A three-dimensional zincophilic current collector composite negative electrode constructed by electrochemical welding

Abstract

The application discloses a three-dimensional zincophilic current collector composite negative electrode constructed by an electrochemical welding method.The negative electrode structure is connected by electrochemical welding of a copper base and ZnO / C fibers prepared by electrostatic spinning through pre-electrodeposition of zinc.The application is characterized in that zincophilic ZnO / C fibers are prepared by an electrostatic spinning process combined with high-temperature carbonization, and then ZnO / C and copper foil are subjected to "electrochemical welding" by using zinc electrochemical deposition technology, so that a Zn@ZnO / C-Cu negative electrode material is obtained.The application introduces zincophilic sites ZnO and a high-conductivity copper foil into a large specific surface area carbon fiber, and designs a negative electrode structure which is beneficial to higher efficiency of a zinc ion battery.The prepared negative electrode material improves the cycle and rate performance of the zinc ion battery, and promotes further development of the negative electrode material of the zinc ion battery.

Description

Technical Field

[0001] This invention relates to a three-dimensional zinc-loving current collector composite negative electrode constructed by electrochemical welding, belonging to the technical field of zinc-ion battery negative electrode materials. Background Technology

[0002] Lithium-ion batteries are the most widely used energy storage devices due to their high energy density and long lifespan. However, their widespread use and further development are hindered by issues such as safety concerns, high cost, and limited lithium resources. The emergence and development of aqueous zinc-ion batteries offer new opportunities for large-scale energy storage applications, reversing the energy crisis, and mitigating environmental pollution, due to their high safety, high stability, and low cost. These batteries possess unique advantages, including a high theoretical capacity (820 mA hg). –1 With its suitable redox potential (-0.76V vs. SHE, standard hydrogen electrode), abundant reserves, and low toxicity, zinc is considered the most common negative electrode in zinc-ion batteries.

[0003] However, the most critical challenge for commercial zinc foil lies in uncontrolled, uneven zinc deposition, caused by the sharp edges on the rough surface of the foil and the resulting accumulation of zinc ions around them. Furthermore, continuous side reactions (such as competitive hydrogen evolution) lead to low zinc utilization, accompanied by volume expansion, electrode corrosion, and short-circuit failures, deteriorating the electrochemical performance of zinc-ion batteries and even causing safety accidents.

[0004] Although zinc-ion batteries offer significant advantages, the development of high-efficiency anode materials for these batteries is still in its early stages. Extensive research indicates that zinc dendrite formation primarily stems from the non-uniform distribution of ions and electrons across the entire electrode. To mitigate zinc dendrite growth, uniform nucleation and Zn... 2+ Ion distribution. Compared with planar anodes, three-dimensional anodes have a highly stable framework structure, which can prevent shape changes or structural collapse during zinc ion deposition and stripping. Secondly, three-dimensional anodes can provide wider channels, which is beneficial for charge and ion transport. In addition, the larger reaction surface area and abundant nucleation sites can also induce uniform distribution of zinc ions.

[0005] Invention application CN114937754A provides a dendrite-free negative electrode for zinc-ion batteries and its 3D printing preparation method. This method uses 3D printing technology to deposit a composite coating on one side of zinc and stainless steel foil to inhibit the growth of zinc dendrites. Invention CN112952053B provides a method for preparing zinc / carbon nanotube foam composite material. The method involves first carbonizing carbon nanotubes, then performing hydrophilic treatment, and finally electrochemically depositing zinc to prepare zinc / carbon nanotube foam composite material to inhibit the growth of zinc dendrites.

[0006] However, the existing zinc-ion battery anode fabrication technologies have the following drawbacks: poor conductivity and high ion diffusion impedance result in slow zinc ion transport and low electrochemical activity, thus affecting the battery's capacity and rate performance; the deposition area is small; and the fabrication process is complex and costly. Therefore, adjustments and improvements are needed to the existing fabrication processes and methods for three-dimensional zinc-ion battery anodes. Summary of the Invention

[0007] The purpose of this invention is to address the problems existing in current zinc-ion battery anode materials by providing a method for preparing three-dimensional zinc-loving anode materials using electrospinning technology and electrochemical welding.

