Single-crystal zinc negative electrode, preparation method and application thereof in assembling high-performance zinc battery

Abstract

The application provides a single-crystal zinc negative electrode, a preparation method and application thereof in assembling high-performance zinc batteries. The preparation of the single-crystal zinc negative electrode comprises the following steps: step S1, cutting, cleaning and drying brass foil to obtain a brass foil substrate; step S2, placing the brass foil substrate in the center area of a tube furnace, and preparing reactants copper acetylacetonate and tetrachloroquinone; step S3, introducing inert gas into the tube furnace, raising the furnace temperature to 300-500 DEG C, and keeping for 1.5-2.5 hours to drive the deposition reaction of the Cu3(C6O6)2 film, after the reaction is completed, cooling to room temperature, and taking out the brass foil substrate with the synthesized Cu3(C6O6)2 film; and step S4, assembling the brass foil substrate with the synthesized Cu3(C6O6)2 film in a button cell as a working electrode, and depositing a zinc layer on the surface of the Cu3(C6O6)2 film by an electrodeposition method to obtain a single-crystal zinc negative electrode with a single crystal surface exposure.

Description

Technical Field

[0001] This invention relates to the field of zinc metal battery technology, specifically to a single-crystal zinc anode, its preparation method, and its application in assembling high-performance zinc batteries. Background Technology

[0002] In recent years, lithium-ion battery technology has become increasingly sophisticated, making it a leader in the next generation of electrochemical energy storage. However, the organic electrolytes used in commercial lithium-ion batteries currently pose a risk of flammability, which has brought significant obstacles to the application of lithium batteries and safety hazards. In addition, the high cost of lithium metal and the uneven distribution of resources have also limited the rapid promotion of lithium batteries in large-scale energy storage applications.

[0003] Benefiting from its high specific capacity and excellent safety performance, aqueous zinc-ion batteries have attracted much attention in the current energy-scarce environment. Zinc metal anodes possess advantages such as low cost, non-toxicity, and high specific capacity, with a volumetric specific capacity reaching as high as 5855 mAh / cm³. 3 Far exceeding lithium metal anode (2061mAh / cm³) 3 Zinc batteries have shown great application potential. However, the electrochemical reaction of zinc anodes in aqueous electrolytes is currently unstable, and side reactions such as corrosion and hydrogen evolution easily occur at the anode / electrolyte interface, forming low-ionic-conductivity compounds such as zinc oxide and zinc hydroxide, which reduces the cycle life of zinc batteries.

[0004] Studies have shown that compared to zinc and The zinc (0002) crystal facet exhibits the lowest surface energy and the slowest hydrogen evolution reaction rate, and can guide the deposition / nucleation of solvated zinc ions. However, commercial zinc plates show the exposure of polycrystalline components, and the insertion / extraction of zinc ions will cause lattice distortion, which will eventually lead to rapid capacity decay and battery failure. Therefore, maintaining the exposure of a single crystal facet can maintain the high performance of zinc anodes, but there are still many challenges. Summary of the Invention

[0005] This invention is made to solve the above-mentioned problems, and aims to provide a single-crystal zinc anode, a preparation method thereof, and its application in aqueous zinc batteries.

[0006] This invention provides a method for preparing a single-crystal zinc anode, characterized by the following steps:

[0007] Step S1: Cut, clean and dry the brass foil to obtain a brass foil substrate;

[0008] Step S2: Place the brass foil substrate in the central area of ​​the tube furnace, prepare the reactants copper acetylacetonate and tetrachlorobenzoquinone, place copper acetylacetonate in the upstream part of the tube furnace and tetrachlorobenzoquinone in the downstream part to ensure uniform distribution of the reactants;

[0009] Step S3: Inert gas is introduced into the tube furnace, and the furnace temperature is gradually increased to 300-500℃ and maintained at this temperature for 1.5-2.5 hours to drive the deposition reaction of Cu3(C6O6)2 film. After the reaction is completed, the furnace is gradually cooled to room temperature and the brass foil substrate on which Cu3(C6O6)2 film has been synthesized is taken out.

[0010] Step S4: Assemble the brass foil substrate with synthesized Cu3(C6O6)2 thin film in a button cell as the working electrode, and deposit a zinc layer on the surface of Cu3(C6O6)2 thin film by electrodeposition to obtain a single crystal zinc anode with a single crystal plane exposure.

[0011] The method for preparing a single-crystal zinc anode provided by the present invention may also have the following feature: wherein the furnace temperature in step S3 is 300°C.

