Preparation method of zinc ion hybrid supercapacitor

Abstract

The invention relates to the technical field of supercapacitors, in particular to a preparation method of a zinc ion hybrid supercapacitor, which comprises the following steps: S1, designing a composite cutting track; s2, nickel sheet treatment; s3, electric discharge machining is carried out; s4, positive electrode treatment; and S5, assembling. According to the method, a numerical control wire cut electrical discharge machining process is adopted, a molybdenum wire is used as an electrode, in-situ oxidation reaction is directly induced to occur on the surface of a nickel substrate through high temperature generated by instantaneous short circuit in the discharging process, and synthesis of NiMoOx bimetallic oxide and electrode patterning machining are synchronously achieved; therefore, an integrated electrode structure without a binder, a conductive additive or a current collector is constructed.

Description

Technical Field

[0001] This invention relates to the field of supercapacitor technology, specifically to a method for preparing a zinc ion hybrid supercapacitor. Background Technology

[0002] Zinc-ion hybrid supercapacitors typically include a zinc negative electrode containing Zn. 2+ The electrolyte and cathode material are used in electrochemical applications, and the electrochemical performance largely depends on the performance of the cathode material. Existing cathode material systems include Prussian blue analogues, organic materials, and layered chalcogenides, but these materials still have certain shortcomings in practical applications. For example, Prussian blue analogues and organic materials generally suffer from poor chemical stability, making it difficult to meet the requirements of long-term cycling and large-scale applications; layered chalcogenides, on the other hand, have defects such as insufficient structural stability and low intrinsic conductivity.

[0003] In contrast, metal oxide materials possess advantages such as high theoretical specific capacitance, high energy density, good structural stability, low raw material cost, and environmental friendliness, and are widely used as cathode materials in zinc-ion hybrid supercapacitors. By controlling the composition, designing the structure, and modifying composites of metal oxides, their ion transport and electronic conductivity can be improved to a certain extent, thereby enhancing the overall electrochemical performance of the device.

[0004] Currently, the main methods for preparing metal oxide cathode materials include hydrothermal methods, electrodeposition methods, 3D printing methods, and laser processing. However, these methods still have limitations in practical applications. For example, the hydrothermal reaction process takes place in a closed, high-pressure environment, making online monitoring difficult and posing certain safety risks. Furthermore, the waste liquid and byproducts generated burden the environment. While electrodeposition requires no binder and is a relatively mature process, subsequent filtration and cleaning steps are cumbersome and can easily introduce uncontrollable impurities. Although 3D printing technology allows for flexible electrode structure design, the mechanical properties and electrochemical stability of the electrodes produced still need improvement. Laser processing technology offers advantages such as high precision and maskless processing, but its high equipment cost and maintenance expenses limit its large-scale application.

[0005] Therefore, there is an urgent need to develop a method for preparing zinc-ion hybrid supercapacitors that is simple to manufacture, requires no mask or template, no binder or conductive additives, is environmentally friendly, and has low cost, in order to overcome the shortcomings of existing technologies. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing a zinc ion hybrid supercapacitor, so as to solve the problems mentioned in the background art.