[0008] The method of the present invention includes the following steps:

[0009] (1) Add zinc precursor and carbon source to organic solvent, heat and stir to obtain uniformly mixed spinning solution, then transfer the spinning solution into spinning syringe and perform electrospinning under appropriate parameters to obtain carbon fiber containing zinc source.

[0010] (2) The spun fibers obtained by electrospinning are pre-oxidized and carbonized to obtain ZnO / C fibers;

[0011] (3) Pre-electrodeposition: A coin cell is composed of a positive electrode, a negative electrode, a separator between the positive and negative electrodes, and an electrolyte. The material obtained in step (2) is used together with copper foil as a substrate. Then, a program is set to deposit zinc onto the substrate to obtain a three-dimensional zinc-loving current collector composite negative electrode structure.

[0012] Further, in step (1), the carbon source is one or more of the following: polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polycaprolactone (PCL), polyurethane (PU), polylactic acid (PLA), polyethersulfone (PES), polystyrene (PS), polyamide (PA), cellulose acetate (CA), chitosan (CS), and silk fibroin (SF).

[0013] Further, in step (1), the zinc precursor is one or more of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, zinc fluoride, zinc hexafluoroate, zinc trifluoromethanesulfonate, and zinc gluconate.

[0014] Further, in step (1), the organic solvent is one or more of water, ethanol, NN-dimethylformamide (DMF), NN-dimethylacetamide (DMAc), acetone, chloroform (TCM), dichloromethane (DCM), formic acid, hexafluoroisopropanol (HFTP), and tetrahydrofuran (THF);

[0015] Furthermore, in step (1), the injection rate is 15-30 μL / s. -1 The collecting cylinder rotates at a speed of 200-500 rpm. -1 The distance between the collecting tube and the spinneret is 10-20cm, and the voltage is set to 15-22kV;

[0016] Furthermore, in step (2), the atmosphere during pre-oxidation is air, and the atmosphere during carbonization is N2 or Ar;

[0017] Furthermore, in step (2), the heating rate during pre-oxidation is 1-3℃ / min. -1 The heating rate during carbonization is 2-5℃ / min. -1 ;

[0018] Furthermore, in step (2), the temperature during pre-oxidation is 100-300℃, and the temperature during carbonization is 500-900℃;

[0019] Furthermore, in step (2), the pre-oxidation holding time is 2-3 hours, and the carbonization holding time is 2-3 hours;

[0020] Furthermore, in step (2), the carbonization cooling rate is 2-5℃ / min. -1 ;

[0021] Furthermore, in step (3), the positive electrode material is zinc foil;

[0022] Further, in step (3), the diaphragm is selected from one of the following: nonwoven fabric, glass fiber, polyacrylonitrile, polyamide, polyterephthalate, polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, and polycarbonate.

[0023] Furthermore, in step (3), the electrolyte contains a soluble zinc salt, which is at least one of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, zinc fluoride, zinc hexafluoroate, zinc trifluoromethanesulfonate, and zinc gluconate.

[0024] Furthermore, in step (3), the negative electrode is composed of the fiber prepared in step (2) and the copper foil.

[0025] Furthermore, in step (3), the deposition process is constant current charging, and the deposition current density is 1-10 mA cm⁻¹. -1 The deposition capacity is 1-10 mAh cm⁻¹ -1 .

[0026] The advantages of this invention are:

[0027] (1) ZnO has excellent chemical stability and surface wettability, and it has been proven that ZnO can enhance the surface wettability of Zn. 2+ Compared to hydrated zinc ions, ZnO has a stronger electrostatic attraction, providing controllable nucleation and deposition sites through electrostatic attraction, which can effectively prevent the precipitation of H2, and ZnO is easier to fabricate into nanostructures than Zn.

