Antioxidant reinforced gradient composite structure copper wire for new energy and preparation process of antioxidant reinforced gradient composite structure copper wire
Through gradient composite structure design and multiple electrodeposition treatments, a dense anti-oxidation barrier and anti-corrosion layer are formed on the surface of the copper wire, which solves the high-temperature oxidation and corrosion problems of copper conductors in new energy vehicles and improves the mechanical strength and conductivity.
Patent Information
- Application Number
- CN202510920851.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-04
- Publication Date
- 2025-09-23
AI Technical Summary
Existing copper conductors in new energy vehicles suffer from decreased conductivity and increased connector resistance due to high-temperature oxidation, erosion by corrosive media, and vibration. The existing nickel/tin composite plating has insufficient bonding strength and poor toughness of the protective layer, which cannot meet the extreme environmental requirements of new energy vehicles.
Adopting gradient composite structure design, through secondary stretching annealing, multiple electrodeposition and pressurized heat treatment, a dense anti-oxidation barrier and anti-corrosion layer is formed on the surface of the copper wire, which has excellent bonding strength and isolates the penetration of corrosive media.
It significantly improves the mechanical strength and anti-oxidation performance of copper wire in the new energy vehicle environment, effectively prevents corrosion, maintains stable conductivity, and extends service life.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of copper wires, and in particular to an antioxidant-strengthened gradient composite structure copper wire for new energy use and a preparation process thereof. Background Art
[0002] The rapid development of the new energy vehicle industry has placed unprecedentedly stringent demands on the core conductor materials of power transmission systems. Key components such as drive motors, power batteries, and high-voltage charging systems operate in extreme environments characterized by high temperatures (peak temperatures >200°C), strong vibration, and complex electrochemical corrosion. When the motor armature operating temperature reaches 180-200°C, the surface oxide layer on the copper substrate thickens exponentially, and conductivity drops by over 15%. Existing nickel / tin composite coatings, due to thermal expansion coefficient mismatch, develop microcracks during thermal cycling and accelerate interfacial delamination. Furthermore, corrosive media such as electrolyte leakage within the battery pack and road salt spray from snowmelt can penetrate the copper substrate through micropores in the coating, inducing intergranular corrosion and stress cracking, resulting in abnormally high resistance in high-voltage connectors.
[0003] Current automotive conductor technology has obvious limitations. The protective layer lacks durability. Although the magnetron sputtered Al2O3 coating is resistant to oxidation, it has poor toughness and cannot cover complex linear shapes. It is prone to cracking under vibration conditions. The bonding strength between the electroplated tin layer and the copper substrate is less than 15MPa, and Kirkendall pores are generated under temperature shock, becoming the preferred diffusion channel for corrosion.
[0004] Therefore, there is an urgent need to develop specialized copper conductors that combine ultra-high strength, long-lasting high-temperature oxidation resistance, and fully sealed corrosion resistance. The core of this approach lies in achieving a synergistic combination of mechanical support, oxidation barrier, and corrosion isolation through a gradient composite structure design. This invention offers a groundbreaking solution specifically designed for the extreme operating conditions of new energy vehicles. Summary of the Invention
[0005] The purpose of the present invention is to provide an antioxidant reinforced gradient composite structure copper wire for new energy and a preparation process thereof, so as to solve the problems existing in the prior art.
[0006] In order to solve the above technical problems, the present invention provides the following technical solutions: an antioxidant reinforced gradient composite structure copper wire for new energy, wherein the high-strength tinned copper wire comprises copper wire and anti-corrosion paint.
[0007] Furthermore, the copper wire is manufactured through secondary stretching annealing treatment, secondary deposition treatment, and pressurized heat treatment.
[0008] Furthermore, the first deposition treatment is to use aluminum nitrate hexahydrate, nickel nitrate hexahydrate, cerium nitrate hexahydrate, potassium acetate, and high-purity water as electrolytes, and then electro-deposit the copper wire raw material for a period of time, and then pressurize and heat treat the copper wire raw material; the second deposition treatment is to use stannous chloride dihydrate, potassium hydrogen phosphate trihydrate, and deionized water as electrolytes, and electro-deposit the copper wire raw material.
[0009] Furthermore, the anti-corrosion paint is prepared from modified polyimide; the modified polyimide is prepared from diacetyl, 2-amino-4-hydroxybenzoic acid, 2,4-dichloro-A-phenylethylamine, erythro-5,6-dodecanediol, aminosulfonic acid, sodium hydroxide, phosphoric acid, and 1,2,4,5-pyromellitic anhydride.