[0007] To achieve the above objectives, the present invention provides the following technical solution: a method for preparing a zinc ion hybrid supercapacitor, comprising the following steps: S1. Design of composite cutting trajectory: Use computer-aided design software to construct a composite machining trajectory that includes rectangular pattern tool path, straight surface cutting tool path and circular pattern tool path, and then convert the composite machining trajectory into an ISO format CNC program through CNC programming software and import it into the CNC wire EDM machine tool. S2. Nickel sheet treatment: Use ultrapure water to rinse the surface of the nickel sheet to remove contaminants and impurities attached to its surface. After rinsing, place it in a 60°C constant temperature drying oven to dry for 10 minutes to obtain a clean and dry nickel-based sheet. S3. Electrical Discharge Machining: On a CNC wire EDM machine, a molybdenum wire is installed as the electrode wire on the machine's wire guide wheel mechanism and adjusted to the correct position. The wire speed is set to 1–4 m / s, the machining current to 1–4 A, the machining voltage to 60–120 V, the pulse width to 6–36 μs, and the ratio of pulse interval to pulse width to 3:1–5:1. The three-stage electrical discharge machining is executed according to the ISO format CNC program. The specific operation is as follows: First stage processing: The nickel-based sheet is horizontally clamped and fixed on the machine tool worktable. The tool setting operation is completed by using molybdenum wire and the work coordinate origin is determined. The rectangular pattern toolpath program is run to perform pulse spark discharge etching on the nickel-based sheet to obtain a nickel rectangular sheet. Second stage processing: The nickel rectangular sheet is removed from the worktable, vertically clamped and fixed on the machine tool worktable. Molybdenum wire is used again for tool setting, and a straight-line machining toolpath program is run to uniformly etch away the two largest rectangular planes of the nickel rectangular sheet using pulsed spark discharge, resulting in in-situ synthesis of NiMoO. x Bimetallic oxides were used to obtain NiMoO. x Rectangular piece; Third-stage processing: The NiMoO x The rectangular piece is removed from the worktable, with its short oxidized side as the leading edge, and horizontally clamped and fixed on the machine tool worktable. A molybdenum wire is used to perform the tool setting operation, ensuring the molybdenum wire is aligned with the NiMoO. x The midpoint of the short side of the front end of the rectangular sheet is oxidized, and a circular pattern toolpath program is run to process the NiMoO. x NiMoO was prepared by pulsed spark discharge etching of rectangular sheets. x Circular electrode; S4. Positive electrode treatment: The NiMoO₂ is treated with ultrapure water. x The circular electrodes are surface rinsed to remove processing debris and impurities adhering to their surface. After rinsing, they are placed in a 60°C constant temperature drying oven to dry for 10 minutes and then cooled to room temperature for use. S5. Assembly: Using the NiMoOx circular electrode as the positive electrode, zinc foil as the negative electrode, glass fiber diaphragm as the capacitor diaphragm, and ZnSO4 solution as the electrolyte, the electrodes are stacked, fixed, and packaged according to conventional electrochemical energy storage device assembly processes to obtain a zinc ion hybrid supercapacitor.

[0008] Optionally, the CNC wire EDM machine tool uses ultrapure water as the working fluid.

[0009] Optionally, the thickness of the nickel substrate is 0.1 to 10.0 mm, and the diameter of the molybdenum wire is 0.12 to 0.24 mm.

[0010] Optionally, the concentration of the ZnSO4 solution is 0.5–2.0 mol / L.

[0011] Compared with the prior art, the present invention has the following beneficial effects: 1. This invention employs CNC wire electrical discharge machining (EDM) with molybdenum wire as the electrode. During the discharge process, the high temperature generated by the instantaneous short circuit directly induces an in-situ oxidation reaction on the surface of a nickel substrate, simultaneously achieving NiMoO. x The synthesis of bimetallic oxides and electrode patterning processes enable the construction of an integrated electrode structure that requires no binder, conductive additives, or current collectors. 2. This invention differs from traditional methods such as hydrothermal methods, electrodeposition methods, 3D printing, or laser processing. It fundamentally avoids problems such as high interfacial contact resistance, weak bonding strength, and cumbersome process steps. The equipment used is less expensive than laser systems, and no toxic or harmful chemical reagents are required throughout the process. It combines green process, simple operation, and economic feasibility. Attached Figure Description

[0012] Figure 1 This is a process flow diagram of the preparation method of the zinc ion hybrid supercapacitor disclosed in this invention; Figure 2 The bar charts show the area-to-capacitance ratios of the zinc-ion hybrid supercapacitors prepared in Examples 1-3 at 12 mV / s and 100 mV / s. Figure 3 The NiMoO prepared in Example 1 x XRD pattern of a circular electrode; Figure 4 The NiMoO prepared in Example 1 x SEM image of a circular electrode and its surface scan distribution of Ni, Mo, and O elements.