[0012] The method for preparing a single-crystal zinc anode provided by the present invention may also have the following feature: the furnace temperature is maintained for 2 hours in step S3.

[0013] The method for preparing a single-crystal zinc anode provided by the present invention may also have the following feature: wherein the mass ratio of copper acetylacetonate to tetrachlorobenzoquinone is 1:(0.2-0.3).

[0014] The method for preparing single-crystal zinc anode provided by the present invention may also have the following feature: the rare gas introduced into the tube furnace is argon, and the argon flow rate is set to 2-5 L / min to ensure that the atmosphere in the reaction zone is pure and oxygen-free.

[0015] The present invention also provides a single-crystal zinc anode, which is characterized by being prepared by a single-crystal zinc anode preparation method.

[0016] The monocrystalline zinc anode provided by the present invention may also have the following features: wherein the monocrystalline zinc anode includes a brass foil substrate, a Cu3(C6O6)2 thin film synthesized on the brass foil substrate, and a zinc layer deposited on the surface of the Cu3(C6O6)2 thin film by electrodeposition.

[0017] This invention also provides an application of a single-crystal zinc anode in the assembly of high-performance zinc batteries.

[0018] In the application of the single-crystal zinc anode provided by this invention in assembling high-performance zinc batteries, it may also have the following characteristics: wherein the zinc battery used for assembly includes a zinc-copper half-cell, a zinc symmetric cell, and a zinc-manganese dioxide full cell; when the battery used for assembly is a zinc symmetric cell, a 1mA cm -2 1mAh cm -2 Conditions; when the battery used for assembly is a zinc-copper half-cell, select a 10mA cm -2 The conditions for assembly are as follows: when the battery used is a zinc manganese dioxide full cell, the current conditions of 1.47Ah and 1A / g should be selected.

[0019] In the application of the monocrystalline zinc anode provided by the present invention in the assembly of high-performance zinc batteries, it can also have the following characteristics: wherein, the monocrystalline zinc anode is used as the anode material of the zinc metal battery, the electrolyte is an aqueous zinc sulfate electrolyte, and during the battery cycle, the zinc ions in the zinc salt are regulated by the monocrystalline zinc anode to form a dense zinc deposition on the brass substrate.

[0020] The role and effect of invention

[0021] According to the present invention, the single-crystal zinc anode, its preparation method, and its application in aqueous zinc batteries, the present invention deposits a metal-organic framework material Cu3(C6O6)2 onto a brass substrate via vapor deposition. Utilizing the low lattice mismatch between the brass substrate and the deposited zinc layer, the zinc atoms in the electroplated zinc layer are effectively aligned along the (0002) crystal plane, significantly improving the uniformity of the zinc anode surface and reducing orientation differences and lattice distortion between different crystal planes. This preferential exposure of a single crystal plane lowers the surface energy of the zinc anode, facilitating a stable zinc ion deposition / stripping process and extending the battery's lifespan.

[0022] The ordered porous Cu3(C6O6)2 film in this invention provides a rapid transport channel for zinc ions while reducing the overpotential of zinc ions during deposition. This design effectively lowers the nucleation energy barrier for zinc ions, prevents disordered dendrite growth, and suppresses the hydrogen evolution reaction commonly seen at low current densities. Attached Figure Description

[0023] Figure 1 This is a schematic diagram of the formation mechanism of the single-crystal zinc anode of the present invention;

[0024] Figure 2 This is a scanning electron microscope image of the single-crystal zinc anode of Embodiment 1 of the present invention;

[0025] Figure 3 This is a transmission electron microscope image of a single-crystal zinc anode from Embodiment 1 of the present invention;

[0026] Figure 4These are contact angle test diagrams of the monocrystalline zinc anode of Embodiment 1 and the commercial zinc sheet of Comparative Example 1 of the present invention;

[0027] Figure 5 This is a test of the charge-discharge efficiency of the zinc negative electrode in each embodiment of the present invention (depth of discharge is 30%).

[0028] Figure 6 This is a test of the charge-discharge efficiency of the zinc negative electrode in each embodiment of the present invention (depth of discharge is 50%).

[0029] Figure 7 These are test curves of the monocrystalline zinc anode of Embodiment 1 and the commercial zinc sheet Tafel of Comparative Example 1.

[0030] Figure 8 These are the overpotential test diagrams of the hydrogen evolution reaction of the single-crystal zinc anode in Embodiment 1 of the present invention and the commercial zinc sheet in Comparative Example 1.