[0028] (2) Carbon-based materials have a high specific surface area, which can balance the ion distribution at the interface;

[0029] (3) The negative electrode material combining Cu and carbon-based zinc-loving materials can provide better conductivity and promote the rapid transfer of ions. Attached Figure Description

[0030] Figure 1 This is a schematic diagram of the Zn@ZnO / C-Cu three-dimensional zinc-loving current collector composite negative electrode structure prepared according to Example 1 of the present invention.

[0031] Figure 2 As a control group, a Zn@Cu assembled symmetrical cell was used at a current density of 5 mA cm⁻¹. -2 The deposition capacity is 1 mAh cm⁻¹ -2 Electrochemical performance at that time.

[0032] Figure 3 The Zn@ZnO / C-Cu assembled symmetric cell prepared according to Example 2 of this invention was tested at a current density of 5 mA / cm². -2 The deposition capacity is 1 mAh cm⁻¹ -2 Electrochemical performance at that time, and Figure 2 There is a significant improvement compared to the previous version.

[0033] Figure 4 As a control group, a Zn@Cu assembled half-cell with Cu as the positive electrode was used at a current density of 1 mA cm⁻¹. -2 The deposition capacity is 0.5 mAh cm⁻¹. -2 Electrochemical performance at that time.

[0034] Figure 5 The Zn@ZnO / C-Cu half-cell assembled according to Example 2 of this invention, with Cu as the positive electrode, was tested at a current density of 1 mA cm⁻¹. -2 The deposition capacity is 0.5 mAh cm⁻¹. -2 Electrochemical performance at that time, and Figure 6 There is a significant improvement compared to the previous version.

[0035] Figure 6 The Zn@Cu and Zn@ZnO / C-Cu half-cells prepared according to Example 2 of this invention, with Cu as the positive electrode, were assembled at a current density of 1 mA cm⁻¹. -2The deposition capacity is 0.5 mAh cm⁻¹. -2 Comparison of electrochemical performance at different times.

[0036] Figure 7 The Zn@Cu and Zn@ZnO / C-Cu assembled symmetric cells prepared according to Examples 2-8 of this invention were tested at a current density of 5 mA cm⁻¹. -2 The deposition capacity is 1 mAh cm⁻¹ -2 And a half-cell with Cu as the positive electrode at a current density of 1 mA cm⁻¹ -2 The deposition capacity is 0.5 mAh cm⁻¹. -2 Comparison of electrochemical performance. Detailed Implementation

[0037] The present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are merely illustrative of the invention and should not be construed as limiting the invention.

[0038] Implementation Example 1

[0039] (1) Dissolve 1.0 g of polyvinylpyrrolidone and 1.0 g of polyacrylonitrile completely in 20 mL of N,N-dimethylacetamide to prepare solution A. Then, dissolve 2 g of zinc acetate dihydrate completely in solution A and stir at 40 °C for 14 h to prepare solution B. (2) For electrospinning, transfer solution B prepared in step (1) to a spinning injector. During rotation, the propulsion rate of the injector is fixed at 15 μL / s. -1 Collection cylinder (rotation speed 200 rpm) -1 (2) The distance between the fiber and the spinneret is 10 cm, and the voltage is maintained at 15 kV; (3) The fiber precursor prepared in step (2) is then calcined. During the calcination process, the precursor is first heated in the open air at 1 °C for 1 min. -1 The temperature was heated to 150°C at a heating rate and held for 3 hours, then heated in an argon atmosphere at a rate of 2°C / min. -1 The temperature was raised to 550℃ at a certain heating rate, and the sample was held at 550℃ for 2 hours, then increased at a rate of 2℃ / min. -1 (3) Cool to room temperature at a cooling rate of 1 mA cm⁻¹; (4) During the electrochemical deposition process, use the fiber obtained in step (3) and Cu together as the negative electrode, zinc foil as the positive electrode, 2M zinc sulfate as the electrolyte, and glass fiber as the separator to assemble a coin cell, and set the current density to 1 mA cm⁻¹ under the charging program. -2 The deposition capacity is 1 mAh cm⁻¹ -2 Zinc was deposited onto the ZnO / C-Cu anode to prepare Zn@ZnO / C-Cu anode material.

