A method for preparing (002) crystal plane-oriented metallic zinc and its application

Abstract

This invention provides a method for preparing (002) crystal-plane oriented metallic zinc and its application. The invention employs a two-electrode electrochemical deposition technique, using iron foil, titanium foil, or copper foil as the working electrode, commercial zinc foil as the counter electrode, and an aqueous zinc salt solution as the electrolyte. Constant current density discharge deposition is used to deposit (002) crystal-plane oriented metallic zinc on the working electrode; the constant current density is 50 mA cm⁻¹. ‑2 ~200 mA cm ‑2 The (002) crystal-plane oriented metallic zinc prepared by this invention can be used in rechargeable zinc-ion batteries. The two-electrode electrolytic cell device used in the preparation of metallic zinc in this invention is simple, the preparation process is straightforward, and the preparation method is more universal. The (002) crystal-plane oriented metallic zinc prepared according to the method of this invention can suppress zinc dendrite growth and hydrogen evolution, thereby improving the service life of rechargeable zinc-ion batteries.

Description

Technical Field

[0001] This invention relates to the field of zinc preparation, specifically to a method for preparing (002) crystal-plane oriented zinc and its application. Background Technology

[0002] Energy and the environment are two major issues that humanity must address for survival and social development. With the depletion of fossil fuels such as coal and oil and the increasing environmental degradation, developing renewable energy sources such as solar, wind, and hydropower has become a global trend. Batteries, as efficient electrochemical energy storage devices, have been widely used in electric vehicles and mobile communications. High-energy-density lithium-ion batteries are widely used in portable electronic products and electric vehicles, but the limited reserves of lithium metal in the Earth's crust, its high price, and safety concerns hinder its large-scale use. Rechargeable aqueous zinc batteries based on zinc anodes offer advantages such as high safety, abundant resources, and environmental friendliness, making them promising candidates for large-scale energy storage.

[0003] Traditional zinc anodes are predominantly oriented with the (101) crystal plane. This (101) zinc exhibits highly reactive thermodynamic properties, making it prone to hydrogen evolution, zinc corrosion, zinc passivation, and zinc dendrite growth in aqueous electrolytes, severely limiting the lifespan of aqueous zinc batteries. Current research indicates that the (002) crystal plane of zinc has higher chemical stability than the (101) crystal plane, inhibiting zinc dendrite growth, and the hydrogen evolution reaction barrier is greater on the (002) crystal plane (making it less likely to occur). Therefore, preparing zinc with a (002) crystal plane orientation can improve the stability of zinc anodes in aqueous electrolytes, thereby extending the lifespan of rechargeable zinc batteries.

[0004] Currently, the methods for preparing (002) crystal-faceted zinc include: (1) thermal annealing; (2) graphene coating-guided epitaxial growth of zinc; and (3) electrolyte-induced orientation deposition of zinc containing specific anions. For example, the thermal annealing process uses pure zinc sheets as raw materials, melts them at a high temperature of 300~500 ℃ under inert gas protection, and then pours the melt into a mold and cools it to room temperature to obtain (002) crystal-faceted zinc. However, this method is energy-intensive and the process is relatively complicated. The graphene coating-controlled epitaxial growth of zinc uses a graphene coating as the epitaxial substrate. By utilizing the low lattice mismatch between graphene and the (002) crystal facet of zinc, the (002) crystal facet zinc can be guided to grow epitaxially along the graphene coating. This method requires expensive graphene as the epitaxial substrate, and the coating process is complex. In actual operation, the coating is prone to peeling off. By designing an electrolyte containing specific anions, namely CF3SO3, - Anions, using CF3SO3 - and Zn 2+ The chemical coordination effect between them can guide the oriented deposition behavior of metallic zinc. However, CF3SO3-containing...- Anionic zinc salt electrolytes (such as Zn(CF3SO3)2) are expensive and difficult to apply on a large scale.

