A copper-nickel composite material for new energy batteries and a preparation method thereof

Abstract

The application belongs to the technical field of alloy materials, and particularly relates to a copper-nickel composite material for new energy batteries and a preparation method thereof. The copper-nickel composite material comprises a copper-nickel composite sheet and a composite coating coated on the surface of the copper-nickel composite sheet. The copper-nickel composite sheet comprises the following raw material components by weight: copper powder 78-84 parts, nickel powder 10-15 parts, tin powder 2-4 parts, aluminum powder 3-7 parts, and modified phosphorene 2-5 parts. The modified phosphorene is prepared by the following process: adding ground black phosphorus crystals into water, ultrasonic stripping under an inert gas atmosphere, then adding an aqueous chloroauric acid solution and stirring, adjusting the pH to 10-11, adding a hydrazine hydrate solution and stirring for 1-2 hours to obtain the modified phosphorene. The copper-nickel composite material for new energy batteries has stable structure, excellent mechanical properties, and excellent corrosion resistance.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of alloy materials, and particularly relates to a copper-nickel composite material for new energy batteries and a preparation method thereof. BACKGROUND

[0002] With the increasing attention of the country to environmental protection and energy saving, green development, new energy vehicles, hybrid vehicles and other products have become popular, and the most core is the power battery pack as the power source, and the demand for materials for the power battery pack is also gradually increasing. The power battery pack is connected by the electrode terminals of each single battery, so that the single batteries are connected in series or parallel to meet the power demand of various new energy products. As can be seen, the connection structure of the electrode terminal has an important influence on the power output stability, safety and durability of the power battery, and the conductivity, weldability, corrosion resistance and mechanical properties of the material used for the connecting piece are closely related to the power output performance.

[0003] The commonly used materials for battery connecting pieces include pure nickel, pure copper and other pure metal materials, and alloy materials such as copper-nickel composite and copper-aluminum composite. Among them, the conductivity of pure copper material is the best, and the heat dissipation is good, but the strength is low, and the welding performance is poor; the pure nickel material has good welding performance and strong corrosion resistance, and can be used in high temperature or corrosive environment, but the internal resistance is high and the conductivity is poor; the copper and nickel are metallurgically combined to retain the high conductivity of copper and have excellent welding performance of nickel, and the copper-nickel composite material has good comprehensive performance as a battery connecting piece, in addition, the copper-nickel composite material also has high mechanical strength and good corrosion resistance, and can also reduce the material cost. However, the copper-nickel composite material also has some problems. For example, the difference between the thermal expansion coefficients of copper and nickel is large, which leads to poor interface bonding and the material strength needs to be further improved; as an electrochemical device, the corrosion resistance also needs to be higher. These problems will affect the long-term stability of the battery and need to be further improved. SUMMARY

[0004] The first object of the application is to provide a copper-nickel composite material for new energy batteries, which has stable structure, excellent mechanical properties and excellent corrosion resistance.

[0005] The second object of the application is to provide a preparation method of the above-mentioned copper-nickel composite material for new energy batteries.

[0006] In order to achieve the above-mentioned objects, the technical scheme adopted by the application is:

[0007] A copper-nickel composite material for new energy batteries, the copper-nickel composite material comprises a copper-nickel composite piece and a composite coating coated on the surface of the copper-nickel composite piece; the copper-nickel composite piece comprises the following raw material components by weight: copper powder 78-84 parts, nickel powder 10-15 parts, tin powder 2-4 parts, aluminum powder 3-7 parts, and modified phosphorene 2-5 parts.

[0008] The modified phosphorene is prepared by the following process:

[0009] The ground black phosphorus crystals were added to water and ultrasonically exfoliated under an inert gas atmosphere. Then, chloroauric acid aqueous solution was added and stirred to adjust the pH to 10-11. Hydrazine hydrate solution was added and stirred for 1-2 hours to obtain modified phosphorene.

[0010] Furthermore, the copper powder, nickel powder, tin powder, and aluminum powder are all atomized metal powders with a particle size of 10-20 μm.