[0013] In the diagram: 1. Nickel-based sheet; 2. Molybdenum wire; 3. Rectangular nickel sheet; 4. NiMoO x 5. Rectangular sheet; 6. Zinc foil; 7. Fiberglass diaphragm; 8. Zinc ion hybrid supercapacitor. Detailed Implementation

[0014] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0015] Example 1 Please see Figure 1 This embodiment provides a method for preparing a zinc ion hybrid supercapacitor, including the following steps: S1. Design of composite cutting trajectory: Use computer-aided design software to construct a composite machining trajectory that includes rectangular pattern tool path, straight surface cutting tool path and circular pattern tool path, and then convert the composite machining trajectory into an ISO format CNC program through CNC programming software and import it into the CNC wire EDM machine tool. S2. Nickel sheet treatment: Use ultrapure water to rinse the surface of nickel sheets with a thickness of 1.0 mm to remove contaminants and impurities attached to their surface. After rinsing, place them in a 60°C constant temperature drying oven to dry for 10 min to obtain clean and dry nickel-based sheets. S3. Electrical Discharge Machining: On a CNC wire EDM machine, a 0.18 mm diameter molybdenum wire is installed as the electrode wire on the machine's wire guide wheel mechanism and adjusted to the correct position. The wire speed is set to 2 m / s, the machining current to 2 A, the machining voltage to 60 V, the pulse width to 24 μs, and the ratio of pulse interval to pulse width to 4:1. The three-stage electrical discharge machining is executed according to the ISO format CNC program. The specific operation is as follows: First stage of processing: The nickel-based sheet is horizontally clamped and fixed on the machine tool worktable. The tool setting operation is completed by using molybdenum wire and the work coordinate origin is determined. The rectangular pattern toolpath program is run to perform pulse spark discharge etching on the nickel-based sheet to obtain a nickel rectangular sheet. Second stage processing: The nickel rectangular sheet is removed from the worktable, vertically clamped and fixed on the machine tool worktable. Molybdenum wire is used again for tool setting, and a straight-line machining toolpath program is run to uniformly etch away the two largest rectangular planes of the nickel rectangular sheet using pulsed spark discharge, resulting in in-situ synthesis of NiMoO. x Bimetallic oxides were used to obtain NiMoO. x Rectangular piece; Third-stage processing: NiMoO x The rectangular piece is removed from the worktable, with its short oxidized side as the leading edge, and horizontally clamped and fixed on the machine tool worktable. A molybdenum wire is used to perform the tool setting operation, ensuring the molybdenum wire is aligned with the NiMoO. xOxidize the midpoint of the short side at the front end of the rectangular sheet, run the circular pattern toolpath program, and process NiMoO. x NiMoO was prepared by pulsed spark discharge etching of rectangular sheets. x Circular electrode; S4. Positive electrode treatment: NiMoO is treated with ultrapure water. x The circular electrodes are surface rinsed to remove processing debris and impurities adhering to their surface. After rinsing, they are placed in a 60°C constant temperature drying oven to dry for 10 minutes and then cooled to room temperature for use. S5. Assembly: Using a NiMoOx circular electrode as the positive electrode, zinc foil as the negative electrode, a glass fiber diaphragm as the capacitor diaphragm, and a 1 mol / L ZnSO4 solution as the electrolyte, the zinc ion hybrid supercapacitor was prepared by stacking, fixing, and encapsulating according to the conventional electrochemical energy storage device assembly process.