[0005] Therefore, developing a simple, effective, and scalable technique for preparing (002) crystal-faceted metallic zinc, especially for achieving (002) oriented deposition of metallic zinc in conventional low-cost zinc salt electrolytes (such as ZnSO4), is of great significance and practical value. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing (002) crystal plane oriented metallic zinc and its application. This method utilizes two-electrode electrochemical deposition technology and controls the current density to achieve the controllable preparation of (002) crystal plane oriented metallic zinc in a traditional low-valent zinc salt electrolyte (such as ZnSO4).

[0007] The present invention is implemented as follows: a method for preparing (002) crystal-oriented metallic zinc, wherein the method uses a simple two-electrode electrolytic cell device (the device includes a working electrode, a counter electrode and an electrolyte) to electrochemically deposit crystal-oriented metallic zinc on the working electrode by constant current density discharge deposition.

[0008] The working electrode is generally any one of iron foil, titanium foil, and copper foil, the counter electrode is commercial zinc foil, the electrolyte is a zinc salt electrolyte, and the constant current density is 50 mA cm⁻¹. -2 ~200 mA cm -2 The size of the deposited (002) oriented zinc can be controlled by the deposition time and the size of the working electrode.

[0009] Preferably, the working electrode is a copper foil.

[0010] Preferably, the zinc salt electrolyte comprises any one of zinc sulfate (ZnSO4) aqueous solution, zinc chloride (ZnCl2) aqueous solution, and zinc acetate (Zn(CH3COO)2) aqueous solution. More preferably, the zinc salt electrolyte is zinc sulfate (ZnSO4) aqueous solution.

[0011] Preferably, the concentration of the zinc salt electrolyte is 0.5 mol / L. -1 ~1.5 mol L -1 .

[0012] More preferably, the zinc salt electrolyte is an aqueous solution of zinc sulfate (ZnSO4) with a concentration of 1 mol / L. -1 .

[0013] Preferably, the constant current density is 50 mA cm⁻¹. -2 ~150 mA cm -2More preferably, the constant current density is 80 mA cm⁻¹. -2 ~120 mA cm -2 .

[0014] This invention enables the preparation of (002) crystal-plane oriented metallic zinc in a low-valent zinc salt electrolyte using a two-electrode electrochemical deposition technique. When this metallic zinc is used in a rechargeable zinc-ion battery, a battery with good cycle stability can be obtained.

[0015] The rechargeable zinc-ion battery includes a positive electrode, (002) crystal-oriented metallic zinc prepared according to the present invention, a separator, and an electrolyte. The separator is a glass fiber membrane, polyethylene nonwoven fabric, or microporous filter paper. Preferably, the electrolyte is a 3 M zinc sulfate (ZnSO4) aqueous solution.

[0016] Preferably, the positive electrode in the battery is a hydrated vanadium pentoxide (V₂O₅·nH₂O) positive electrode. The hydrated vanadium pentoxide (V₂O₅·nH₂O) positive electrode is prepared by the following method:

[0017] a) Add 0.091 g of commercial vanadium pentoxide (V2O5) to 5 mL of deionized water and sonicate for 20 minutes until uniformly dispersed.

[0018] b) Slowly add 450 μL of a 30% (w / w) aqueous solution of hydrogen peroxide (H2O2) to the solution in step a). Let stand at room temperature for 6 h.

[0019] c) Wash, centrifuge, and dry the solution obtained in step b) to obtain hydrated vanadium pentoxide (V2O5·nH2O) positive electrode active material.

[0020] d) The hydrated vanadium pentoxide positive electrode active material obtained in step c), conductive carbon, and binder are mixed at a mass ratio of 7:2:1, dispersed in an electrode material dispersion solvent to form a slurry, uniformly coated onto a titanium foil with a thickness of 10-30 µm, and vacuum dried to obtain the final product. The binder is sodium carboxymethyl cellulose (CMC). The conductive carbon material is conductive carbon black, activated carbon, porous carbon, BP-2000, Vulcan XC-72, Super P, or carbon nanotubes. The electrode material dispersion solvent is distilled water.