[0031] Figure 9 This is a test diagram of the nucleation potential of a zinc-copper half-cell assembled from a single-crystal zinc anode in Embodiment 1 of the present invention and a commercial zinc sheet in Comparative Example 1.

[0032] Figure 10 These are deposition potential test diagrams of a zinc-copper half-cell assembled from a single-crystal zinc anode in Embodiment 1 of the present invention and a commercial zinc sheet in Comparative Example 1.

[0033] Figure 11 This is a coulombic efficiency test chart of a zinc-copper half-cell assembled from a single-crystal zinc anode of Embodiment 1 and a commercial zinc sheet of Comparative Example 1.

[0034] Figure 12 These are coulombic efficiency test graphs of a zinc-zinc symmetric battery assembled from a single-crystal zinc anode of Embodiment 1 and a commercial zinc sheet of Comparative Example 1.

[0035] Figure 13 This is a capacity test diagram of a zinc-manganese dioxide battery assembled from a monocrystalline zinc anode in Embodiment 1 of the present invention and a commercial zinc sheet in Comparative Example 1. Detailed Implementation

[0036] In the description of this application, it should be noted that, unless otherwise expressly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection, an electrical connection, or a connection that allows communication between them; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication between two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.

[0037] To make the technical means, creative features, objectives and effects of this invention easy to understand, the following embodiments, in conjunction with the accompanying drawings, specifically illustrate a single-crystal zinc anode, its preparation method, and its application in assembling high-performance zinc batteries.

[0038] Example 1

[0039] The method for preparing a single-crystal zinc anode according to this embodiment includes the following steps:

[0040] Step S1: Cut the brass foil to 3×3cm with a thickness of 0.05μm, clean and dry it to obtain a brass foil substrate with no contaminants on the surface;

[0041] Step S2: Place the brass foil substrate in the center area of ​​the tube furnace, prepare 8 mg of copper acetylacetonate and 2 mg of tetrachlorobenzoquinone reactants, place the copper acetylacetonate in the upstream part of the tube furnace and the tetrachlorobenzoquinone in the downstream part to ensure uniform distribution of reactants;

[0042] Step S3: Argon gas is introduced into the tube furnace at a flow rate of 3L / min. The furnace temperature is gradually increased to 300°C and maintained at this temperature for 2 hours to drive the deposition reaction of Cu3(C6O6)2 film. After the reaction is completed, the furnace is gradually cooled to room temperature and the brass foil substrate with the synthesized Cu3(C6O6)2 film is removed.

[0043] Step S4: Assemble the brass foil substrate with the synthesized Cu3(C6O6)2 thin film as the working electrode in a coin cell. Deposit a zinc layer on the surface of the Cu3(C6O6)2 thin film using electrodeposition. Add 2M zinc sulfate electrolyte. Use commercial zinc foil as the negative electrode. Set the electroplating program to a current density of 0.1 mA cm⁻¹. -2 The electroplating time is 100 hours. After the program is completed, the battery is removed, the electroplated brass foil substrate is taken out, and it is cleaned with deionized water to obtain a single crystal zinc anode with a single (0002) crystal plane exposure.

[0044] The monocrystalline zinc anode obtained above is used in the assembly of high-performance zinc batteries. The specific application method is as follows:

[0045] An aqueous zinc-manganese dioxide full battery is provided, wherein the electrolyte is a 2M zinc sulfate electrolyte, the negative electrode is a single crystal zinc prepared by the above preparation method, the positive electrode is MnO2 material, and the battery is assembled using a GE-Whatman glass fiber membrane.

[0046] The positive electrode of the battery is prepared as follows: 8 mg of sodium hypophosphite and 10 mg of potassium permanganate are dissolved in 20 mL of deionized water. The potassium permanganate solution is slowly added to the sodium hypophosphite solution through a constant pressure titration funnel with stirring for 0.5 h. After centrifugation, the precipitate is collected and washed with water to remove residual salt. Then, it is dried in a freeze dryer for 24 h. 60 wt% of polytetrafluoroethylene emulsion (purchased from Shanghai Sanai Fu New Material Co., Ltd.) and graphite are added to the above manganese dioxide material. The mass ratio of manganese dioxide material: 60 wt% polytetrafluoroethylene emulsion: graphite is controlled to be 8:1:1. After mixing evenly, it is placed in an oven to dry. The dried sample is pressed onto a stainless steel mesh (purchased from Jiangsu Ningcong Wire Mesh) under a pressure of 20 MPa and vacuum dried at 60 °C for 24 h to obtain the positive electrode of the battery.