[0011] Further, the concentration of the chloroauric acid aqueous solution is 0.01-0.03 mol / L; the concentration of the hydrazine hydrate solution is 3-5 mol / L.

[0012] Furthermore, the ratio of the amount of chloroauric acid aqueous solution, black phosphorus crystals, water and hydrazine hydrate solution is 1 mL: (40-80) mg: (120-140) mL: (0.03-0.05) mL.

[0013] Furthermore, the composite coating is composed of the following raw materials in parts by weight: 40-50 parts pyrrole, 20-25 parts surfactant, 9-18 parts stabilizer, and 8-12 parts composite conductive agent.

[0014] Furthermore, the composite conductive agent is prepared by the following process:

[0015] Ti3C2T X The composite conductive agent is obtained by ultrasonic dispersion in NaOH solution, followed by the addition of magnesium and aluminum salts, stirring to dissolve, heating to react, centrifuging, and drying.

[0016] Furthermore, the Ti3C2T X The ratio of magnesium salt, aluminum salt and NaOH solution is 1g:(4-5)g:(6-7)g:(200-400)mL; the concentration of NaOH solution is 1.0-2.0mol / L; the heating reaction temperature is 60-80℃ and the time is 1-3h.

[0017] The magnesium salt is any one of magnesium chloride, magnesium sulfate, and magnesium nitrate; the aluminum salt is any one of aluminum chloride, aluminum sulfate, and aluminum nitrate; the surfactant is sodium dodecylbenzenesulfonate; and the stabilizer is zinc oxide.

[0018] The preparation method of the aforementioned copper-nickel composite material for new energy batteries includes the following steps:

[0019] (1) Weigh each raw material of copper-nickel composite sheet, ball mill and mix, pre-press and sinter under pressure to obtain copper-nickel composite sintered body;

[0020] (2) In an inert gas atmosphere, the copper-nickel composite sintered body is preheated, hot extruded and annealed to obtain a copper-nickel composite sheet;

[0021] (3) Weigh each raw material of the composite coating, add water to prepare an electrolyte, use the copper-nickel composite sheet as the anode for electroplating, and obtain the copper-nickel composite material after electroplating.

[0022] Further, the pressure of the pre-pressing in step (1) is 1-2 GPa; the temperature of the pressure holding sintering is 750-850℃, and the time is 2-5h.

[0023] Furthermore, the deformation amount of the hot extrusion in step (2) is 40-70%.

[0024] Further, in step (2), the preheating temperature is 400-500℃ and the time is 20-30min; the hot extrusion temperature is 550-650℃; and the annealing temperature is 600-650℃ and the time is 2-5min.

[0025] Furthermore, in step (3), the mass ratio of the total mass of each raw material of the composite coating to the mass of water is 1:(20-25).

[0026] Furthermore, the electroplating current in step (3) is 3-6 mA / cm. 2 The time is 20-40 minutes.

[0027] Furthermore, the thickness of the composite coating of the copper-nickel composite material in step (3) is 10-15 μm.

[0028] The beneficial technical effects of this invention are as follows:

[0029] 1. This invention adds modified phosphorene to a copper-nickel composite material as a reinforcing phase, which improves the material's conductivity and structural stability. Phosphorene has a two-dimensional layered structure similar to graphene, with high electron mobility and good tensile properties. Modification is achieved by depositing Au nanoparticles on the phosphorene surface and between the intercalation layers. Au possesses excellent stability and good conductivity; its deposition on the phosphorene surface isolates the phosphorene from contact with water and oxygen, slowing its oxidation rate and inhibiting volume expansion, thus enhancing structural stability. Adding modified phosphorene to the composite material ensures that the phosphorene maintains good conductivity while improving structural stability, thereby enhancing the overall mechanical properties.