[0021] This invention prepares (002) crystal-plane oriented metallic zinc using a two-electrode electrochemical deposition technique. The apparatus used is simple, the preparation process is straightforward, and the preparation method is more universal. The (002) crystal-plane oriented metallic zinc prepared according to this invention can suppress zinc dendrite growth and hydrogen evolution, thereby improving the service life of rechargeable zinc batteries. Attached Figure Description

[0022] Figure 1This is a simplified diagram of the experimental setup for preparing (002) crystal-faceted metallic zinc in Example 1. In the diagram: 1. Electrolytic cell, 2. Inert working electrode, 3. Zinc foil counter electrode, 4. DC power supply, 5. Zinc salt electrolyte.

[0023] Figure 2 a and Figure 2 b is an SEM image of the (002) crystal plane metallic zinc prepared in Example 1.

[0024] Figure 3 The image is the XRD characterization pattern of the (002) crystal plane metallic zinc prepared in Example 1.

[0025] Figure 4 This is a Tafel curve of the (002) crystal plane metallic zinc prepared in Example 1.

[0026] Figure 5 This is a test diagram of the cycle stability of (002) crystal plane metallic zinc prepared in Example 1 in a Zn / / Zn symmetric cell with 3 M ZnSO4 electrolyte.

[0027] Figure 6 This is a cycle performance diagram of the Zn / / V2O5 full cell with (002) crystal plane zinc prepared in Example 1.

[0028] Figure 7 The charge-discharge curves are those of the (002) crystal plane zinc Zn / / V2O5 full cell prepared in Example 1.

[0029] Figure 8 a and Figure 8 b is a SEM image of the (101) crystal plane metallic zinc prepared in Comparative Example 1.

[0030] Figure 9 The XRD characterization pattern of the (101) crystal plane metallic zinc prepared in Comparative Example 1 is shown.

[0031] Figure 10 This is a Tafel curve of the (101) crystal plane metallic zinc prepared in Comparative Example 1.

[0032] Figure 11 This is a test graph showing the cycle stability of the (101) crystal plane metallic zinc prepared in Comparative Example 1 in a Zn / / Zn symmetric cell with 3 M ZnSO4 electrolyte.

[0033] Figure 12 This is a cycle performance diagram of the Zn / / V2O5 full cell with (101) crystal plane zinc prepared in Example 1.

[0034] Figure 13 The charge-discharge curves are those of the Zn / / V2O5 full cell with (101) crystal plane zinc prepared in Example 1. Detailed Implementation

[0035] The present invention will be further described below with reference to the embodiments. The embodiments described below are for illustration only and do not limit the scope of protection of the present invention in any way.

[0036] The processes and methods not described in detail in the following examples are conventional methods known in the art. All reagents used in the examples are analytically pure or chemically pure, and can be commercially available or prepared by methods known to those skilled in the art.

[0037] In the following examples or comparative examples, the rechargeable zinc-ion battery includes a positive electrode, a (002) crystal zinc negative electrode or a (101) crystal zinc negative electrode, a separator, and an electrolyte, wherein hydrated vanadium pentoxide (V2O5·nH2O) is used as the positive electrode, 3 M zinc sulfate (ZnSO4) is used as the electrolyte, and a glass fiber membrane is used as the separator.

[0038] The positive electrode is prepared as follows: A mixture of hydrated vanadium pentoxide (V₂O₅·nH₂O) positive electrode active material, Super P as conductive carbon, and sodium carboxymethyl cellulose (CMC) as a binder is prepared in a mass ratio of 7:2:1, dispersed in water to form a slurry, and uniformly coated onto a titanium foil with a thickness of 20 µm, controlling the coating amount to be 2–3 mg / cm². -2 The positive electrode was prepared by drying it in a vacuum oven at 80 °C for 12 hours.