[0010] Furthermore, a method for preparing an antioxidant-strengthened gradient composite structure copper wire for new energy use includes the following preparation steps: (1) The copper strip was drawn at 400-500°C for 15-25 minutes, kept at this temperature for 30-40 minutes, annealed at 430-450°C for 1 hour, and cooled to room temperature at a rate of 6-8°C / s to obtain the pretreated copper wire; (2) The pretreated copper wire was washed twice with anhydrous ethanol, immersed in deionized water 2 to 3 times the mass of the pretreated copper wire, and ultrasonically cleaned at 600W for 8 to 12 minutes. Then, it was taken out and immersed in 4.2% hydrochloric acid 2 to 3 times the mass of the pretreated copper wire. After ultrasonic washing for 15 minutes, it was washed 6 times with deionized water and alcohol in sequence. The pretreated copper wire was used as the working electrode, the saturated calomel electrode was used as the reference electrode, and the platinum sheet was used as the counter electrode. After electroplating at -1.0V for 500 to 700s, the copper wire was reacted at 3 to 5MPa pressure and 80℃ for 2 to 4h, and then reacted at 5 to 10MPa and 160℃ for 6h to obtain the copper wire raw material. (3) Use copper wire as working electrode and graphite plate as counter electrode, 1~4mA / cm 2 , electroplated at 30°C for 10 min, washed with deionized water 5 times, dried at 50°C for 8 h, drawn at 400~500°C to a diameter of 0.1~0.3 mm, annealed at 430~450°C for 1 h, and cooled to room temperature at 6~8°C / s to obtain copper wire.
[0011] Furthermore, the copper bar preparation method in step (1) is as follows: copper, magnesium, chromium, and titanium are mixed in a mass ratio of 100:10:10:10 to 100:15:15:15, melted until liquid, cast to obtain an ingot, forged at 300-350° C. for 10-15 minutes, then kept at 580-620° C. for 30-45 minutes, and cooled to room temperature.
[0012] Furthermore, the electrolyte used for the electrodeposition in step (2) is an aluminum-nickel-cerium electrolyte, and the aluminum-nickel-cerium electrolyte is prepared by mixing aluminum nitrate hexahydrate, nickel nitrate hexahydrate, cerium nitrate hexahydrate, potassium acetate, and high-purity water in a mass ratio of 1:0.8:0.5:2.8:293, and stirring at 100-150 rpm for 1 hour.
[0013] Furthermore, the electrolyte used for the electrodeposition in step (3) is a tin electrolyte, and the tin electrolyte is prepared by mixing stannous chloride dihydrate, potassium hydrogen phosphate trihydrate, and deionized water in a mass ratio of 15:120:1000.
[0014] Compared with the prior art, the beneficial effects achieved by the present invention are: (1) The present invention successfully constructs a copper-based conductor with a gradient composite structure through the synergistic effects of secondary stretching annealing, secondary deposition, and pressurized heat treatment. This structure and its preparation process significantly improve the comprehensive performance of copper wire in harsh new energy application environments.
[0015] (2) The present invention achieves grain refinement and atomic arrangement optimization through component design optimization of copper bar alloy components copper, magnesium, chromium, and titanium and secondary stretching annealing process, thereby significantly improving the mechanical strength of the copper wire.
[0016] (3) The present invention performs a first deposition treatment, using nickel nitrate, aluminum nitrate, and cerium nitrate as raw materials, which are electro-deposited on the surface of the copper strip. After pressurized heat treatment, a strong metallurgical bond is formed with the substrate, forming a dense high-temperature anti-oxidation barrier, which effectively resists high-temperature oxidation and corrosive medium erosion inside new energy equipment.
[0017] (4) A second deposition process is performed to electroplate tin onto the middle layer, which not only fills the surface micropores and improves the surface density and smoothness, but more importantly, forms an excellent corrosion-resistant layer. Its layered structure design greatly enhances the bonding strength with the core copper layer and the outer protective layer, effectively isolating the penetration of corrosive media. DETAILED DESCRIPTION
[0018] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. 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.
[0019] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the various index testing methods of the high-strength tinned copper wire prepared in the following examples. High strength: The embodiment and comparative example of the same size were taken and the determination method disclosed in GB / T10623-2008 Tests for Mechanical Properties of Metal Materials was referred to.
