Supercapacitor bimetallic oxide electrode and preparation method thereof and planar micro supercapacitor

Abstract

The present invention provides a supercapacitor bimetallic oxide electrode and a preparation method thereof and a planar micro supercapacitor, belonging to the technical field of supercapacitors. The present invention uses electric spark wire cutting to etch a copper sheet to obtain a molybdenum-copper bimetallic oxide material, and then uses electric spark wire cutting to pattern the molybdenum-copper bimetallic oxide material. This method can be digitally controlled, the preparation process is simple, easy to pattern, and the preparation process is low-cost and pollution-free. The obtained electrode material has excellent electrochemical properties and good versatility. The results of the embodiment show that the supercapacitor bimetallic oxide electrode prepared by the present invention has a high electrochemical performance at 5mV s ‑1 The area specific capacitance can reach 27.5mF cm at a scan rate of ‑2 , with excellent electrochemical performance.

Description

Technical Field

[0001] The present invention relates to the technical field of supercapacitors, and in particular to a supercapacitor bimetallic oxide electrode and a preparation method thereof, and a planar micro supercapacitor. Background Art

[0002] Faced with the increasingly severe energy crisis, the whole society is actively seeking strategies to increase revenue and reduce expenditure to meet this challenge. Clean energy, such as solar energy, tidal energy and wind energy, provides hope for the sustainable development of energy, but these clean energy sources face a key problem: how to effectively store and utilize these unstable energy outputs. Supercapacitors, with their unique fast charging and discharging and stable cycling characteristics, have become an ideal choice to meet the needs of unstable energy storage. Among supercapacitors, planar interdigitated supercapacitors with interdigitated electrodes have attracted much attention due to their advantages such as ultra-thin thickness, small size, easy integration, high power density and long cycle life. However, planar interdigitated supercapacitors currently face two technical challenges: one is the efficient and controllable preparation of high-performance electrode materials, and the other is the high-precision processing of extremely small-sized interdigitated electrodes.

[0003] First, metal oxide electrode materials have become an important choice for supercapacitor electrode materials due to their high specific capacity, rich pseudocapacitive reactions, good structural stability, wide electrochemical window, abundant resources, high cost-effectiveness and environmental friendliness. Compared with single metal oxides, the different metal particles of bimetallic oxides can improve the electrochemical activity through synergistic effects. The current method for preparing metal oxide electrode materials is usually to first prepare a bimetallic composite material and then spray it on the interdigitated electrode current collector. For example, the preparation method of an all-solid-state planar micro-supercapacitor disclosed in Chinese patent CN 201911034372.5. However, this method for preparing a bimetallic composite material is relatively complicated and requires the use of a mask plate. The thickness uniformity of the bimetallic composite material on the interdigitated electrode current collector is difficult to ensure.

[0004] Secondly, the current preparation methods for planar micro-supercapacitors include technologies such as photolithography, screen printing, and 3D printing. However, although photolithography can achieve high-precision patterning, its equipment cost is high, maintenance costs are expensive, and the environmental conditions are extremely strict. The preparation process is cumbersome and complicated, a mask plate is required, and the photoresist is very easy to cause contamination. The resolution of screen printing technology is low, making it difficult to produce fine patterns, and controlling the uniform thickness of the printed layer is quite challenging. 3D printing has the advantages of customized manufacturing and design flexibility, but the types of printing materials currently available for supercapacitor manufacturing are relatively limited and often cannot meet the high performance requirements of supercapacitors.

[0005] Therefore, there is an urgent need to develop a method for preparing supercapacitor electrodes that is simple to operate, low-cost, green, environmentally friendly, high-precision and widely applicable. Summary of the Invention

[0006] The purpose of the present invention is to provide a supercapacitor bimetallic oxide electrode and a preparation method thereof and a planar micro supercapacitor. The preparation method provided by the present invention is simple to operate, low-cost, green, environmentally friendly, high-precision and widely applicable.