[0039] The present invention prepares (002) crystal plane oriented metallic zinc anodes using the following methods: Figure 1 The two-electrode electrolytic cell device shown includes an electrolytic cell 1 containing zinc salt electrolyte 5, an inert working electrode 2 and a zinc foil counter electrode 3 placed in the zinc salt electrolyte 5, and the positive terminal of a DC power supply 4 connected to the inert working electrode 2 and the negative terminal of the DC power supply 4 connected to the zinc foil counter electrode 3.

[0040] Example 1

[0041] (002) The zinc crystal surface adopts the following method: Figure 1 The two-electrode electrolytic cell apparatus shown is prepared as follows:

[0042] a) Cut a 3 cm × 3 cm × 50 μm copper foil as the working electrode and wipe it clean with alcohol.

[0043] b) Cut a 3 cm × 3 cm × 100 μm commercial zinc foil as the counter electrode and wipe it clean with alcohol.

[0044] c) Weigh 9.687 g of zinc sulfate (ZnSO4) and dilute to 60 mL with distilled water to obtain a 1 M zinc sulfate (ZnSO4) aqueous solution as the electrolyte.

[0045] d) Apply 120 mA cm -2 A constant current discharge deposition process is performed to reach a certain capacity (e.g., 30 mAh). The zinc sheet size can be controlled by the deposition time and the size of the working electrode. After the working electrode is cleaned with distilled water, the complete (002) crystal plane metallic zinc can be obtained by simple manual peeling.

[0046] The obtained (002) crystal plane metallic zinc was subjected to the following physical characterization and electrochemical tests:

[0047] (1) (002) Physical characterization of zinc crystal plane

[0048] The morphology of the prepared (002) crystal plane metallic zinc was characterized by scanning electron microscopy (SEM), and the results are as follows: Figure 2 As shown in a and 2b. From Figure 2 As can be seen from a and 2b, the (002) crystal zinc prepared in this embodiment is a zinc foil made of (002) crystal surfaces tightly stacked together.

[0049] The crystal phase of the prepared (002) crystal plane metallic zinc was characterized and analyzed by X-ray powder diffraction (XRD), and the results are as follows: Figure 3 As shown. From Figure 3 It can be seen that the prepared zinc sheet is indeed zinc (Zn) with the peak position that matches PDF 87-0713 and has the strongest peak at position (002).

[0050] (2) Corrosion resistance test

[0051] The corrosion resistance performance was tested using a three-electrode electrolytic cell. The (002) crystal plane zinc prepared in this embodiment was used as the working electrode, titanium (Ti) as the counter electrode, and Ag / AgCl as the reference electrode. The electrolyte was a 3 M zinc sulfate (ZnSO4) aqueous solution. The LSV test was converted to a Tafel curve method, with a test voltage range of -0.68 V to -1.28 V and a scan rate of 0.1 mV / s. -1 Data was recorded using a CHI660E electrochemical workstation.

[0052] The results are as follows Figure 4 As shown, the results indicate that the (002) crystal plane zinc prepared in this embodiment has a corrosion potential of -1.012 V and a corrosion current of 4.37 mA cm⁻¹ in 3 M zinc sulfate (ZnSO₄) electrolyte. -2 .

[0053] (3) Cyclic stability of zinc anode

[0054] Cyclic stability test of Zn / / Zn symmetric cells: All electrodes used were (002) crystal-faceted zinc prepared in this embodiment. A glass fiber diaphragm was used between two zinc foils. 80 μL of 3 M ZnSO4 electrolyte was added to assemble a Zn / / Zn symmetric cell, and the stability of the electrolyte during long-term cycling was tested. The test was conducted using a CT2001A blue battery testing system at 10 mA cm⁻¹. -2 The system was subjected to cyclic charging and discharging at current density. In each cycle, the system first discharged at a constant current for 30 minutes, and then charged at a constant current for 30 minutes.

[0055] The results are as follows Figure 5 As shown in the figure, it can be seen that the (002) crystal plane zinc prepared using this embodiment can cycle stably for more than 200 hours in a Zn / / Zn symmetric cell, exhibiting excellent cycle stability.