[0020] Corrosion resistance: The embodiment and comparative example of the same size were subjected to a neutral salt spray test in a 5% mass concentration sodium chloride solution environment according to GB / T 10125 to observe the surface rust.
[0021] Antioxidation: Measure the oxidation weight gain after keeping at 150℃ for 250h in an oxygen environment.
[0022] Example 1 (1) Copper, magnesium, chromium and titanium were mixed in a mass ratio of 100:10:10:10, melted until liquid, cast to obtain an ingot, forged at 300°C for 10 minutes, then kept at 580°C for 30 minutes, and cooled to room temperature to obtain a copper bar; the copper bar was drawn at 400°C for 15 minutes, kept at this temperature for 30 minutes, annealed at 430°C for 1 hour, and cooled to room temperature at 6°C / s to obtain a pretreated copper wire; (2) The pretreated copper wire was washed twice with anhydrous ethanol, immersed in deionized water twice the mass of the pretreated copper wire, ultrasonically cleaned at 600W for 8 minutes, taken out, immersed in 4.2% hydrochloric acid twice the mass of the pretreated copper wire, and ultrasonically cleaned for 15 minutes. Then, the pretreated copper wire was washed six times with deionized water and alcohol in sequence. The pretreated copper wire was used as the working electrode, a saturated calomel electrode was used as the reference electrode, and a platinum sheet was used as the counter electrode. After electroplating at -1.0V for 500s, the reaction was carried out at 3MPa pressure and 80℃ for 2h, and then at 5MPa and 160℃ for 6h to obtain the copper wire raw material. The electrolyte used for the electroplating was aluminum nickel cerium electrolyte. The preparation method of the aluminum nickel cerium electrolyte was as follows: aluminum nitrate hexahydrate, nickel nitrate hexahydrate, cerium nitrate hexahydrate, potassium acetate, and high-purity water were mixed in a mass ratio of 1:0.8:0.5:2.8:293, and stirred at 100rpm for 1h. (3) Using copper wire as the working electrode and graphite plate as the counter electrode, 1 mA / cm 2 , electroplating at 30°C for 10 minutes, washing with deionized water 5 times, drying at 50°C for 8 hours, drawing at 400°C to a diameter of 0.1 mm, annealing at 430°C for 1 hour, and cooling to room temperature at 6°C / s to obtain a copper wire; the electrolyte used in the electroplating is a tin electrolyte, and the tin electrolyte is prepared by mixing stannous chloride dihydrate, potassium hydrogen phosphate trihydrate, and deionized water in a mass ratio of 15:120:1000.
[0023] Example 2 (1) Copper, magnesium, chromium and titanium were mixed in a mass ratio of 100:12:12:12, melted until liquid, cast to obtain an ingot, forged at 325°C for 13 minutes, then kept at 600°C for 38 minutes, and cooled to room temperature to obtain a copper bar; the copper bar was drawn at 450°C for 20 minutes, kept at this temperature for 35 minutes, annealed at 440°C for 1 hour, and cooled to room temperature at 7°C / s to obtain a pretreated copper wire; (2) The pretreated copper wire was washed twice with anhydrous ethanol, immersed in deionized water 2.5 times the mass of the pretreated copper wire, ultrasonically cleaned at 600W for 10 minutes, taken out, immersed in 4.2% hydrochloric acid 2.5 times the mass of the pretreated copper wire, and ultrasonically cleaned for 15 minutes. Then, it was washed 6 times with deionized water and alcohol in sequence. The pretreated copper wire was used as the working electrode, a saturated calomel electrode was used as the reference electrode, and a platinum sheet was used as the counter electrode. After electroplating at -1.0V for 600s, the reaction was carried out at 4MPa pressure and 80℃ for 3h, and then reacted at 7MPa and 160℃ for 6h to obtain the copper wire raw material. The electrolyte used in the electroplating was aluminum nickel cerium electrolyte. The preparation method of the aluminum nickel cerium electrolyte was as follows: aluminum nitrate hexahydrate, nickel nitrate hexahydrate, cerium nitrate hexahydrate, potassium acetate, and high-purity water were mixed in a mass ratio of 1:0.8:0.5:2.8:293, and stirred at 130rpm for 1h. (3) Using copper wire as the working electrode and graphite plate as the counter electrode, 3 mA / cm 2 , electroplating at 30°C for 10 minutes, washing with deionized water 5 times, drying at 50°C for 8 hours, drawing at 450°C to a diameter of 0.2 mm, annealing at 440°C for 1 hour, and cooling to room temperature at 7°C / s to obtain a copper wire; the electrolyte used in the electroplating is a tin electrolyte, and the tin electrolyte is prepared by mixing stannous chloride dihydrate, potassium hydrogen phosphate trihydrate, and deionized water in a mass ratio of 15:120:1000.