[0047] The energy storage performance of the aqueous zinc-manganese dioxide full battery was tested using a CHI660E electrochemical workstation and a Blue Electric testing device. The capacity retention rate of the aqueous zinc-manganese dioxide full battery after 1500 charge-discharge cycles was over 76%, demonstrating excellent energy density and outstanding cycle life.

[0048] Figure 1 This is a schematic diagram of the formation mechanism of the single-crystal zinc anode of the present invention.

[0049] like Figure 1 As shown, the synergistic effect of the brass substrate and the Cu3(C6O6)2 film achieves efficient desolvation of zinc ions and a low lattice mismatch of 4.24%, thereby promoting the directional nucleation and epitaxial growth of Zn. This design helps to improve the stability and uniformity of the zinc layer and optimize battery performance.

[0050] Figure 2 This is a scanning electron microscope image of the single-crystal zinc anode of Embodiment 1 of the present invention.

[0051] like Figure 2 As shown, the dense negative electrode texture exhibits stable epitaxial growth, which is beneficial to the long-cycle performance of zinc batteries.

[0052] Figure 3 This is a transmission electron microscope image of the single-crystal zinc anode of Embodiment 1 of the present invention.

[0053] like Figure 3 As shown, the exposed crystal planes can be determined based on the growth direction of the zinc negative electrode layer and the orientation of the epitaxial growth layer. Since zinc metal is hexagonal, Since it is perpendicular to the (0002) crystal plane, it can be concluded that the exposed crystal plane of the prepared negative electrode is the (0002) plane.

[0054] Example 2

[0055] In this embodiment, based on the preparation conditions of Example 1, the mass of copper acetylacetonate(II) and tetrachlorobenzoquinone added in step S2 was replaced with 4 mg and 2 mg, respectively.

[0056] Tests show that the zinc anode prepared under these conditions has high surface flatness, but its (0002) crystal plane exposure is slightly reduced, resulting in a slight decrease in specific capacity compared to Example 1, and the operating discharge depth can only reach 50%.

[0057] Example 3

[0058] In this embodiment, based on the preparation conditions of Example 1, the mass of copper acetylacetonate(II) and tetrachlorobenzoquinone added in step S2 was replaced with 6 mg and 2 mg, respectively.

[0059] Example 4

[0060] In this embodiment, based on the preparation conditions of Example 1, the furnace temperature in step S3 is set to 400°C and maintained for 2 hours.

[0061] Example 5

[0062] In this embodiment, based on the preparation conditions of Example 1, the furnace temperature in step S3 is set to 500°C.

[0063] Figure 5 This is a test of the charge-discharge efficiency of the zinc negative electrode in each embodiment of the present invention (depth of discharge is 30%).

[0064] A higher efficiency value indicates better reversibility of the negative electrode. Example 1 shows a higher coulombic efficiency of 99% compared to the other examples, indicating that the zinc negative electrode of Example 1 has higher reversibility and more stable cycle performance.

[0065] Figure 6 This is a test of the charge-discharge efficiency of the zinc negative electrode in each embodiment of the present invention (depth of discharge is 50%).

[0066] A higher efficiency value indicates better reversibility of the negative electrode, such as Figure 6 As shown, Example 1 exhibits a higher coulombic efficiency of 99% compared to the other examples, indicating that the zinc anode of Example 1 has higher reversibility and more stable cycling performance.

[0067] Comparative Example 1

[0068] In this comparative example, based on the preparation conditions of Example 1, commercial zinc sheets were selected as the negative electrode material.

[0069] Figure 4 These are contact angle test diagrams of the monocrystalline zinc anode of Embodiment 1 and the commercial zinc sheet of Comparative Example 1 of the present invention.

[0070] like Figure 4 As shown, Example 1 exhibits a smaller contact angle compared to Comparative Example 1. A smaller contact angle indicates stronger hydrophilicity in the material, which is beneficial for uniform electrolyte distribution and ion conduction, thereby improving the overall battery performance. This test result provides an important reference for selecting the optimal negative electrode material.

[0071] Figure 7 These are test curves of the monocrystalline zinc anode of Embodiment 1 of the present invention and the commercial zinc sheet Tafel of Comparative Example 1.