[0056] The (002) crystal-faceted zinc prepared in this embodiment was applied to a full cell. The preparation method of the full cell is as follows: a prepared hydrated vanadium pentoxide (V2O5·nH2O) positive electrode was used as the positive electrode, the (002) crystal-faceted zinc prepared in this embodiment was used as the negative electrode, a glass fiber membrane was used as the separator, 80 μL of 3M ZnSO4 electrolyte was added, the cell was encapsulated, and a Zn / / V2O5 full cell was obtained. Its electrochemical performance was tested.

[0057] Cyclic stability test: The Zn / / V2O5 full cell assembled in this embodiment was charged and discharged within a voltage range of 0.3~1.6 V, with a current density of 2C.

[0058] The cycling performance of the prepared Zn / / V2O5 full cell is shown in the figure below. Figure 6 As shown in the figure, after 100 cycles, the capacity retention rate is as high as 93.2%, demonstrating good cycle reversibility. Figure 7 The charge-discharge curve of the battery after 50 cycles shows an average discharge voltage of 0.9 V.

[0059] Example 2

[0060] (002) The zinc crystal surface adopts the following method: Figure 1 The two-electrode electrolytic cell device was prepared as follows:

[0061] a) Cut a 3 cm × 3 cm × 50 μm copper foil as the working electrode and wipe it clean with alcohol.

[0062] b) Cut a 3 cm × 3 cm × 100 μm commercial zinc foil as the counter electrode and wipe it clean with alcohol.

[0063] c) Weigh 11.01 g of zinc acetate (Zn(CH3COO)2) and dilute to 60 mL with distilled water to obtain a 1 M zinc acetate (Zn(CH3COO)2) aqueous solution as the electrolyte.

[0064] d) Apply 100 mA cm -2 A constant current discharge deposition process is performed to reach a certain capacity (e.g., 30 mAh). The zinc sheet size can be controlled by the deposition time and the size of the working electrode. After the working electrode is cleaned with distilled water, the complete (002) crystal plane metallic zinc can be obtained by simple manual peeling.

[0065] Example 3

[0066] (002) The zinc crystal surface adopts the following method: Figure 1 The two-electrode electrolytic cell device was prepared as follows:

[0067] a) Cut a 3 cm × 3 cm × 50 μm copper foil as the working electrode and wipe it clean with alcohol.

[0068] b) Cut a 3 cm × 3 cm × 100 μm commercial zinc foil as the counter electrode and wipe it clean with alcohol.

[0069] c) Weigh 8.178 g of zinc chloride (ZnCl2) and dilute to 60 mL with distilled water to obtain a 1 M zinc chloride (ZnCl2) aqueous solution as the electrolyte.

[0070] d) Apply 110 mA cm -2 A constant current discharge deposition process is performed to reach a certain capacity (e.g., 30 mAh). The zinc sheet size can be controlled by the deposition time and the size of the working electrode. After the working electrode is cleaned with distilled water, the complete (002) crystal plane metallic zinc can be obtained by simple manual peeling.

[0071] Example 4

[0072] (002) The zinc crystal surface adopts the following method: Figure 1 The two-electrode electrolytic cell device was prepared as follows:

[0073] a) Cut a 3 cm × 3 cm × 50 μm titanium foil as the working electrode and wipe it clean with alcohol.

[0074] b) Cut a 3 cm × 3 cm × 100 μm commercial zinc foil as the counter electrode and wipe it clean with alcohol.

[0075] c) Weigh 9.687 g of zinc sulfate (ZnSO4) and dilute to 60 mL with distilled water to obtain a 1 M zinc sulfate (ZnSO4) aqueous solution as the electrolyte.

[0076] d) Apply 120 mA cm -2 A constant current discharge deposition process is performed to reach a certain capacity (e.g., 30 mAh). The zinc sheet size can be controlled by the deposition time and the size of the working electrode. After the working electrode is cleaned with distilled water, the complete (002) crystal plane metallic zinc can be obtained by simple manual peeling.