[0016] Example 2 This embodiment provides a method for preparing a zinc ion hybrid supercapacitor, including the following steps: S1. Design of composite cutting trajectory: Use computer-aided design software to construct a composite machining trajectory that includes rectangular pattern tool path, straight surface cutting tool path and circular pattern tool path, and then convert the composite machining trajectory into an ISO format CNC program through CNC programming software and import it into the CNC wire EDM machine tool. S2. Nickel sheet treatment: Use ultrapure water to rinse the surface of a 1 mm thick nickel sheet to remove contaminants and impurities attached to its surface. After rinsing, place it in a 60°C constant temperature drying oven and dry for 10 min to obtain a clean and dry nickel-based sheet. S3. Electrical Discharge Machining: On a CNC wire EDM machine, a 0.18 mm diameter molybdenum wire is installed as the electrode wire on the machine's wire guide wheel mechanism and adjusted to the correct position. The wire speed is set to 2 m / s, the machining current to 2 A, the machining voltage to 60 V, the pulse width to 6 μs, and the ratio of pulse interval to pulse width to 4:1. The three-stage electrical discharge machining is executed according to the ISO format CNC program. The specific operation is as follows: First stage of processing: The nickel-based sheet is horizontally clamped and fixed on the machine tool worktable. The tool setting operation is completed by using molybdenum wire and the work coordinate origin is determined. The rectangular pattern toolpath program is run to perform pulse spark discharge etching on the nickel-based sheet to obtain a nickel rectangular sheet. Second stage processing: The nickel rectangular sheet is removed from the worktable, vertically clamped and fixed on the machine tool worktable. Molybdenum wire is used again for tool setting, and a straight-line machining toolpath program is run to uniformly etch away the two largest rectangular planes of the nickel rectangular sheet using pulsed spark discharge, resulting in in-situ synthesis of NiMoO. x Bimetallic oxides were used to obtain NiMoO. x Rectangular piece; Third-stage processing: NiMoOx The rectangular piece is removed from the worktable, with its short oxidized side as the leading edge, and horizontally clamped and fixed on the machine tool worktable. A molybdenum wire is used to perform the tool setting operation, ensuring the molybdenum wire is aligned with the NiMoO. x Oxidize the midpoint of the short side at the front end of the rectangular sheet, run the circular pattern toolpath program, and process NiMoO. x NiMoO was prepared by pulsed spark discharge etching of rectangular sheets. x Circular electrode; S4. Positive electrode treatment: NiMoO is treated with ultrapure water. x The circular electrodes are surface rinsed to remove processing debris and impurities adhering to their surface. After rinsing, they are placed in a 60°C constant temperature drying oven to dry for 10 minutes and then cooled to room temperature for use. S5. Assembly: Using a NiMoOx circular electrode as the positive electrode, zinc foil as the negative electrode, a glass fiber diaphragm as the capacitor diaphragm, and a 1 mol / ZnSO4 solution as the electrolyte, the zinc ion hybrid supercapacitor is prepared by stacking, fixing, and encapsulating according to conventional electrochemical energy storage device assembly processes.

[0017] Example 3 This embodiment provides a method for preparing a zinc ion hybrid supercapacitor, including the following steps: S1. Design of composite cutting trajectory: Use computer-aided design software to construct a composite machining trajectory that includes rectangular pattern tool path, straight surface cutting tool path and circular pattern tool path, and then convert the composite machining trajectory into an ISO format CNC program through CNC programming software and import it into the CNC wire EDM machine tool. S2. Nickel sheet treatment: Use ultrapure water to rinse the surface of a 1 mm thick nickel sheet to remove contaminants and impurities attached to its surface. After rinsing, place it in a 60°C constant temperature drying oven and dry for 10 min to obtain a clean and dry nickel-based sheet. S3. Electrical Discharge Machining: On a CNC wire EDM machine, a 0.18 mm diameter molybdenum wire is installed as the electrode wire on the machine's wire guide wheel mechanism and adjusted to the correct position. The wire speed is set to 2 m / s, the machining current to 2 A, the machining voltage to 60 V, the pulse width to 36 μs, and the ratio of pulse interval to pulse width to 4:1. The three-stage electrical discharge machining is executed according to the ISO format CNC program. The specific operation is as follows: First stage of processing: The nickel-based sheet is horizontally clamped and fixed on the machine tool worktable. The tool setting operation is completed by using molybdenum wire and the work coordinate origin is determined. The rectangular pattern toolpath program is run to perform pulse spark discharge etching on the nickel-based sheet to obtain a nickel rectangular sheet. Second stage processing: The nickel rectangular sheet is removed from the worktable, vertically clamped and fixed on the machine tool worktable. Molybdenum wire is used again for tool setting, and a straight-line machining toolpath program is run to uniformly etch away the two largest rectangular planes of the nickel rectangular sheet using pulsed spark discharge, resulting in in-situ synthesis of NiMoO. x Bimetallic oxides were used to obtain NiMoO. x Rectangular piece; Third-stage processing: NiMoO x The rectangular piece is removed from the worktable, with its short oxidized side as the leading edge, and horizontally clamped and fixed on the machine tool worktable. A molybdenum wire is used to perform the tool setting operation, ensuring the molybdenum wire is aligned with the NiMoO. x Oxidize the midpoint of the short side at the front end of the rectangular sheet, run the circular pattern toolpath program, and process NiMoO. x NiMoO was prepared by pulsed spark discharge etching of rectangular sheets. x Circular electrode; S4. Positive electrode treatment: NiMoO is treated with ultrapure water. x The circular electrodes are surface rinsed to remove processing debris and impurities adhering to their surface. After rinsing, they are placed in a 60°C constant temperature drying oven to dry for 10 minutes and then cooled to room temperature for use. S5. Assembly: Using a NiMoOx circular electrode as the positive electrode, zinc foil as the negative electrode, a glass fiber diaphragm as the capacitor diaphragm, and a 1 mol / L ZnSO4 solution as the electrolyte, the zinc ion hybrid supercapacitor was prepared by stacking, fixing, and encapsulating according to the conventional electrochemical energy storage device assembly process.