[0030] 2. This invention prepares a coating on the surface of a copper-nickel composite material, which can improve the corrosion resistance of the material. Pyrrole can form a polypyrrole layer on the material surface under the action of an electric current, exhibiting good conductivity. However, the polypyrrole coating has poor chemical stability and weak interfacial adhesion to the metal substrate. Adding a composite conductive agent and stabilizer, magnesium oxide, to the coating improves the corrosion resistance of the material in the Ti3C2T composite.X In-situ growth of magnesium aluminum hydrotalcite between layers and on the surface can enable Ti3C2T X The material forms a denser interlayer structure, filling the pores of the polypyrrole coating, significantly improving the coating's corrosion resistance and adhesion strength. Zinc oxide, as a stabilizer, fills the pores of the polypyrrole coating, absorbing ultraviolet light, inhibiting the photo-oxidative degradation of the coating, and also delaying microbial corrosion. Attached Figure Description

[0031] Figure 1 This is a scanning electron microscope image of the modified phosphorene obtained in Example 1 of the present invention;

[0032] Figure 2 This is a scanning electron microscope image of the composite conductive agent prepared in Example 1 of the present invention. Detailed Implementation

[0033] The following is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it should not be construed that the specific implementation of the present invention is limited to these descriptions. For those skilled in the art, various simple deductions or substitutions can be made without departing from the concept of the present invention, and all such modifications and substitutions should be considered within the scope of protection of the present invention. Specific conditions not specified in the embodiments are performed according to conventional conditions or conditions recommended by the manufacturer. Unless otherwise specified, all reagents or instruments used are conventional products obtained through commercial channels.

[0034] The Ti3C2T used in this invention X Titanium carbide (Ti3C2T) X MXene multilayer nanosheets (2-10μm), CAS number 12316-56-2.

[0035] The copper powder, nickel powder, tin powder and aluminum powder used in this invention are all atomized metal powders with a particle size of 10-20μm.

[0036] (I) Implementation Examples

[0037] Example 1

[0038] Example 1 provides a copper-nickel composite material for new energy batteries. The copper-nickel composite material includes a copper-nickel composite sheet and a composite coating on the surface of the copper-nickel composite sheet. The copper-nickel composite sheet is composed of the following raw materials in parts by weight: 80 parts copper powder, 12 parts nickel powder, 3 parts tin powder, 4 parts aluminum powder, and 4 parts modified phosphorus.

[0039] The modified phosphorene is prepared by the following process:

[0040] Black phosphorus crystals were crushed and ground to a cross-sectional and longitudinal dimension of less than 200 μm and a thickness of less than 50 μm. The black phosphorus crystals were added to water in a ratio of 1 mL:60 mg:120 mL:0.04 mL using chloroauric acid aqueous solution, black phosphorus crystals, water, and hydrazine hydrate solution. The mixture was then ultrasonically exfoliated for 50 hours under argon atmosphere (ultrasonic power 900 W, ultrasonic frequency 15 kHz). A 0.02 mol / L chloroauric acid aqueous solution was then added and stirred until homogeneous. NaOH solution was added dropwise to adjust the pH to 10, and then 4 mol / L hydrazine hydrate solution was added and the reaction was stirred for 2 hours to obtain modified phosphorene. The scanning electron microscope image of the modified phosphorene is shown below. Figure 1 As shown.

[0041] The composite coating is composed of the following raw materials in parts by weight: 45 parts pyrrole, 24 parts sodium dodecylbenzenesulfonate surfactant, 14 parts zinc oxide stabilizer, and 10 parts composite conductive agent.

[0042] The composite conductive agent is prepared by the following process:

[0043] According to Ti3C2T X The ratio of magnesium chloride, aluminum chloride, and NaOH solution used is 1g:4g:6g:300mL. Ti3C2T X The mixture was ultrasonically dispersed in a 2.0 mol / L NaOH solution, followed by the addition of magnesium chloride and aluminum chloride, followed by stirring to dissolve. The mixture was then heated at 60°C for 2 hours. After centrifugation and drying, the resulting product was obtained from Ti3C2T. X A composite conductive agent consisting of magnesium aluminum hydrotalcite grown in situ between layers and on the surface was obtained. The scanning electron microscope image of this composite conductive agent is shown below. Figure 2 As shown.