[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0008] The present invention provides a method for preparing a bimetallic oxide electrode for a supercapacitor, comprising the following steps:

[0009] (1) etching the outer surface of the copper sheet to obtain a molybdenum-copper bimetallic oxide material; the etching method is electric spark wire cutting, and the working electrode wire of the electric spark wire cutting is a molybdenum wire;

[0010] (2) performing pattern cutting on the molybdenum-copper bimetallic oxide material obtained in step (1) to obtain a supercapacitor bimetallic oxide electrode; the pattern cutting method is electric spark wire cutting; the processing pattern of the pattern cutting is an interdigitated electrode pattern.

[0011] Preferably, the thickness of the copper sheet in step (1) is 0.2 to 10 mm.

[0012] Preferably, the parameters of the electric spark wire cutting in step (1) include: current of 1 to 5A, pulse width of 1 to 96μs, operating voltage of 60V to 140V, and interval ratio of 2 to 20.

[0013] Preferably, the working fluid of the electric spark wire cutting in step (1) is deionized water.

[0014] Preferably, the diameter of the molybdenum wire in step (1) is 0.05-0.3 mm.

[0015] Preferably, the finger width of the interdigitated electrode pattern in step (2) is 0.4 to 5 mm.

[0016] Preferably, the gap between the interdigital electrode patterns in step (2) is 0.1 to 1 mm.

[0017] The present invention also provides a supercapacitor bimetallic oxide electrode prepared by the preparation method described in the above technical solution. The supercapacitor bimetallic oxide electrode is an interdigitated electrode, and the outer surface of the interdigitated electrode includes an in-situ grown molybdenum-copper bimetallic oxide layer.

[0018] The present invention also provides a planar micro supercapacitor comprising interdigital electrodes and an electrolyte solution; the interdigital electrodes are the supercapacitor bimetallic oxide electrodes described in the above technical solution.

[0019] Preferably, the electrolyte solution is potassium hydroxide solution, sodium hydroxide solution or lithium hydroxide solution.

[0020] The present invention provides a method for preparing a supercapacitor bimetallic oxide electrode, comprising the following steps: etching the outer surface of a copper sheet to obtain a molybdenum-copper bimetallic oxide material; the etching method is electric spark wire cutting, and the working electrode wire of the electric spark wire cutting is a molybdenum wire; patterning the molybdenum-copper bimetallic oxide material to obtain a supercapacitor bimetallic oxide electrode; the patterning cutting method is electric spark wire cutting; and the processing pattern of the patterned cutting is an interdigitated electrode pattern. The present invention uses molybdenum wire as the electrode wire and uses wire-cut electrospark cutting to etch the outer surface of a copper sheet. Under the instantaneous high temperature generated by the electric spark discharge, the molybdenum and copper surfaces undergo an instant redox reaction, causing the material to melt or even vaporize. Under the flushing and cooling of the wire-cut electrospark working fluid, a pseudocapacitive active material, molybdenum-copper bimetallic oxide, is directly formed in situ on the copper substrate without any adhesive. The molybdenum-copper bimetallic oxide can generate more electronic reactions, improve the conductivity of the electrode material, provide more redox active sites, and thus enhance the capacitance and stability of the electrode. In addition, the high temperature conditions of the wire-cut electrospark cutting also introduce more oxygen vacancies, which help improve the conductivity and ion diffusion rate of the electrode material, thereby enhancing the charge and discharge capacity of the electrode. The present invention performs patterned cutting of the molybdenum-copper bimetallic oxide material, has wide applicability, can accurately control the morphology of the interdigitated electrodes according to the pattern, and improves the precision of the interdigitated electrodes.

[0021] The present invention uses wire-cut electrospark cutting to etch copper sheets to form a molybdenum-copper bimetallic oxide material, and then uses wire-cut electrospark cutting to pattern the molybdenum-copper bimetallic oxide material. This method can be digitally controlled, has a simple preparation process, is easy to pattern, and is low-cost and pollution-free. The resulting electrode material has excellent electrochemical properties and good versatility. The results of the embodiment show that the supercapacitor bimetallic oxide electrode prepared by the present invention has a high electrochemical performance at 5mV s -1 The area specific capacitance can reach 27.5mF cm at a scan rate of -2 , with excellent electrochemical performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 Schematic diagram of a method for preparing a bimetallic oxide electrode for a supercapacitor and assembling a planar micro-supercapacitor according to an embodiment of the present invention;

[0023] Figure 2 This is a SEM image of the supercapacitor bimetallic oxide electrode prepared in Example 1 of the present invention;