[0072] like Figure 7 As shown, this invention conducted Tafel polarization tests on commercial zinc sheets and monocrystalline zinc sheets. The test results show that the corrosion current density of the monocrystalline zinc sheet is 3.04 mA cm⁻², significantly lower than the 6.22 mA cm⁻² of the commercial zinc sheet. This indicates that the monocrystalline zinc sheet has a lower corrosion rate, which is more conducive to long-term stable operation in aqueous electrolytes.

[0073] Figure 8 These are the overpotential test diagrams of the hydrogen evolution reaction of the single-crystal zinc anode in Embodiment 1 of the present invention and the commercial zinc sheet in Comparative Example 1.

[0074] like Figure 8 As shown, the hydrogen evolution overpotential of the monocrystalline zinc sheet is 341.18 mA dec⁻¹, significantly higher than the 232.30 mA dec⁻¹ of commercial zinc sheets. This indicates that the monocrystalline zinc sheet has a slower hydrogen evolution rate, which is more conducive to long-term stable operation in aqueous electrolytes.

[0075] Figure 9 This is a test diagram of the nucleation potential of a zinc-copper half-cell assembled from a single-crystal zinc anode in Embodiment 1 of the present invention and a commercial zinc sheet in Comparative Example 1.

[0076] like Figure 9 As shown, this potential test graph uses voltage as the vertical axis and electroplating capacity as the horizontal axis. The smaller the deposition voltage, the lower the nucleation overpotential of the negative electrode, which is more conducive to the stable nucleation of zinc ions and the epitaxial growth of the zinc layer.

[0077] Figure 10 This is a test diagram of the deposition potential of a zinc-copper half-cell assembled from a single-crystal zinc anode in Embodiment 1 of the present invention and a commercial zinc sheet in Comparative Example 1.

[0078] like Figure 10 As shown, the potential test graph uses voltage as the vertical axis and time as the horizontal axis. The smaller the cycle voltage, the stronger the stability of the negative electrode. The final stripping capacity is used to measure the reversibility efficiency of the negative electrode. The closer it is to 120h, the better the reversibility of the corresponding zinc negative electrode.

[0079] Figure 11The figures show the coulombic efficiency test results of the zinc-copper half-cell assembled from the monocrystalline zinc anode of Embodiment 1 and the commercial zinc sheet of Comparative Example 1.

[0080] like Figure 11 As shown, the potential test graph uses coulombic efficiency as the vertical axis and the number of cycles as the horizontal axis. The higher the cycle efficiency, the better the reversibility of the negative electrode. The more cycles, the better the long-term cycle performance of the negative electrode, which is more conducive to long-term stable operation in aqueous electrolytes.

[0081] Figure 12 The figures show the coulombic efficiency test results of a zinc-zinc symmetric battery assembled from a monocrystalline zinc anode of Embodiment 1 and a commercial zinc sheet of Comparative Example 1.

[0082] like Figure 12 As shown, the potential test graph uses voltage as the vertical axis and time as the horizontal axis. The smaller the cycle voltage, the stronger the stability of the negative electrode. The longer the cycle time, the better the long-cycle performance of the negative electrode, which is more conducive to long-term stable operation in aqueous electrolytes.

[0083] Figure 13 This is a capacity test diagram of a zinc-manganese dioxide battery assembled from a monocrystalline zinc anode in Embodiment 1 of the present invention and a commercial zinc sheet in Comparative Example 1.

[0084] like Figure 13 As shown in the figure, the cycle performance test graph uses specific capacity as the vertical axis and the number of cycles as the horizontal axis. The larger the specific capacity and the more cycles, the better the battery performance. The comparison shows that the performance of the Zn-MnO2 full battery assembled in Example 1 is significantly better than that of Comparative Example 1. Moreover, the capacity retention rate of the assembled Zn-MnO2 full battery after 1500 charge-discharge cycles is more than 76%, which indicates a longer cycle life.

[0085] The role and effect of the embodiments

[0086] According to the present invention, the single-crystal zinc anode, its preparation method, and its application in aqueous zinc batteries, the present invention deposits a metal-organic framework material Cu3(C6O6)2 onto a brass substrate via vapor deposition. Utilizing the low lattice mismatch between the brass substrate and the deposited zinc layer, the zinc atoms in the electroplated zinc layer are effectively aligned along the (0002) crystal plane, significantly improving the uniformity of the zinc anode surface and reducing orientation differences and lattice distortion between different crystal planes. This preferential exposure of a single crystal plane lowers the surface energy of the zinc anode, facilitating a stable zinc ion deposition / stripping process and extending the battery's lifespan.