[0044] This embodiment also provides a method for preparing the above-mentioned copper-nickel composite material for new energy batteries, the specific steps of which are as follows:

[0045] (1) Weigh the raw material powders of the above copper-nickel composite sheet, pour them into a ball mill for ball milling and mixing, mix evenly, pre-press and form under 2GPa pressure, and sinter under pressure at 800℃ for 4h to obtain copper-nickel composite sintered body;

[0046] (2) Under an argon atmosphere, the copper-nickel composite sintered body is preheated at 450℃ for 20 min, and then hot extruded at 600℃ with an extrusion speed of 6 mm / s and an extrusion deformation of 50%. Finally, it is annealed at 650℃ for 3 min to obtain a copper-nickel composite sheet.

[0047] (3) Weigh the raw materials of the above composite coating, add them to water at a mass ratio of 1:24 (composite coating to water), stir evenly to make an electrolyte, and use the copper-nickel composite sheet as the anode, with an electrolysis current of 5 mA / cm. 2A constant current is applied for 30 minutes to deposit a 10-15 μm composite coating on the surface of the copper-nickel composite sheet, thus obtaining the copper-nickel composite material.

[0048] Example 2

[0049] Example 2 provides a copper-nickel composite material for new energy batteries. The copper-nickel composite material includes a copper-nickel composite sheet and a composite coating on the surface of the copper-nickel composite sheet. The copper-nickel composite sheet comprises the following raw materials in parts by weight: 78 parts copper powder, 10 parts nickel powder, 2 parts tin powder, 3 parts aluminum powder, and 2 parts modified phosphorus.

[0050] The modified phosphorene is prepared by the following process:

[0051] Black phosphorus crystals were crushed and ground to a cross-sectional and longitudinal dimension of less than 200 μm and a thickness of less than 50 μm. The black phosphorus crystals were added to water in a ratio of 1 mL: 40 mg: 120 mL: 0.03 mL using chloroauric acid aqueous solution, black phosphorus crystals, water, and hydrazine hydrate solution. The mixture was then ultrasonically exfoliated for 40 hours under argon atmosphere (ultrasonic power 850 W, ultrasonic frequency 15 kHz). Then, 0.01 mol / L chloroauric acid aqueous solution was added and stirred until homogeneous. NaOH solution was added dropwise to adjust the pH to 10, and finally, 3 mol / L hydrazine hydrate solution was added and stirred for 1 hour to obtain modified phosphorene.

[0052] The composite coating is composed of the following raw materials in parts by weight: 40-50 parts of pyrrole, 20 parts of sodium dodecylbenzene sulfonate surfactant, 9 parts of zinc oxide stabilizer, and 8 parts of composite conductive agent.

[0053] The composite conductive agent is prepared by the following process:

[0054] According to Ti3C2T X The ratio of magnesium chloride, aluminum chloride, and NaOH solution used is 1g:4g:6g:200mL. Ti3C2T X The mixture was ultrasonically dispersed in a 1.0 mol / L NaOH solution, followed by the addition of magnesium chloride and aluminum chloride, followed by stirring to dissolve. The mixture was then heated at 60°C for 1 hour. After centrifugation and drying, the resulting product was obtained from Ti3C2T. X Composite conductive agent for in-situ growth of magnesium aluminum hydrotalcite between layers and on the surface.

[0055] This embodiment also provides a method for preparing the above-mentioned copper-nickel composite material for new energy batteries, the specific steps of which are as follows:

[0056] (1) Weigh the raw material powders of the above copper-nickel composite sheet, pour them into a ball mill for ball milling and mixing, mix evenly, pre-press and form under 1GPa pressure, and sinter under pressure at 750℃ for 2h to obtain copper-nickel composite sintered body;

[0057] (2) Under an argon atmosphere, the copper-nickel composite sintered body is preheated at 400℃ for 20 min, and then hot extruded at 550℃ with an extrusion speed of 2 mm / s and an extrusion deformation of 40%. Finally, it is annealed at 600℃ for 2 min to obtain a copper-nickel composite sheet.

[0058] (3) Weigh the raw materials of the above composite coating, add them to water at a mass ratio of 1:20, stir evenly to make an electrolyte, and use the copper-nickel composite sheet as the anode, with an electrode current of 3 mA / cm 2 A constant current was applied for 40 minutes to deposit a 10-15 μm composite coating on the surface of the copper-nickel composite sheet, thus obtaining the copper-nickel composite material.

