroughly to prepare solution A. Next, 0.485 g of 4,4'-biphenyl dicarboxylic acid was also dissolved in 20 mL of DMF and stirred until completely dissolved to form solution B. Then, 2 g of polyvinylpyrrolidone (PVP) was dissolved in 40 mL of DMF. After complete dissolution, 0.42 g of zinc acetate was added, and stirring continued to form solution C. Finally, solutions A, B, and C were sequentially added to a mixed solution containing 20 mL of DMF, 4 mL of methanol, and 2 mL of deionized water, and stirring continued until the mixture was homogeneous. After stirring, the mixture was washed three times with DMF and then dried at 80 °C for 10 h to obtain Bio-MOF-100 powder.

[0062] Bio-MOF-100 powder was annealed at 600°C under an inert atmosphere. The annealed powder was then mixed with Ketjen Black and PTFE in an 8:1:1 ratio, and finally pressed onto a titanium mesh using a tablet press.

[0063] The pressed sample was combined with a zinc sheet to assemble a battery. (At 2 mA cm⁻¹) -2 Electrodeposition was performed at a current density of 40 mAh / cm³ for 20 h, with a deposition amount of 40 mAh / cm³. -2 The prepared samples were assembled into symmetrical cells with a glass fiber separator and a 2 M ZnSO4 solution as the electrolyte.

[0064] The obtained scanning electron microscope images of Bare Zn are as follows: Figure 7 As shown.

[0065] The materials prepared in this comparative example, when assembled into a symmetrical battery, exhibit the following cycle performance: Figure 8 As shown, at 2 mA cm -2 At a current density, the areal capacity is 1 mAh cm⁻¹ -2 In this case, the cycle time is only 125 h and the polarization voltage is 120 mV.

[0066] The preferred embodiments of the present invention have been described in detail above. It should be understood that those skilled in the art can make numerous modifications and variations based on the concept of the present invention without creative effort. Therefore, all technical solutions that can be obtained by those skilled in the art based on the concept of the present invention through logical analysis, reasoning, or limited experimentation on the basis of existing technology should be within the scope of protection defined by the claims.

Claims

1. A method for preparing a zinc negative electrode material with a heterogeneous metal interface, the method comprising: S1: First, adenine is dissolved in N,N-dimethylformamide and stirred thoroughly to prepare solution A; then, 4,4'-biphenyl dicarboxylic acid is also dissolved in DMF and stirred until completely dissolved to form solution B; next, polyvinylpyrrolidone is dissolved in DMF, and after it is completely dissolved, zinc acetate is added and stirring continues to form solution C; finally, solutions A, B, and C are added sequentially to a mixed solution containing N,N-dimethylformamide, methanol, and deionized water, and stirring is continued until the mixture is homogeneous. After stirring, the mixture is washed three times with DMF, and then dried at 80 °C for 10 h to obtain Bio-MOF-100 powder, wherein the mass of adenine is 0.02~0.2 g, the mass of 4,4'-biphenyl dicarboxylic acid is 0.05~0.5 g, the mass of PVP is 0.5~2 g, and the mass of zinc acetate is 0.2~0.5 g. g, the amount of DMF used in solutions A, B, C and the mixed solution is 10~20 mL, the amount of methanol is 1~5 mL, and the amount of deionized water is 1~5 mL. S2: Anneal the Bio-MOF-100 powder under high temperature and inert atmosphere conditions; S3: After annealing, Bio-MOF-100 powder is mixed with Ketjen black and PTFE, rolled into a film, and pressed onto a titanium mesh using a tablet press. The Bio-MOF-100 powder is mixed with Ketjen black and PTFE in a ratio of 8:1:1 or 7:2:

1. S4: Combine the pressed sample with a zinc sheet to assemble a battery. The battery uses the sample prepared in S3 as the working electrode and the zinc sheet as the counter electrode, operating at a current density of 2~10 mA cm⁻¹. -2 Under certain conditions, the electrodeposition process is carried out, and the amount of zinc deposited is precisely controlled by adjusting the electrodeposition time; S5: The electrodeposited sample is immersed in solutions of indium trichloride, antimony trichloride, bismuth trifluoromethanesulfonate, and tin trichloride to carry out a displacement reaction. After the reaction is completed, the sample is rinsed and dried in an oven to obtain the desired electrode material. In S5, the sample prepared in S4 is immersed in a 0.1~2 mol / L solution of indium trichloride, antimony trichloride, bismuth trifluoromethanesulfonate, and tin trichloride for 1~10 minutes. The drying process is carried out in a constant temperature oven at 60 ℃ for 1~10 minutes. After assembling into a symmetrical cell, the electrode material is dried at a current density of 2 mA cm⁻¹. -2 Surface capacity is 1 mAh cm -2 It was cycled for 700 h under these conditions, and the polarization voltage was only 16 mV.

2. In the preparation method according to claim 1, in S2, the annealing temperature is 400~800 ℃, the inert gas is argon, the heating rate is 3~5 ℃ / min, and the holding time is 5~10 h.

3. The preparation method according to claim 1, wherein in S4, the zinc deposition amounts corresponding to deposition times of 10, 15, 20, 25, and 30 h are 20, 30, 40, 50, and 60 mAh cm⁻¹, respectively. -2 .

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