[0024] Figure 3 This is an EDS image of the supercapacitor bimetallic oxide electrode prepared in Example 1 of the present invention;

[0025] Figure 4 This is the XRD pattern of the supercapacitor bimetallic oxide electrode prepared in Example 1 of the present invention;

[0026] Figure 5 CV curves of the planar micro supercapacitor prepared in Example 2 of the present invention at different scan rates;

[0027] Figure 6 CV curves of the planar micro supercapacitor prepared in Example 4 of the present invention at different scan rates;

[0028] Figure 7 CV curves of the planar micro supercapacitor prepared in Example 6 of the present invention at different scan rates;

[0029] Figure 8 The planar micro supercapacitors prepared in Examples 2, 4 and 6 of the present invention were tested at 5 mV s -1 Comparison of area specific capacitance at different scan rates. DETAILED DESCRIPTION

[0030] The present invention provides a method for preparing a bimetallic oxide electrode for a supercapacitor, comprising the following steps:

[0031] (1) etching the outer surface of the copper sheet to obtain a molybdenum-copper bimetallic oxide material; the etching method is electric spark wire cutting, and the working electrode wire of the electric spark wire cutting is a molybdenum wire;

[0032] (2) performing pattern cutting on the molybdenum-copper bimetallic oxide material obtained in step (1) to obtain a supercapacitor bimetallic oxide electrode; the pattern cutting method is electric spark wire cutting; the processing pattern of the pattern cutting is an interdigitated electrode pattern.

[0033] The present invention performs etching treatment on the outer surface of the copper sheet to obtain a molybdenum-copper bimetallic oxide material.

[0034] In the present invention, the thickness of the copper sheet is preferably 0.2 to 10 mm, more preferably 1 to 5 mm. The copper sheet of the above thickness can react with molybdenum to form a molybdenum-copper bimetallic oxide material with a supporting effect.

[0035] The present invention has no particular limitation on the size of the copper sheet, and the size can be selected according to the size of the electrode to be prepared. In an embodiment of the present invention, the copper sheet is a rectangular copper sheet with a width of 10 mm and a length of 30 mm.

[0036] The present invention preferably cleans and dries the copper sheet before etching. The present invention removes contaminants from the copper sheet's surface through cleaning and drying. The present invention does not specifically limit the cleaning and drying procedures; conventional cleaning and drying procedures are sufficient to remove contaminants from the copper sheet's surface. In an embodiment of the present invention, the cleaning agent is deionized water, the number of cleaning cycles is 2-3, the drying temperature is 60°C, and the drying time is 20 minutes.

[0037] In the present invention, the etching process is performed using wire electrospark cutting (EDC), and the working electrode wire for the EDM is molybdenum wire. By using wire electrospark cutting (EDC) and molybdenum wire as the working electrode, the present invention can induce an in-situ oxidation reaction of the molybdenum wire on the surface of a copper sheet under high temperature to form nanoscale molybdenum-copper bimetallic oxide nanoparticles. This introduces bimetallic and oxygen vacancies into the electrode, and the synergistic effect of the different metal particles enhances electrochemical activity. The two metals also provide more valence for redox reactions, increasing the active sites and conductivity of the electrode material, improving the electrode's specific capacitance, and its stability during multiple charge-discharge cycles. Furthermore, this method eliminates the traditional complex and expensive mask and photolithography equipment, greatly simplifying the electrode manufacturing process while providing easy-to-implement pattern design capabilities, reducing the complexity of the manufacturing process, and making it suitable for large-scale industrial production of electrode materials.

[0038] In the present invention, the diameter of the molybdenum wire is preferably 0.05 to 0.3 mm, more preferably 0.15 to 0.18 mm. The use of molybdenum wire with the above diameter is more conducive to improving processing efficiency and surface quality of the molybdenum-copper bimetallic oxide material.

[0039] In the present invention, the wire EDM parameters preferably include: a current of 1 to 5A, a pulse width of 1 to 96μs, an operating voltage of 60V to 100V, and an interval ratio of 2 to 20. More preferably, the current is 2 to 3A, a pulse width of 24 to 50μs, an operating voltage of 60V to 100V, and an interval ratio of 4 to 10. By controlling the wire EDM parameters within the above ranges, the present invention is more conducive to forming high-quality molybdenum-copper bimetallic oxide particles on the surface of the copper sheet.