[0077] Example 5

[0078] (002) The zinc crystal surface adopts the following method: Figure 1 The two-electrode electrolytic cell device was prepared as follows:

[0079] a) Cut a 3 cm × 3 cm × 50 μm iron foil as the working electrode and wipe it clean with alcohol.

[0080] b) Cut a 3 cm × 3 cm × 100 μm commercial zinc foil as the counter electrode and wipe it clean with alcohol.

[0081] c) Weigh 9.687 g of zinc sulfate (ZnSO4) and dilute to 60 mL with distilled water to obtain a 1 M zinc sulfate (ZnSO4) solution as the electrolyte.

[0082] d) Apply 50 mA cm -2 A constant current discharge deposition process is performed to reach a certain capacity (e.g., 30 mAh). The zinc sheet size can be controlled by the deposition time and the size of the working electrode. After the working electrode is cleaned with distilled water, the complete (002) crystal plane metallic zinc can be obtained by simple manual peeling.

[0083] Comparative Example 1

[0084] (101) The zinc crystal plane adopts the following method: Figure 1 The two-electrode electrolytic cell device was prepared as follows:

[0085] a) Cut a 3 cm × 3 cm × 50 μm copper foil as the working electrode and wipe it clean with alcohol.

[0086] b) Cut a 3 cm × 3 cm × 100 μm commercial zinc foil as the counter electrode and wipe it clean with alcohol.

[0087] c) Weigh 9.687 g of zinc sulfate (ZnSO4) and dilute to 60 mL with distilled water to obtain a 1 M zinc sulfate (ZnSO4) aqueous solution as the electrolyte.

[0088] d) Apply 30 mA cm -2A constant current discharge deposition process is performed to reach a certain capacity (e.g., 30 mAh). The zinc sheet size can be controlled by the deposition time and the size of the working electrode. After the working electrode is cleaned with distilled water, the complete (101) crystal plane metallic zinc can be obtained by simple manual peeling.

[0089] The obtained (101) crystal plane metallic zinc was subjected to the following physical characterization and electrochemical tests:

[0090] (1) Physical characterization of (101) crystal plane metallic zinc

[0091] The morphology of the prepared (101) crystal plane metallic zinc was characterized by scanning electron microscopy (SEM), and the results are as follows: Figure 8 As shown in a and 8b. From Figure 8 As can be seen from a and 8b, the (101) crystal plane metallic zinc prepared in this comparative example is a zinc foil formed by the close intercalation of the (101) crystal plane.

[0092] The crystal phase of the prepared (101) crystal plane metallic zinc was characterized and analyzed by X-ray powder diffraction (XRD), and the results are as follows: Figure 9 As shown. From Figure 9 As can be seen from this, the prepared zinc sheet is indeed zinc (Zn) with the peak position that matches the peak position of PDF 87-0713 and has the strongest peak at position (101).

[0093] (2) Corrosion resistance test

[0094] The corrosion resistance performance was tested using a three-electrode electrolytic cell. The (101) crystal plane zinc prepared in Comparative Example 1 was used as the working electrode, titanium foil (Ti) as the counter electrode, and Ag / AgCl as the reference electrode. The electrolyte was a 3 M zinc sulfate (ZnSO4) aqueous solution. The LSV test was converted to a Tafel curve, with a test voltage range of -0.68 V to -1.28 V and a scan rate of 0.1 mV s. -1 Data was recorded using a CHI660E electrochemical workstation.

[0095] The results are as follows Figure 10 As shown, the results indicate that the (101) crystal plane metallic zinc prepared in Comparative Example 1 has a corrosion potential of -1.016 V and a corrosion current of 7.87 mA cm⁻¹ in 3 M zinc sulfate (ZnSO₄) electrolyte. -2 It is much larger than the (002) crystal plane zinc prepared in Example 1.