[0059] Example 3

[0060] Example 3 provides a copper-nickel composite material for new energy batteries. The copper-nickel composite material includes a copper-nickel composite sheet and a composite coating on the surface of the copper-nickel composite sheet. The copper-nickel composite sheet is composed of the following raw materials in parts by weight: 84 parts copper powder, 15 parts nickel powder, 4 parts tin powder, 7 parts aluminum powder, and 5 parts modified phosphorus.

[0061] The modified phosphorene is prepared by the following process:

[0062] Black phosphorus crystals were crushed and ground to a cross-sectional and longitudinal dimension of less than 200 μm and a thickness of less than 50 μm. The black phosphorus crystals were added to water in a ratio of 1 mL: 80 mg: 140 mL: 0.05 mL using chloroauric acid aqueous solution, black phosphorus crystals, water, and hydrazine hydrate solution. The mixture was then ultrasonically exfoliated for 60 hours under argon atmosphere (ultrasonic power 950 W, ultrasonic frequency 20 kHz). Then, 0.03 mol / L chloroauric acid aqueous solution was added and stirred until homogeneous. NaOH solution was added dropwise to adjust the pH to 11, and finally, 5 mol / L hydrazine hydrate solution was added and the mixture was stirred for 2 hours to obtain modified phosphorene.

[0063] The composite coating is composed of the following raw materials in parts by weight: 50 parts pyrrole, 25 parts sodium dodecylbenzenesulfonate surfactant, 18 parts zinc oxide stabilizer, and 12 parts composite conductive agent.

[0064] The composite conductive agent is prepared by the following process:

[0065] According to Ti3C2T X The ratio of magnesium chloride, aluminum chloride, and NaOH solution is 1g:5g:7g:400mL. Ti3C2T X The mixture was ultrasonically dispersed in a 2.0 mol / L NaOH solution, followed by the addition of magnesium chloride and aluminum chloride, followed by stirring to dissolve. The mixture was then heated at 80°C for 3 hours. After centrifugation and drying, the resulting product was obtained from Ti3C2T. X Composite conductive agent for in-situ growth of magnesium aluminum hydrotalcite between layers and on the surface.

[0066] This embodiment also provides a method for preparing the above-mentioned copper-nickel composite material for new energy batteries, the specific steps of which are as follows:

[0067] (1) Weigh the raw material powders of the above copper-nickel composite sheet, pour them into a ball mill for ball milling and mixing, mix evenly, pre-press and form under 2GPa pressure, and sinter under pressure at 850℃ for 5h to obtain copper-nickel composite sintered body;

[0068] (2) Under an argon atmosphere, the copper-nickel composite sintered body is preheated at 500℃ for 30 min, and then hot extruded at 650℃ with an extrusion speed of 8 mm / s and an extrusion deformation of 70%. Finally, it is annealed at 650℃ for 5 min to obtain a copper-nickel composite sheet.

[0069] (3) Weigh the raw materials of the above composite coating, add them to water at a mass ratio of 1:25, stir evenly to make an electrolyte, and use the copper-nickel composite sheet as the anode, with an electrolysis rate of 6 mA / cm 2 A constant current is applied for 20 minutes to deposit a 10-15 μm composite coating on the surface of the copper-nickel composite sheet, thus obtaining the copper-nickel composite material.

[0070] (ii) Comparative Example

[0071] Comparative Example 1

[0072] Comparative Example 1 is basically the same as Example 1, except that the modified phosphorene in Example 1 is omitted.

[0073] Comparative Example 2

[0074] Comparative Example 2 is basically the same as Example 1, except that the modified phosphorene in Example 1 is replaced with an equal amount of phosphorene nanosheets.

[0075] In this comparative example, the phosphorene nanosheets were prepared by the following process: black phosphorus crystals were crushed and ground to a cross-sectional and longitudinal dimension of less than 200 μm and a thickness of less than 50 μm, and then ultrasonically exfoliated in an argon atmosphere for 50 hours, wherein the ultrasonic power was 900 W and the ultrasonic frequency was 15 kHz, to obtain phosphorene nanosheets.