[0040] Implementation Example 2

[0041] (1) Dissolve 1.0 g of polyacrylonitrile completely in 20 mL of N,N-dimethylformamide to prepare solution A, then dissolve 0.5 g of zinc acetate dihydrate completely in solution A and stir at 45 °C for 12 h to prepare solution B; (2) For electrospinning, transfer solution B prepared in step (1) to a spinning injector, and during rotation, the propulsion rate of the injector is fixed at 25 μL / s. -1 Collection cylinder (rotation speed 400 rpm) -1 (2) The distance between the fiber and the spinneret is 15cm, and the voltage is maintained at 22kV; (3) The fiber precursor prepared in step (2) is then calcined. During the calcination process, the precursor is first heated in the open air at 2℃ for 1 minute. -1 The temperature was heated to 240°C at a heating rate and held for 3 hours, then heated in an argon atmosphere at a rate of 3°C / min. -1 The temperature was raised to 600℃ at a certain heating rate, and the sample was held at 600℃ for 2 hours, then increased at 3℃ / min. -1 The cooling rate was reduced to room temperature; (4) During the electrochemical deposition process, the fiber obtained in step (3) and Cu were used together as the negative electrode (ZnO / C-Cu), with zinc foil as the positive electrode, 1M zinc acetate as the electrolyte, and glass fiber as the separator to assemble a coin cell. The current density was set to 5 mA cm⁻¹ under the charging program. -2 The deposition capacity is 5 mAh cm⁻¹ -2 Zinc was deposited onto the ZnO / C-Cu anode to prepare Zn@ZnO / C-Cu anode material.

[0042] Implementation Example 3

[0043] (1) Dissolve 1.0 g of polyvinylidene fluoride completely in 20 mL of N,N-dimethylacetamide to prepare solution A, then dissolve 0.75 g of anhydrous zinc acetate completely in solution A and stir at 50 °C for 10 h to prepare solution B; (2) For the electrospinning process, transfer solution B prepared in step (1) into the spinning injector, and during the rotation, the propulsion rate of the injector is fixed at 20 μL / s. -1 Collection cylinder (rotation speed 400 rpm) -1 (2) The distance between the fiber and the spinneret is 12cm, and the voltage is maintained at 20kV; (3) The fiber precursor prepared in step (2) is then calcined. During the calcination process, the precursor is first heated in the open air at 3℃ for 1 minute. -1 The temperature was heated to 150°C at a heating rate and held for 3 hours, then heated in an argon atmosphere at 5°C / min. -1 The temperature was raised to 700℃ at a certain heating rate, and the sample was held at 700℃ for 2.5 hours, then heated at 5℃ / min. -1(3) Cool to room temperature at a cooling rate of 100°C; (4) During the electrochemical deposition process, use the fiber obtained in step (3) and Cu together as the negative electrode, zinc foil as the positive electrode, 3M zinc chloride as the electrolyte, and polycarbonate as the separator to assemble a coin cell, and set the current density to 3 mA cm⁻¹ under the charging program. -2 The deposition capacity is 3 mAh / cm³. -2 Zinc was deposited onto the ZnO / C-Cu anode to prepare Zn@ZnO / C-Cu anode material.