[0096] (3) Cyclic stability of zinc anode

[0097] Cyclic stability test of Zn / / Zn symmetric cells: All electrodes used were (101) crystal-plane zinc prepared in this comparative example. A glass fiber diaphragm was used between two zinc foils. 80 μL of 3 M ZnSO4 electrolyte was added to assemble a Zn / / Zn symmetric cell, and the stability of the electrolyte during long-term cycling was tested. The test was conducted using a CT2001A blue battery testing system at 10 mA cm⁻¹. -2 The system was subjected to cyclic charging and discharging at current density. In each cycle, the system first discharged at a constant current for 30 minutes, and then charged at a constant current for 30 minutes.

[0098] The results are as follows Figure 11 As shown in the figure, it can be seen from the figure that the (101) crystal plane metallic zinc prepared using this comparative example can only cycle for 60 hours in a Zn / / Zn symmetric cell before short-circuiting, indicating poor cycle stability.

[0099] The (101) crystal-faceted zinc prepared in this comparative example was used in a full cell. The preparation method of the full cell is as follows: In a dry environment, the prepared hydrated vanadium pentoxide (V2O5·nH2O) positive electrode was used as the positive electrode, the (101) crystal-faceted zinc prepared in this comparative example was used as the negative electrode, and a glass fiber membrane was used as the separator. 80 μL of 3M ZnSO4 electrolyte was added, the cell was sealed, and a Zn / / V2O5 full cell was obtained. Its electrochemical performance was tested.

[0100] Cyclic stability test: The Zn / / V2O5 full cell of this comparative example was charged and discharged in the voltage range of 0.3~1.6 V and the current density was 2C.

[0101] The cycling performance of the prepared Zn / / V2O5 full cell is shown in the figure below. Figure 12 As shown in the figure, after 100 cycles, the capacity retention rate is only 72%, indicating poor cycle stability. Figure 13 The charge-discharge curve of the battery after 50 cycles is shown, with an average discharge voltage of 0.9 V.

[0102] Comparative Example 2

[0103] (101) The zinc crystal plane adopts the following method: Figure 1 The two-electrode electrolytic cell device was prepared as follows:

[0104] a) Cut a 3 cm × 3 cm × 50 μm copper foil as the working electrode and wipe it clean with alcohol.

[0105] b) Cut a 3 cm × 3 cm × 100 μm commercial zinc foil as the counter electrode and wipe it clean with alcohol.

[0106] c) Weigh 11.01 g of zinc acetate (Zn(CH3COO)2) and dilute to 60 mL with distilled water to obtain a 1 M zinc acetate (Zn(CH3COO)2) aqueous solution as the electrolyte.

[0107] d) Apply 20 mA cm -2 A constant current discharge deposition process is performed to reach a certain capacity (e.g., 30 mAh). The zinc sheet size can be controlled by the deposition time and the size of the working electrode. After the working electrode is cleaned with distilled water, the complete (101) crystal plane zinc can be obtained by simple manual peeling.

[0108] Comparative Example 3

[0109] (101) The zinc crystal plane adopts the following method: Figure 1 The two-electrode electrolytic cell device was prepared as follows:

[0110] a) Cut a 3 cm × 3 cm × 50 μm copper foil as the working electrode and wipe it clean with alcohol.

[0111] b) Cut a 3 cm × 3 cm × 100 μm commercial zinc foil as the counter electrode and wipe it clean with alcohol.

[0112] c) Weigh 8.178 g of zinc chloride (ZnCl2) and dilute to 60 mL with distilled water to obtain a 1 M zinc chloride (ZnCl2) aqueous solution as the electrolyte.

[0113] d) Apply 30 mA cm -2 A constant current discharge deposition process is performed to a certain capacity (e.g., 30 mAh). The zinc sheet size can be controlled by the deposition time and the size of the working electrode. After the working electrode is cleaned with distilled water, the complete (101) crystal plane zinc can be obtained by simple manual peeling.