[0018] In Examples 1-3, the computer-aided design software is AutoCAD, the CNC programming software is EAPT, and the CNC wire EDM machine tool uses ultrapure water as the working fluid.

[0019] Test case 1. Experimental System Experimental setup: CHI 660E dual potentiostat.

[0020] Test samples: Zinc ion hybrid supercapacitors prepared in Examples 1-3.

[0021] Voltage window: 0 to 1.0 V.

[0022] Test temperature: room temperature (25±2°C).

[0023] 2. Test Methods The three samples were subjected to CV tests at scan rates of 12 mV / s and 100 mV / s, respectively, and the current response was recorded. Based on the CV curves, the formula was used:

[0024] Calculate the Cs value. Where Cs: the areal capacitance (mF / cm²) 2 S: Positive electrode geometric surface area (cm²) 2 I(V): Current density (mA / cm²) 2 ), ΔV: voltage window (1.0 V).

[0025] The Cs values ​​under different pulse width conditions were plotted as a bar chart to compare their performance at low speeds (12 mV / s) and high speeds (100 mV / s). The results are as follows: Figure 2 As shown Please see Figure 2 It can be seen that all three examples can prepare high-performance zinc-ion hybrid supercapacitors. When the pulse width used in the discharge processing is 24 μs, the formed NiMoO x The electrode exhibits optimal overall performance. Under this pulse width condition, the electric spark discharge energy is moderate, which can effectively remove the nickel substrate and achieve in-situ doping and oxidation of molybdenum, while avoiding adverse phenomena such as local melting, structural collapse or amorphization caused by excessive energy. Thus, an ideal electrode structure with high specific surface area, good conductivity and abundant active sites is obtained.

[0026] Please see Figure 3 The NiMoO prepared in Example 1 x The XRD pattern of the circular electrode shows strong peaks near 2θ≈44°, 52°, and 77°, corresponding to the characteristic peaks of Ni (ICDD No. 01-070-1849), indicating that the substrate is incompletely oxidized nickel metal; a strong peak near 2θ≈54°, corresponding to the characteristic peaks of NiO (ICDD No. 01-089-5881), indicating that some nickel has been oxidized to form nickel oxide; strong peaks near 2θ≈36° and 42°, corresponding to the characteristic peaks of MoO2 (ICDD No. 01-076-1807), indicating that molybdenum exists in the form of molybdenum trioxide or participates in the reaction; and strong peaks near 2θ≈26° and 75°, corresponding to the characteristic peaks of NiMoO4 (ICDD No. 00-045-0142), with clear and high intensity, indicating that NiMoO4... x In-situ synthesis has been successfully achieved. Furthermore, no unexpected impurities such as carbides or sulfides were detected in the chromatogram, indicating that the entire process was carried out in an ultrapure water environment with excellent cleanliness, effectively preventing contamination from foreign impurities.

[0027] In summary, this invention utilizes wire electrical discharge machining (EDM) technology to in-situ construct a multiphase composite oxide layer composed of Ni, NiO, MoO2, and NiMoO4 on the surface of a nickel substrate, successfully synthesizing the target active material NiMoO4. xIt also retains the metallic nickel framework which is conducive to electron conduction and introduces defect structures such as oxygen vacancies, providing an effective way to construct high-performance zinc-ion hybrid supercapacitor cathode materials.

[0028] Please see Figure 4 , Figure 4 (a) The electrode surface exhibits a uniform and dense micro-nano-scale rough structure without cracks or peeling. Figure 4 (b) The uniform distribution of Ni elements throughout the field of view indicates that the nickel matrix not only exists as a conductive framework but also fully participates in the surface oxidation reaction. Figure 4 (c) The Mo element is shown to be diffusely distributed with a wide coverage area, confirming that the molybdenum wire evaporates and is in situ incorporated into the nickel-based surface during the discharge process, forming a molybdenum-containing composite phase. Figure 4 (d) shows that the O element signal is strong and highly uniformly distributed, indicating that the O element has deeply participated in the reaction and generated a stable metal oxide.