[0044] Implementation Example 4

[0045] (1) Dissolve 1.0 g of polyamide completely in 20 mL of formic acid to prepare solution A, then dissolve 1 g of zinc sulfate completely in solution A and stir at 42 °C for 11 h to prepare solution B; (2) For the electrospinning process, transfer solution B prepared in step (1) to the spinning injector, and during the rotation, the propulsion rate of the injector is fixed at 22 μL / s. -1 Collection cylinder (rotation speed 200 rpm) -1 (2) The distance between the fiber and the spinneret is 18cm, and the voltage is maintained at 18kV; (3) The fiber precursor prepared in step (2) is then calcined. During the calcination process, the precursor is first heated in the open air at 3℃ for 1 minute. -1 Heated to 250°C at a heating rate and held for 2 hours, then heated in an argon atmosphere at 3°C / min. -1 The temperature was raised to 800℃ at a certain heating rate, and the sample was held at 800℃ for 2 hours, then increased at 3℃ / min. -1 (3) Cool to room temperature at a cooling rate of 100°C; (4) During the electrochemical deposition process, use the fiber obtained in step (3) and Cu together as the negative electrode, zinc foil as the positive electrode, 1M zinc trifluoromethanesulfonate as the electrolyte, and polyacrylonitrile as the separator to assemble a coin cell, and set the current density to 10 mA cm⁻¹ under the charging program. -2 The deposition capacity is 10 mAh cm⁻¹ -2 Zinc was deposited onto the ZnO / C-Cu anode to prepare Zn@ZnO / C-Cu anode material.

[0046] Implementation Example 5

[0047] (1) Dissolve 1.0 g of polyamide completely in 20 mL of N,N-dimethylformamide to prepare solution A, then dissolve 0.5 g of zinc chloride completely in solution A and stir at 35 °C for 15 h to prepare solution B; (2) For electrospinning, transfer solution B prepared in step (1) to a spinning injector, and during rotation, the injector's propulsion rate is fixed at 30 μL / s. -1 Collection cylinder (rotation speed 500 rpm) -1(2) The distance between the fiber and the spinneret is 20cm, and the voltage is maintained at 22kV; (3) The fiber precursor prepared in step (2) is then calcined. During the calcination process, the precursor is first heated in the open air at 2℃ for 1 minute. -1 The temperature was heated to 300°C at a heating rate and held for 3 hours, then heated in an argon atmosphere at a rate of 1.5°C / min. -1 The temperature was raised to 500℃ at a certain heating rate, and the sample was held at 500℃ for 5 hours, then heated at 1.5℃ / min. -1 The cooling rate was reduced to room temperature; (4) During the electrochemical deposition process, the fiber obtained in step (3) and Cu were used together as the negative electrode (ZnO / C-Cu), with zinc foil as the positive electrode, 1M zinc formate as the electrolyte, and polyvinylidene fluoride as the separator to assemble a coin cell, and the current density was set to 10 mA cm⁻¹ under the charging program. -2 The deposition capacity is 1 mAh cm⁻¹ -2 Zinc was deposited onto the ZnO / C-Cu anode to prepare Zn@ZnO / C-Cu anode material.

[0048] Implementation Example 6

[0049] (1) Dissolve 1.0 g of polyacrylonitrile completely in 20 mL of N,N-dimethylacetamide to prepare solution A, then dissolve 2 g of zinc gluconate completely in solution A and stir at 55 °C for 8 h to prepare solution B; (2) For electrospinning, transfer solution B prepared in step (1) to a spinning injector, and during rotation, the advance rate of the injector is fixed at 16 μL / s. -1 Collection cylinder (rotation speed 220 rpm) -1 (2) The distance between the fiber and the spinneret is 18cm, and the voltage is maintained at 20kV; (3) The fiber precursor prepared in step (2) is then calcined. During the calcination process, the precursor is first heated in the open air at 3℃ for 1 minute. -1 Heated to 100°C at a heating rate and held for 5 hours, then heated in an argon atmosphere at 3°C / min. -1 The temperature was raised to 900℃ at a certain heating rate, and the sample was held at 900℃ for 2 hours, then increased at 3℃ / min. -1 (3) Cool to room temperature at a cooling rate of 100°C; (4) During the electrochemical deposition process, use the fiber obtained in step (3) and Cu together as the negative electrode (ZnO / C-Cu), with zinc foil as the positive electrode, 2M ZnSO4 as the electrolyte, and polyamide as the separator to assemble a coin cell, and set the current density to 7 mA cm⁻¹ under the charging program. -2 The deposition capacity is 7 mAh / cm³. -2 Zinc was deposited onto the ZnO / C-Cu anode to prepare Zn@ZnO / C-Cu anode material.