[0114] Comparative Example 4

[0115] (101) The zinc crystal plane adopts the following method: Figure 1 The two-electrode electrolytic cell device was prepared as follows:

[0116] a) Cut a 3 cm × 3 cm × 50 μm titanium foil as the working electrode and wipe it clean with alcohol.

[0117] b) Cut a 3 cm × 3 cm × 100 μm commercial zinc foil as the counter electrode and wipe it clean with alcohol.

[0118] c) Weigh 9.687 g of zinc sulfate (ZnSO4) and dilute to 60 mL with distilled water to obtain a 1 M zinc sulfate (ZnSO4) aqueous solution as the electrolyte.

[0119] d) Apply 30 mA cm -2 A constant current discharge deposition process is performed to reach a certain capacity (e.g., 30 mAh). The zinc sheet size can be controlled by the deposition time and the size of the working electrode. After the working electrode is cleaned with distilled water, the complete (101) crystal plane zinc can be obtained by simple manual peeling.

[0120] Comparative Example 5

[0121] (101) The zinc crystal plane adopts the following method: Figure 1 The two-electrode electrolytic cell device was prepared as follows:

[0122] a) Cut a 3 cm × 3 cm × 50 μm iron foil as the working electrode and wipe it clean with alcohol.

[0123] b) Cut a 3 cm × 3 cm × 100 μm commercial zinc foil as the counter electrode and wipe it clean with alcohol.

[0124] c) Weigh 9.687 g of zinc sulfate (ZnSO4) and dilute to 60 mL with distilled water to obtain a 1 M zinc sulfate (ZnSO4) aqueous solution as the electrolyte.

[0125] d) Apply 10 mA cm -2 A constant current discharge deposition process is performed to reach a certain capacity (e.g., 30 mAh). The zinc sheet size can be controlled by the deposition time and the size of the working electrode. After the working electrode is cleaned with distilled water, the complete (101) crystal plane zinc can be obtained by simple manual peeling.

Claims

1. A method for producing a metal zinc having a (002) crystal plane orientation, characterized by, The two-electrode electrochemical deposition technology is adopted, iron foil, titanium foil or copper foil is used as a working electrode, commercial zinc foil is used as a counter electrode, zinc salt aqueous solution is used as an electrolyte, and constant current density discharge deposition is adopted to deposit (002) crystal surface oriented metal zinc on the working electrode; the constant current density is 50 mA cm -2 ~200 mA cm -2 .

2. The method of producing a (002) plane-oriented metal zinc according to claim 1, wherein The constant current density is 80 mA cm -2 120 mA cm -2 .

3. The method of producing the (002) plane-oriented metal zinc according to claim 2, characterized by, The constant current density is 120 mA cm -2 .

4. The method of producing the (002) plane-oriented metal zinc according to claim 1, characterized by, The zinc salt aqueous solution is a zinc sulfate aqueous solution, a zinc chloride aqueous solution or a zinc acetate aqueous solution.

5. The method of producing a (002) plane-oriented metal zinc according to claim 4, characterized by, The electrolyte concentration is 0.5 mol L -1 ~1.5 mol L -1 .

6. The method of producing a (002) plane-oriented metal zinc according to claim 5, wherein The aqueous zinc salt solution is an aqueous zinc sulfate solution, and the aqueous zinc sulfate solution has a concentration of 1 mol / L -1 .

7. The use of the (002) crystal plane oriented metal zinc prepared according to any one of claims 1-6 in a rechargeable zinc ion battery.

8. Use of the metal zinc having a (002) crystal plane orientation according to claim 7 in a rechargeable zinc ion battery, characterized in that, The rechargeable zinc ion battery comprises a hydrated vanadium pentoxide positive electrode, a negative electrode, a separator and a 3 M zinc sulfate aqueous solution electrolyte; the negative electrode is (002) crystal plane oriented metal zinc.

9. Use of the metal zinc of the (002) crystal plane orientation according to claim 8 in a rechargeable zinc ion battery, characterized in that, The separator is a glass fiber membrane, a polyethylene non-woven fabric or a microporous filter paper.

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