[0040] The present invention does not specifically limit the operation method of the wire EDM. Conventional wire EDM operation methods can be used to form a molybdenum-copper bimetallic oxide material on the outer surface of the copper sheet. In the present invention, the outer surface of the copper sheet includes the upper and lower surfaces and side surfaces of the copper sheet.

[0041] In an embodiment of the present invention, the operating method of the wire electric discharge cutting preferably includes:

[0042] Design and compile CNC Wire EDM programs based on Wire EDM machining parameters;

[0043] Clamp the rectangular copper sheet horizontally on the workbench of the CNC wire-cut EDM machine, ensuring that it is fixed firmly without loosening; use molybdenum wire as the cutting wire;

[0044] Retrieving and executing a CNC wire-cutting program to etch the surface of the copper sheet to obtain a first rectangular block;

[0045] The first rectangular block is longitudinally clamped on the workbench of a CNC wire-cut electric discharge machine to ensure that it is stable and vibration-free; the CNC wire-cut electric discharge machining program is called and executed to perform linear electric spark etching on the two unoxidized sides of the first rectangular block, and molybdenum-copper bimetallic oxide nanoparticle clusters are evenly formed on the sides to obtain a second rectangular block.

[0046] The present invention performs etching treatment by the above method, so that the outer surface of the copper sheet can be formed with molybdenum-copper bimetallic oxide nanomaterials.

[0047] In the present invention, the working fluid of the wire electric discharge cutting is preferably deionized water. The present invention uses deionized water as the working fluid, which is more conducive to forming high-quality molybdenum-copper bimetallic oxide particles on the outer surface of the copper sheet.

[0048] After obtaining the molybdenum-copper bimetallic oxide material, the present invention performs patterned cutting on the molybdenum-copper bimetallic oxide material to obtain a supercapacitor bimetallic oxide electrode.

[0049] In the present invention, the patterned cutting method is wire electric discharge cutting (WEC). Wire electric discharge cutting (WEC) is used for patterned cutting, enabling digital patterned cutting and high-precision control of electrode morphology. The present invention does not specifically limit the operation method of WEC; conventional WEC methods can be used to cut the molybdenum-copper bimetallic oxide material into an electrode with the desired morphology.

[0050] In the present invention, the pattern processed by the pattern cutting is an interdigital electrode pattern. The present invention can obtain the interdigital electrodes required for the supercapacitor by pattern cutting the interdigital electrode pattern.

[0051] In the present invention, the wire electric discharge cutting method preferably includes: first setting a programmed interdigital pattern, and then executing the programmed interdigital pattern on a CNC wire electric discharge machine to obtain a supercapacitor bimetallic oxide electrode.

[0052] In an embodiment of the present invention, the patterned cutting method is preferably: the molybdenum-copper bimetallic oxide material is horizontally clamped on the workbench of a CNC wire-cut electric discharge machine, and the clamping is ensured to be fixed and stable, the interdigitated pattern programmed by the CNC wire-cut electric discharge machine is called and executed, and then the machine is started again to cut into an interdigitated microelectrode structure.

[0053] In the present invention, the interdigital electrode pattern preferably has a finger width of 0.4 to 5 mm, more preferably 1.25 to 3 mm; the interdigital electrode pattern preferably has a gap of 0.1 to 1 mm, more preferably 0.5 to 1 mm. The present invention utilizes an interdigital electrode pattern having the aforementioned parameters to produce an interdigital electrode within the aforementioned parameter ranges, wherein the interdigital electrode comprises a first electrode and a second electrode.

[0054] In the present invention, the number of pairs of interdigital electrodes is preferably 1 to 5, more preferably 2 to 5. The present invention prepares interdigital electrodes of the above number of pairs to form 1 to 5 pairs of first electrodes and second electrodes, thereby obtaining electrodes with excellent performance.

[0055] The present invention preferably sequentially cleans and dries the electrodes obtained by patterned cutting to obtain a supercapacitor bimetallic oxide electrode. In an embodiment of the present invention, the cleaning agent is preferably deionized water, the number of cleanings is preferably 2-3 times, the drying temperature is preferably 60°C, and the drying time is preferably 20 minutes.