[0050] Implementation Example 7

[0051] (1) Dissolve 2.0 g of chitosan completely in 20 mL of N,N-dimethylacetamide to prepare solution A, then dissolve 1 g of zinc trifluoromethanesulfonate completely in solution A and stir at 40 °C for 12 h to prepare solution B; (2) For electrospinning, transfer solution B prepared in step (1) to a spinning injector, and during rotation, the propulsion rate of the injector is fixed at 15 μL / s. -1 Collection cylinder (rotation speed 300 rpm) -1 (2) The distance between the fiber and the spinneret is 15cm, and the voltage is maintained at 22kV; (3) The fiber precursor prepared in step (2) is then calcined. During the calcination process, the precursor is first heated in the open air at 3℃ for 1 minute. -1 The temperature was heated to 240°C at a heating rate and held for 3 hours, then heated in an argon atmosphere at a rate of 3°C / min. -1 The temperature was raised to 700℃ at a certain heating rate, and the sample was held at 700℃ for 2 hours, then increased at 3℃ / min. -1 The cooling rate was reduced to room temperature; (4) During the electrochemical deposition process, the fiber obtained in step (3) and Cu were used together as the negative electrode (ZnO / C-Cu), with zinc foil as the positive electrode, 2M ZnSO4 as the electrolyte, and polyamide as the separator to assemble a coin cell. The current density was set to 6 mA cm⁻¹ under the charging program. -2 The deposition capacity is 6 mAh / cm³. -2 Zinc was deposited onto the ZnO / C-Cu anode to prepare Zn@ZnO / C-Cu anode material.

[0052] Implementation Example 8

[0053] (1) Dissolve 1.0g of silk fibroin completely in 20mL of formic acid to prepare solution A, then dissolve 2g of zinc chloride completely in solution A and stir at 40℃ for 10h to prepare solution B; (2) For electrospinning, transfer solution B prepared in step (1) into a spinning injector, and during rotation, the propulsion rate of the injector is fixed at 20μL / s. -1 Collection cylinder (rotation speed 250 rpm) -1 (2) The distance between the fiber and the spinneret is 20cm, and the voltage is maintained at 18kV; (3) The fiber precursor prepared in step (2) is then calcined. During the calcination process, the precursor is first heated in the open air at 3℃ for 1 minute. -1 The temperature was heated to 220°C at a heating rate and held for 1.5 hours, then heated in an argon atmosphere at a rate of 2°C / min. -1 The temperature was raised to 600℃ at a certain heating rate, and the sample was held at 600℃ for 2 hours, then increased at 2℃ / min. -1The cooling rate was reduced to room temperature; (4) During the electrochemical deposition process, the fiber obtained in step (3) and Cu were used together as the negative electrode (ZnO / C-Cu), with zinc foil as the positive electrode, 2M ZnSO4 as the electrolyte, and polyamide as the separator to assemble a coin cell. The current density was set to 1 mA cm⁻¹ under the charging program. -2 The deposition capacity is 10 mAh cm⁻¹ -2 Zinc was deposited onto the ZnO / C-Cu anode to prepare Zn@ZnO / C-Cu anode material.

[0054] The above description is merely a preferred embodiment of the present invention and does not constitute any limitation on the present invention. Any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention, or modify it into equivalent embodiments, without departing from the scope of the present invention. Therefore, those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of raw materials for the product of the present invention, additions of auxiliary components, and selection of specific methods all fall within the protection and disclosure scope of the present invention.