[0087] The ordered porous Cu3(C6O6)2 film in this invention provides a rapid transport channel for zinc ions while reducing the overpotential of zinc ions during deposition. This design effectively lowers the nucleation energy barrier for zinc ions, prevents disordered dendrite growth, and suppresses the hydrogen evolution reaction commonly seen at low current densities.

[0088] The raw materials used in this invention are widely available, inexpensive, and environmentally friendly. The preparation process of the zinc battery electrolyte and aqueous zinc battery is simple and easy to operate, and does not involve toxic or harmful reagents or vacuum preparation conditions.

[0089] The monocrystalline zinc anode of this invention exhibits excellent performance in various battery configurations. For example, a zinc-zinc battery using the monocrystalline zinc anode of this invention achieves excellent performance at 1 mA / cm². -2 1mAh cm -2 Under these conditions, it can operate stably for over 2000 hours, demonstrating an exceptionally long cycle life; furthermore, the zinc-copper battery performs well at 10 mA cm⁻¹. -2 Under these conditions, the average coulombic efficiency reaches 99.55%, and it maintains excellent performance even after 4000 cycles. The zinc||manganese dioxide pouch cell (1.47Ah) using the zinc anode of this invention maintains good stability after 500 cycles at a current of 1A / g.

[0090] Those skilled in the art should understand that this invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to this invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A method for producing a single-crystal zinc negative electrode, characterized by, It comprises the following steps: Step S1, cutting, cleaning and drying brass foil to obtain a brass foil substrate; Step S2, placing the brass foil substrate in the center area of the tube furnace, preparing the reactants acetylacetone copper and chloranil, placing the acetylacetone copper in the upstream part of the tube furnace, and placing the chloranil in the downstream part, ensuring uniform distribution of the reactants; Step S3, introducing inert gas into the tube furnace, gradually increasing the furnace temperature to 300-500℃, and keeping the temperature for 1.5-2.5 hours to drive the deposition reaction of Cu3(C6O6)2 thin film, after the reaction is completed, gradually cooling to room temperature, and taking out the brass foil substrate with synthesized Cu3(C6O6)2 thin film; Step S4: Assembling the brass foil substrate with synthesized Cu3(C6O6)2 thin film in a button cell as a working electrode, depositing a zinc layer on the surface of the Cu3(C6O6)2 thin film by electrodeposition to obtain a single-crystal zinc negative electrode with single-crystal surface exposure.

2. The method according to claim 1, wherein the furnace temperature in step S3 is 300℃. wherein 3. The method according to claim 2, wherein the furnace temperature in step S3 is kept for 2 hours.

4. The method according to claim 3, wherein the mass ratio of acetylacetone copper to chloranil is 1:(0.2-0.3). wherein, 5. The method according to claim 1, wherein the noble gas introduced into the tube furnace is argon, and the argon flow rate is set to 2-5 L / min to ensure that the atmosphere in the reaction zone is pure and oxygen-free. The single-crystal zinc negative electrode is prepared by the method according to any one of claims 1-5. wherein The single-crystal zinc negative electrode comprises a brass foil substrate, a Cu3(C6O6)2 thin film synthesized on the brass foil substrate, and a zinc layer deposited on the surface of the Cu3(C6O6)2 thin film by electrodeposition.

8. Use of the single-crystal zinc negative electrode according to claim 6 or 7 in assembling high-performance zinc batteries.

9. Use of the single-crystal zinc negative electrode according to claim 8 in assembling high-performance zinc batteries, wherein the zinc battery electrolyte is a zinc sulfate aqueous electrolyte.

6. The single-crystalline zinc anode of claim 1, wherein the zinc anode is characterized by:

10. Use of the single-crystal zinc negative electrode according to claim 9 in assembling high-performance zinc batteries, wherein the zinc battery electrolyte is a zinc sulfate aqueous electrolyte.

7. A single-crystalline zinc anode according to claim 6, characterized in that, ​ ​ ​ wherein The zinc battery for assembly includes zinc copper half battery, zinc symmetric battery and zinc manganese dioxide full battery, the battery for assembly is zinc symmetric battery, selects 1mA cm -2 , 1mAh cm -2 The condition; the battery for assembly is zinc copper half battery, selects 10mA cm -2 The condition; the battery for assembly is zinc manganese dioxide full battery, selects 1.47Ah, 1A / g current condition. ​ wherein, ​

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