[0056] The method provided by the present invention uses electric spark wire cutting to etch a copper sheet to form a molybdenum-copper bimetallic oxide material, and then uses electric spark wire cutting to pattern the molybdenum-copper bimetallic oxide material. This method can be digitally controlled, the preparation process is simple and easy to pattern, and the preparation process is low-cost and pollution-free. The obtained electrode material has excellent electrochemical properties and good versatility.

[0057] The present invention also provides a supercapacitor bimetallic oxide electrode prepared by the preparation method described in the above technical solution.

[0058] In the present invention, the supercapacitor bimetallic oxide electrode is an interdigitated electrode, and the outer surface of the interdigitated electrode includes an in-situ grown molybdenum-copper bimetallic oxide layer.

[0059] The present invention also provides a planar micro supercapacitor comprising interdigital electrodes and an electrolyte solution; the interdigital electrodes are the supercapacitor bimetallic oxide electrodes described in the above technical solution.

[0060] In the present invention, the electrolyte solution is preferably a potassium hydroxide solution, a sodium hydroxide solution, a lithium hydroxide solution, or a potassium hydroxide solution, more preferably a potassium hydroxide solution. In the present invention, the concentration of the electrolyte solution is preferably 0.1 to 6 mol / L, more preferably 1 to 5 mol / L. The use of such electrolyte solutions in the present invention is more conducive to improving the electrochemical performance of the capacitor.

[0061] In the present invention, the method for assembling the planar micro supercapacitor preferably includes: arranging and fixing the interdigitated electrodes in a cross-shaped manner, clamping them with acrylic plates, immersing them in an electrolyte solution, and assembling them into a planar micro supercapacitor.

[0062] In the present invention, the fixing method is preferably glue bonding. The present invention has no particular limitation on the type of glue, as long as it can fix the interdigital electrodes.

[0063] The schematic diagram of the preparation method of the supercapacitor bimetallic oxide electrode and the assembled planar micro supercapacitor provided by the present invention is preferably as follows Figure 1 As shown. Figure 1 It can be seen that the present invention first etches the outer surface of the copper sheet to obtain a molybdenum-copper bimetallic oxide material, and then cuts the molybdenum-copper bimetallic oxide material into interdigitated electrodes, wherein the interdigitated electrodes include a first electrode and a second electrode, and finally the interdigitated electrodes are assembled into a planar micro supercapacitor.

[0064] The supercapacitor bimetallic oxide electrode provided by the present invention introduces bimetallic and oxygen vacancies. The synergistic effect of different metal particles enhances electrochemical activity. The two metals also provide more valence for redox reactions, increasing the active sites and conductivity of the electrode material, significantly improving specific capacitance. Simultaneously, the nanoscale structural characteristics and uniform element distribution ensure the stability and performance consistency of the electrode material over multiple charge and discharge cycles. Therefore, when assembled into a planar micro-supercapacitor, it exhibits excellent electrochemical performance.

[0065] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0066] Example 1

[0067] A method for preparing a planar micro-supercapacitor bimetallic oxide electrode, comprising the following steps:

[0068] (1) After cleaning the surface of a copper sheet with a width of 10 mm, a length of 30 mm, and a thickness of 1 mm twice with deionized water, the sheet was placed in a constant temperature drying oven at 60°C and dried for 20 min to obtain a dry copper sheet;

[0069] Molybdenum wire was used as the working electrode wire, deionized water was used as the working fluid, the working current was set to 2A, the pulse width was 24μs, the working voltage was 60V, the interval ratio was 4, and the diameter of the molybdenum wire was 0.18mm;

[0070] Clamp the dry copper sheet horizontally on the workbench of the CNC wire-cut EDM machine and ensure that it is clamped securely without loosening; replace the cutting wire with molybdenum wire and adjust the tightness;

[0071] Retrieving and executing a CNC wire-cutting program to etch the copper sheet to obtain a first rectangular block;