Claims

1. A three-dimensional zinc-loving current collector composite negative electrode constructed by electrochemical welding, characterized in that: A ZnO / C-Cu@Zn composite anode material was prepared by electrospinning technology and carbonization and electrochemical deposition. The material consists of Cu as the substrate, ZnO uniformly dispersed in carbon fibers, and the substrate and fibers are connected together by Zn in the form of electrochemical welding, forming a three-dimensional zinc-loving current collector composite anode structure.

2. The three-dimensional zinc-loving current collector composite negative electrode constructed by electrochemical welding according to claim 1, characterized in that... The specific steps are as follows: (1) Add zinc precursor and carbon source to organic solvent, heat and stir to obtain uniformly mixed spinning solution, then transfer the spinning solution into spinning syringe and perform electrospinning under appropriate parameters to obtain carbon fiber containing zinc source. (2) The spun fibers obtained by electrospinning are pre-oxidized and carbonized to obtain ZnO / C fibers; (3) Pre-electrodeposition: A coin cell is composed of a positive electrode, a negative electrode, a separator between the positive and negative electrodes, and an electrolyte. The material obtained in step (2) is used together with copper foil as a substrate. Then, a program is set to deposit zinc onto the substrate to obtain a three-dimensional zinc-loving current collector composite negative electrode structure.

3. The three-dimensional zinc-loving current collector composite negative electrode constructed by electrochemical welding according to claim 2, characterized in that: In step (1), the carbon source is one or more of polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polycaprolactone (PCL), polyurethane (PU), polylactic acid (PLA), polyethersulfone (PES), polystyrene (PS), polyamide (PA), cellulose acetate (CA), chitosan (CS), and silk fibroin (SF); the zinc precursor is one or more of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, zinc fluoride, zinc hexafluoroate, zinc trifluoromethanesulfonate, and zinc gluconate; and the organic solvent is one or more of ethanol, NN-dimethylformamide (DMF), NN-dimethylacetamide (DMAc), acetone, chloroform (TCM), dichloromethane (DCM), formic acid, hexafluoroisopropanol (HFIP), and tetrahydrofuran (THF).

4. The three-dimensional zinc-loving current collector composite negative electrode constructed by electrochemical welding according to claim 2, characterized in that: In step (1), the feed rate of the electrospinning injector is 15-30 μL / s. -1 The collecting cylinder rotates at a speed of 200-500 rpm. -1 The distance between the collecting tube and the spinneret is 10-20cm, and the voltage is set to 15-22kV.

5. The three-dimensional zinc-loving current collector composite negative electrode constructed by electrochemical welding according to claim 2, characterized in that: In step (2), the atmosphere during pre-oxidation is air, and the atmosphere during carbonization is N2 or Ar; the heating rate during pre-oxidation is 1-3℃ min. -1 The heating rate during carbonization is 2-5℃ / min. -1 The pre-oxidation holding time is 2-5 hours, and the carbonization holding time is 2-5 hours; the carbonization cooling rate is 2-5℃ / min. -1 .

6. The three-dimensional zinc-loving current collector composite negative electrode constructed by electrochemical welding according to claim 2, characterized in that: In step (3), the pre-electrodeposition selective diaphragm includes one of the following: nonwoven fabric, glass fiber, polyacrylonitrile, polyamide, polyterephthalate, polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, and polycarbonate; the pre-electrodeposition selective electrolyte contains a soluble zinc salt, which is at least one of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, zinc fluoride, zinc hexafluoroate, zinc trifluoromethanesulfonate, and zinc gluconate.

7. The three-dimensional zinc-loving current collector composite negative electrode constructed by electrochemical welding according to claim 2, characterized in that: In step (3), the deposition current density for pre-electrodeposited zinc is 1-10 mA / cm². 2 The deposition capacity is 1-10 mAh / cm³. 2 .

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