[0076] Comparative Example 3

[0077] Comparative Example 3 is basically the same as Example 1, except that the composite conductive agent in Example 1 is omitted.

[0078] Comparative Example 4

[0079] Comparative Example 4 is basically the same as Example 1, except that the composite conductive agent in Example 1 is replaced with Ti3C2T. X A mixture with magnesium aluminum hydrotalcite.

[0080] In this comparative example, the magnesium aluminum hydrotalcite was prepared by the following process: Following a ratio of magnesium chloride, aluminum chloride, and NaOH solution of 2g:3g:150mL, Ti3C2T... X The mixture was added to a 2.0 mol / L NaOH solution and ultrasonically dispersed. Then, magnesium chloride and aluminum chloride were added and stirred to dissolve. The mixture was heated at 60°C for 2 hours, and then centrifuged and dried to obtain the final product.

[0081] (III) Test Examples

[0082] The copper-nickel composite materials prepared in Examples 1-3 and Comparative Examples 1-4 were subjected to performance tests.

[0083] Tensile test: The tensile properties of the copper-nickel composite materials of Examples 1-3 and Comparative Examples 1-4 were tested according to GB / T 228.1-2021 "Metallic materials - Tensile testing - Part 1: Test method at room temperature". The results are shown in Table 1.

[0084] Hardness test: The hardness of the copper-nickel composite materials in Examples 1-3 and Comparative Examples 1-4 was tested according to GB / T 4340.1-2024 "Metallic materials - Vickers hardness test - Part 1: Test method". The results are shown in Table 1.

[0085] Corrosion resistance test: The corrosion resistance of copper-nickel composite materials in Examples 1-3 and Comparative Examples 1-4 was tested according to GB / T 10125-2021 "Artificial Atmosphere Corrosion Test - Salt Spray Test". The results are shown in Table 1.

[0086] Coating adhesion test: The adhesion of the copper-nickel composite coatings of Examples 1-3 and Comparative Examples 1-4 was tested according to GB / T 9286-2021 "Paints and Varnishes Cross-cut Test". The results are shown in Table 1.

[0087]

[0088] Table 1 shows that the copper-nickel composite materials prepared in Examples 1-3 of this invention exhibit high hardness, good electrical conductivity, and excellent corrosion resistance. Compared to Example 1, Comparative Example 1 omits the modified phosphorusene in Example 1, Comparative Example 2 replaces the modified phosphorusene in Example 1 with an equal amount of phosphorusene, Comparative Example 3 omits the composite conductive agent in Example 1, and Comparative Example 4 replaces the composite conductive agent in Example 1 with Ti3C2T. XThe mixtures of magnesium aluminum hydrotalcite and magnesium aluminum hydrotalcite, in proportions 1-4, showed varying degrees of decrease in hardness, conductivity, corrosion resistance, and coating adhesion. Specific analysis revealed two main points: Firstly, the addition of modified phosphorene to the copper-nickel composite material, as a reinforcing phase, improves the material's conductivity and structural stability. Phosphorene possesses a two-dimensional layered structure similar to graphene, exhibiting high electron mobility and good tensile properties. However, phosphorene is prone to oxidative degradation and undergoes significant volume changes during conductivity. Modification is achieved by depositing Au nanoparticles on the phosphorene surface and between intercalation layers. Au possesses excellent stability and good conductivity; its deposition on the phosphorene surface isolates it from water and oxygen, slowing its oxidation rate and inhibiting volume expansion, thus enhancing structural stability. Adding modified phosphorene to the composite material ensures that phosphorene maintains good conductivity while improving structural stability, thereby enhancing overall mechanical properties. Secondly, the coating prepared on the surface of the copper-nickel composite material improves its corrosion resistance. Adding a composite conductive agent and stabilizer, magnesium oxide, to the coating in Ti3C2T... X In-situ growth of magnesium aluminum hydrotalcite between layers and on the surface can enable Ti3C2T X The material forms a denser interlayer structure, filling the pores of the polypyrrole coating, significantly improving the coating's corrosion resistance and adhesion strength.