[0072] The first rectangular block is longitudinally clamped on a workbench of a CNC wire-cut electric discharge machine and ensured to be stable and vibration-free; a CNC wire-cut electric discharge machining program is retrieved and executed to perform linear electric spark etching on two unoxidized sides of the first rectangular block, thereby uniformly forming molybdenum-copper bimetallic oxide nanoparticle clusters on the sides, thereby obtaining a second rectangular block, namely, a molybdenum-copper bimetallic oxide material;

[0073] (2) The molybdenum-copper bimetallic oxide material obtained in step (1) is horizontally clamped on a workbench of a CNC wire-cut electric discharge machine and ensured to be fixed and stable; a processing pattern is drawn with a finger width of 1.25 mm and a gap of 0.5 mm; the CNC wire-cut electric discharge machine is called and executed to program the finger pattern, and then the machine is restarted to perform pattern cutting to obtain a supercapacitor bimetallic oxide electrode; the supercapacitor bimetallic oxide electrode is a pair of finger electrodes, respectively named as a first electrode and a second electrode; the finger widths of the first electrode and the second electrode are both 1.25 mm, the gaps between the first electrode and the second electrode are both 0.5 mm, and the number of electrode pairs is 3.

[0074] Example 2

[0075] A planar micro supercapacitor, comprising interdigital electrodes, an electrolyte solution, and an acrylic plate; the interdigital electrodes are the supercapacitor bimetallic oxide electrodes of Example 1;

[0076] The preparation method of the planar micro supercapacitor is as follows: the first electrode and the second electrode of the supercapacitor bimetallic oxide electrode prepared in Example 1 are arranged crosswise, serving as the positive and negative electrodes of the planar micro supercapacitor, respectively, and glue is applied to the ends of the electrodes for fixation. After standing for 15 minutes, they are clamped using an acrylic plate and immersed in a 1 mol / L KOH electrolyte solution to assemble into a planar micro supercapacitor.

[0077] Example 3

[0078] A method for preparing a bimetallic oxide electrode for a supercapacitor, comprising the following steps:

[0079] (1) After cleaning the surface of a copper sheet with a width of 10 mm, a length of 30 mm, and a thickness of 1 mm twice with deionized water, the sheet was placed in a constant temperature drying oven at 60°C and dried for 20 min to obtain a dry copper sheet;

[0080] Molybdenum wire was used as the working electrode wire, deionized water was used as the working fluid, the working current was set to 2A, the pulse width was 24μs, the working voltage was 80V, the interval ratio was 4, and the diameter of the molybdenum wire was 0.18mm;

[0081] Clamp the dry copper sheet horizontally on the workbench of the CNC wire-cut EDM machine and ensure that it is clamped securely without loosening; replace the cutting wire with molybdenum wire and adjust the tightness;

[0082] Retrieving and executing a CNC wire-EDM program to etch clusters on the copper sheet to obtain a first rectangular block;

[0083] The first rectangular block is longitudinally clamped on a workbench of a CNC wire-cut electric discharge machine and ensured to be stable and vibration-free; a CNC wire-cut electric discharge machining program is retrieved and executed to perform linear electric spark etching on two unoxidized sides of the first rectangular block, thereby uniformly forming molybdenum-copper bimetallic oxide nanoparticle clusters on the sides, thereby obtaining a second rectangular block, namely, a molybdenum-copper bimetallic oxide material;

[0084] (2) The molybdenum-copper bimetallic oxide material obtained in step (1) is horizontally clamped on a workbench of a CNC wire-cut electric discharge machine and ensured to be fixed and stable; a processing pattern is drawn with a finger width of 1.25 mm and a gap of 0.5 mm; the CNC wire-cut electric discharge machine is called and executed to program the finger pattern, and then the machine is restarted to perform pattern cutting to obtain a supercapacitor bimetallic oxide electrode; the supercapacitor bimetallic oxide electrode is a pair of finger electrodes, respectively named as a first electrode and a second electrode; the finger widths of the first electrode and the second electrode are both 1.25 mm, the gaps between the first electrode and the second electrode are both 0.5 mm, and the number of electrode pairs is 3.

[0085] Example 4

[0086] A planar micro supercapacitor, comprising interdigital electrodes, an electrolyte solution, and an acrylic plate; the interdigital electrodes are the supercapacitor bimetallic oxide electrodes of Example 3;

[0087] The preparation method of the planar micro supercapacitor device is the same as that of Example 2.