[0029] In summary, NiMoO x The circular electrode achieves the synergistic coexistence and rational distribution of Ni, Mo, and O elements, forming a NiMoO with a complete structure, uniform composition, and rich active sites. x The micro / nano composite oxide layer showed no obvious impurity phases or elemental segregation, fully demonstrating that the present invention can successfully achieve NiMoO in an ultrapure water environment using wire electrical discharge machining technology. x The in-situ synthesis and controllable construction of bimetallic oxides provide a highly active and stable cathode material for zinc-ion hybrid supercapacitors.

[0030] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a zinc-ion hybrid supercapacitor, characterized in that, Includes the following steps: S1. Design of composite cutting trajectory: Use computer-aided design software to construct a composite machining trajectory that includes rectangular pattern tool path, straight surface cutting tool path and circular pattern tool path, and then convert the composite machining trajectory into an ISO format CNC program through CNC programming software and import it into the CNC wire EDM machine tool. S2. Nickel sheet treatment: Use ultrapure water to rinse the surface of the nickel sheet to remove contaminants and impurities attached to its surface. After rinsing, place it in a 60°C constant temperature drying oven to dry for 10 minutes to obtain a clean and dry nickel-based sheet. S3. Electrical Discharge Machining: On a CNC wire EDM machine, a molybdenum wire is installed as the electrode wire on the machine's wire guide wheel mechanism and adjusted to the correct position. The wire speed is set to 1–4 m / s, the machining current to 1–4 A, the machining voltage to 60–120 V, the pulse width to 6–36 μs, and the ratio of pulse interval to pulse width to 3:1–5:

1. The three-stage electrical discharge machining is executed according to the ISO format CNC program. The specific operation is as follows: First stage processing: The nickel-based sheet is horizontally clamped and fixed on the machine tool worktable. The tool setting operation is completed by using molybdenum wire and the work coordinate origin is determined. The rectangular pattern toolpath program is run to perform pulse spark discharge etching on the nickel-based sheet to obtain a nickel rectangular sheet. Second stage processing: The nickel rectangular sheet is removed from the worktable, vertically clamped and fixed on the machine tool worktable. Molybdenum wire is used again for tool setting, and a straight-line machining toolpath program is run to uniformly etch away the two largest rectangular planes of the nickel rectangular sheet using pulsed spark discharge, resulting in in-situ synthesis of NiMoO. x Bimetallic oxides were used to obtain NiMoO. x Rectangular piece; Third-stage processing: The NiMoO x The rectangular piece is removed from the worktable, with its short oxidized side as the leading edge, and horizontally clamped and fixed on the machine tool worktable. A molybdenum wire is used to perform the tool setting operation, ensuring the molybdenum wire is aligned with the NiMoO. x The midpoint of the short side of the front end of the rectangular sheet is oxidized, and a circular pattern toolpath program is run to process the NiMoO. x NiMoO was prepared by pulsed spark discharge etching of rectangular sheets. x Circular electrode; S4. Positive electrode treatment: The NiMoO₂ is treated with ultrapure water. x The circular electrodes are surface rinsed to remove processing debris and impurities adhering to their surface. After rinsing, they are placed in a 60°C constant temperature drying oven to dry for 10 minutes and then cooled to room temperature for use. S5. Assembly: Using the NiMoOx circular electrode as the positive electrode, zinc foil as the negative electrode, glass fiber diaphragm as the capacitor diaphragm, and ZnSO4 solution as the electrolyte, the electrodes are stacked, fixed, and packaged according to conventional electrochemical energy storage device assembly processes to obtain a zinc ion hybrid supercapacitor.

2. The method for preparing a zinc-ion hybrid supercapacitor according to claim 1, characterized in that, The CNC wire EDM machine tool uses ultrapure water as its working fluid.

3. The method for preparing a zinc-ion hybrid supercapacitor according to claim 1, characterized in that, The nickel-based sheet has a thickness of 0.1 to 10.0 mm, and the molybdenum wire has a diameter of 0.12 to 0.24 mm.

4. The method for preparing a zinc-ion hybrid supercapacitor according to claim 1, characterized in that, The concentration of the ZnSO4 solution is 0.5–2.0 mol / L.

Images