[0089] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them. The basic principles and main features of the present invention have been described above with specific implementation schemes. Based on the present invention, some modifications or substitutions can be made, but these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of protection claimed by the present invention.

Claims

1. A copper-nickel composite material for new energy batteries, characterized in that, The copper-nickel composite material includes a copper-nickel composite sheet and a composite coating covering the surface of the copper-nickel composite sheet; The copper-nickel composite sheet comprises the following raw materials in parts by weight: 78-84 parts copper powder, 10-15 parts nickel powder, 2-4 parts tin powder, 3-7 parts aluminum powder, and 2-5 parts modified phosphorusene. The modified phosphorene is prepared by the following process: The ground black phosphorus crystals were added to water and ultrasonically exfoliated under an inert gas atmosphere. Then, chloroauric acid aqueous solution was added and stirred to adjust the pH to 10-11. Hydrazine hydrate solution was added and stirred for 1-2 hours to obtain modified phosphorene.

2. The copper-nickel composite material for new energy batteries according to claim 1, characterized in that, The concentration of the chloroauric acid aqueous solution is 0.01-0.03 mol / L; the concentration of the hydrazine hydrate solution is 3-5 mol / L.

3. The copper-nickel composite material for new energy batteries according to claim 1, characterized in that, The ratio of the amount of chloroauric acid aqueous solution, black phosphorus crystals, water and hydrazine hydrate solution used is 1 mL: (40-80) mg: (120-140) mL: (0.03-0.05) mL.

4. The copper-nickel composite material for new energy batteries according to claim 1, characterized in that, The composite coating is composed of the following raw materials in parts by weight: 40-50 parts pyrrole, 20-25 parts surfactant, 9-18 parts stabilizer, and 8-12 parts composite conductive agent.

5. The copper-nickel composite material for new energy batteries according to claim 4, characterized in that, The composite conductive agent is prepared by the following process: Ti3C2T X The composite conductive agent is obtained by ultrasonic dispersion in NaOH solution, followed by the addition of magnesium and aluminum salts, stirring to dissolve, heating to react, centrifuging, and drying.

6. The copper-nickel composite material for new energy batteries according to claim 5, characterized in that, The Ti3C2T X The ratio of magnesium salt, aluminum salt and NaOH solution is 1g:(4-5)g:(6-7)g:(200-400)mL; the concentration of NaOH solution is 1.0-2.0mol / L; the heating reaction temperature is 60-80℃ and the time is 1-3h. The magnesium salt is any one of magnesium chloride, magnesium sulfate, and magnesium nitrate; the aluminum salt is any one of aluminum chloride, aluminum sulfate, and aluminum nitrate; the surfactant is sodium dodecylbenzenesulfonate; and the stabilizer is zinc oxide.

7. The method for preparing copper-nickel composite material for new energy batteries according to any one of claims 1-6, characterized in that, Includes the following steps: (1) Weigh each raw material of copper-nickel composite sheet, ball mill and mix, pre-press and sinter under pressure to obtain copper-nickel composite sintered body; (2) In an inert gas atmosphere, the copper-nickel composite sintered body is preheated, hot extruded and annealed to obtain a copper-nickel composite sheet; (3) Weigh each raw material of the composite coating, add water to prepare an electrolyte, use the copper-nickel composite sheet as the anode for electroplating, and obtain the copper-nickel composite material after electroplating.

8. The method for preparing copper-nickel composite material for new energy batteries according to claim 7, characterized in that, The pressure for pre-pressing in step (1) is 1-2 GPa; the temperature for pressure holding sintering is 750-850℃, and the time is 2-5h.

9. The method for preparing copper-nickel composite material for new energy batteries according to claim 7, characterized in that, The preheating temperature in step (2) is 400-500℃ and the time is 20-30 min; the hot extrusion temperature is 550-650℃; and the annealing temperature is 600-650℃ and the time is 2-5 min.

10. The method for preparing copper-nickel composite material for new energy batteries according to claim 7, characterized in that, The electroplating current in step (3) is 3-6 mA / cm. 2 The time is 20-40 minutes.

Images