[0088] Example 5

[0089] A method for preparing a bimetallic oxide electrode for a supercapacitor, comprising the following steps:

[0090] (1) After cleaning the surface of a copper sheet with a width of 10 mm, a length of 30 mm, and a thickness of 1 mm twice with deionized water, the sheet was placed in a constant temperature drying oven at 60°C and dried for 20 min to obtain a dry copper sheet;

[0091] Molybdenum wire was used as the working electrode wire, deionized water was used as the working fluid, the working current was set to 2A, the pulse width was 24μs, the working voltage was 100V, the interval ratio was 4, and the diameter of the molybdenum wire was 0.18mm;

[0092] Clamp the dry copper sheet horizontally on the workbench of the CNC wire-cut EDM machine and ensure that it is clamped securely without loosening; replace the cutting wire with molybdenum wire and adjust the tightness;

[0093] Retrieving and executing a CNC wire-EDM program to etch clusters on the copper sheet to obtain a first rectangular block;

[0094] The first rectangular block is longitudinally clamped on a workbench of a CNC wire-cut electric discharge machine and ensured to be stable and vibration-free; a CNC wire-cut electric discharge machining program is retrieved and executed to perform linear electric spark etching on two unoxidized sides of the first rectangular block, thereby uniformly forming molybdenum-copper bimetallic oxide nanoparticle clusters on the sides, thereby obtaining a second rectangular block, namely, a molybdenum-copper bimetallic oxide material;

[0095] (2) The molybdenum-copper bimetallic oxide material obtained in step (1) is horizontally clamped on a workbench of a CNC wire-cut electric discharge machine and ensured to be fixed and stable; a processing pattern is drawn with a finger width of 1.25 mm and a gap of 0.5 mm; the CNC wire-cut electric discharge machine is called and executed to program the finger pattern, and then the machine is restarted to perform pattern cutting to obtain a supercapacitor bimetallic oxide electrode; the supercapacitor bimetallic oxide electrode is a pair of finger electrodes, respectively named as a first electrode and a second electrode; the finger widths of the first electrode and the second electrode are both 1.25 mm, the gaps between the first electrode and the second electrode are both 0.5 mm, and the number of electrode pairs is 3.

[0096] Example 6

[0097] A planar micro supercapacitor, comprising interdigital electrodes, an electrolyte solution, and an acrylic plate; the interdigital electrodes are the supercapacitor bimetallic oxide electrodes of Example 5;

[0098] The preparation method of the planar micro supercapacitor is the same as that in Example 2.

[0099] Test Example 1

[0100] The SEM image of the supercapacitor bimetallic oxide electrode prepared in Example 1 is as follows: Figure 2As shown. Figure 2 It can be seen that uniform nanoscale oxide particle clusters can be observed on the electrode surface. This morphology allows ions to quickly enter the material during energy storage reactions, thereby increasing the charge and discharge rates. In addition, the electrode surface is rough and does not show a large amount of agglomeration, which ensures that as much molybdenum-copper bimetallic oxide as possible participates in the energy storage reaction while increasing the specific surface area. This structure provides a large number of active sites for redox reactions and effectively reduces the ion transmission path, which is more conducive to the penetration of electrolytes and significantly improves the electrochemical performance of the electrode.

[0101] The EDS image of the supercapacitor bimetallic oxide electrode prepared in Example 1 is as follows: Figure 3 As shown. Figure 3 It can be seen that the elements on the surface of the supercapacitor bimetallic oxide electrode prepared in Example 1 are evenly distributed, with the presence of three elements: molybdenum (Mo), copper (Cu), and oxygen (O). This indicates that the wire EDM etching process achieves uniform fusion of the molybdenum wire and the copper metal sheet during processing, ensuring the consistency and stability of the material. In addition, both metal oxides participate in the redox reaction, which can reduce the charge transfer impedance of the electrochemical supercapacitor.

[0102] The XRD pattern of the supercapacitor bimetallic oxide electrode prepared in Example 1 is as follows: Figure 4 As shown. Figure 4 It can be seen that the bimetallic oxide MoCuO on the surface of the electrode prepared by the present invention x The main components are Cu, Cu2O, and MoO2. Cu as a current collector provides good mechanical properties, ensuring the mechanical strength and stability of the electrode material. x As an active material, it participates in the pseudocapacitive energy storage process; in addition, MoCuO x The synergistic effect of the ions and oxygen vacancies can further enhance the ion transport efficiency and charge storage capacity.

[0103] Test Example 2

[0104] The CV curves of the planar micro supercapacitor prepared in Example 2 at different scan rates are shown in Figure 2. Figure 5 As shown, the CV curves of the planar micro supercapacitor prepared in Example 4 at different scan rates are shown in FIG. Figure 6 As shown; the CV curves of the planar micro supercapacitor prepared in Example 6 at different scan rates are shown Figure 7 As shown. Figures 5-7 It can be seen that the CV curves at different scan rates show ideal capacitance behavior close to a rectangle. The results show that the electrode prepared in Example 1 has a capacitance of 5 mV s -1 The area specific capacitance can reach 27.5mF cm at a scan rate of -2 .

[0105] The planar micro supercapacitors prepared in Example 2, Example 4 and Example 6 were -1 The comparison of area specific capacitance at the scan rate is shown in the figure below. Figure 8 As shown. Figure 8 It can be seen that the area specific capacitance of the supercapacitor bimetallic oxide electrode prepared in Example 1 is 27.5 mF cm -2 The area specific capacitance of the supercapacitor bimetallic oxide electrode prepared in Example 2 is 20 mF cm -2 The area specific capacitance of the supercapacitor bimetallic oxide electrode prepared in Example 3 is 15 mF cm -2 The results show that the best capacitance performance can be obtained when the processing voltage is 60V.

[0106] This method uses CNC wire-cut electric discharge (ED) technology to precisely machine copper sheets. Using the principle of discharge etching, it forms a molybdenum-copper bimetallic oxide on the copper sheet's surface, enabling precise control of electrode morphology. This preparation method offers advantages such as ease of operation, strong patterning capabilities, high cost-effectiveness, and environmental friendliness, making it suitable for large-scale industrial production. The planar micro-supercapacitor electrodes prepared using this method exhibit significant advantages, including high specific capacitance, excellent cycling stability, rapid charge-discharge performance, and environmental friendliness.

[0107] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for preparing a bimetallic oxide electrode for a supercapacitor, comprising the following steps: (1) etching the outer surface of the copper sheet to obtain a molybdenum-copper bimetallic oxide material; the etching method is electric spark wire cutting, and the working electrode wire of the electric spark wire cutting is a molybdenum wire; (2) performing pattern cutting on the molybdenum-copper bimetallic oxide material obtained in step (1) to obtain a supercapacitor bimetallic oxide electrode; the pattern cutting method is wire electric discharge cutting; The processing pattern of the patterned cutting is an interdigitated electrode pattern; The parameters of the wire electric discharge cutting in step (1) include: current of 1 to 5A, pulse width of 1 to 96 μs, operating voltage of 60V to 140V, and interval ratio of 2 to 20; The working fluid of the electric spark wire cutting in step (1) is deionized water.

2. The preparation method according to claim 1, characterized in that The thickness of the copper sheet in step (1) is 0.2 to 10 mm.

3. The preparation method according to claim 1, characterized in that The diameter of the molybdenum wire in step (1) is 0.05-0.3 mm.

4. The preparation method according to claim 1, characterized in that The finger width of the interdigitated electrode pattern in step (2) is 0.4 to 5 mm.

5. The preparation method according to claim 1 or 4, characterized in that In the step (2), the gap between the interdigitated electrode patterns is 0.1 to 1 mm.

6. A supercapacitor bimetallic oxide electrode prepared by the preparation method according to any one of claims 1 to 5, wherein the supercapacitor bimetallic oxide electrode is an interdigitated electrode, and the outer surface of the interdigitated electrode comprises an in-situ grown molybdenum-copper bimetallic oxide layer.

7. A planar micro supercapacitor comprising interdigital electrodes and an electrolyte solution; the interdigital electrodes are the supercapacitor bimetallic oxide electrodes according to claim 6.

8. The planar micro supercapacitor according to claim 7, characterized in that: The electrolyte solution is potassium hydroxide solution, sodium hydroxide solution or lithium hydroxide solution.

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