[0024] Example 3 (1) Copper, magnesium, chromium and titanium were mixed in a mass ratio of 100:15:15:15, melted until liquid, cast to obtain an ingot, forged at 350°C for 15 minutes, then kept at 620°C for 45 minutes, and cooled to room temperature to obtain a copper bar; the copper bar was drawn at 500°C for 25 minutes, kept at this temperature for 40 minutes, annealed at 450°C for 1 hour, and cooled to room temperature at 8°C / s to obtain a pretreated copper wire; (2) The pretreated copper wire was washed twice with anhydrous ethanol, immersed in deionized water 3 times the mass of the pretreated copper wire, ultrasonically cleaned at 600W for 12 minutes, taken out, immersed in 4.2% hydrochloric acid 3 times the mass of the pretreated copper wire, and ultrasonically cleaned for 15 minutes. Then, it was washed 6 times with deionized water and alcohol in sequence. The pretreated copper wire was used as the working electrode, a saturated calomel electrode was used as the reference electrode, and a platinum sheet was used as the counter electrode. After electroplating at -1.0V for 700s, the reaction was carried out at 5MPa pressure and 80℃ for 4h, and then at 10MPa and 160℃ for 6h to obtain the copper wire raw material. The electrolyte used in the electroplating was aluminum nickel cerium electrolyte. The preparation method of the aluminum nickel cerium electrolyte was as follows: aluminum nitrate hexahydrate, nickel nitrate hexahydrate, cerium nitrate hexahydrate, potassium acetate, and high-purity water were mixed in a mass ratio of 1:0.8:0.5:2.8:293, and stirred at 150rpm for 1h. (3) Using copper wire as the working electrode and graphite plate as the counter electrode, 4 mA / cm 2 , electroplating at 30°C for 10 minutes, washing with deionized water 5 times, drying at 50°C for 8 hours, drawing at 500°C to a diameter of 0.3 mm, annealing at 450°C for 1 hour, and cooling to room temperature at 8°C / s to obtain a copper wire; the electrolyte used in the electroplating is a tin electrolyte, and the tin electrolyte is prepared by mixing stannous chloride dihydrate, potassium hydrogen phosphate trihydrate, and deionized water in a mass ratio of 15:120:1000.
[0025] Example 4 (1) Copper, magnesium, chromium and titanium were mixed in a mass ratio of 100:12:12:15, melted until liquid, cast to obtain an ingot, forged at 350°C for 10 minutes, then kept at 590°C for 35 minutes, and cooled to room temperature to obtain a copper bar; the copper bar was drawn at 420°C for 20 minutes, kept at this temperature for 30 minutes, annealed at 430°C for 1 hour, and cooled to room temperature at 6°C / s to obtain a pretreated copper wire; (2) The pretreated copper wire was washed twice with anhydrous ethanol, immersed in deionized water twice the mass of the pretreated copper wire, ultrasonically cleaned at 600W for 8 minutes, taken out, immersed in 4.2% hydrochloric acid three times the mass of the pretreated copper wire, and ultrasonically cleaned for 15 minutes. Then, it was washed 6 times with deionized water and alcohol in sequence. The pretreated copper wire was used as the working electrode, the saturated calomel electrode was used as the reference electrode, the platinum sheet was used as the counter electrode, and the electrolyte was aluminum nickel cerium electrolyte. The preparation method of aluminum nickel cerium electrolyte was as follows: aluminum nitrate hexahydrate, nickel nitrate hexahydrate, cerium nitrate hexahydrate, potassium acetate, and high-purity water were mixed in a mass ratio of 1:0.8:0.5:2.8:293, stirred at 100rpm for 1 hour, electroplated at -1.0V for 550s, reacted at 3MPa pressure and 80℃ for 2 hours, and then reacted at 5MPa and 160℃ for 6 hours to obtain the copper wire raw material; (3) The copper wire material was used as the working electrode, the graphite plate was used as the counter electrode, and the electrolyte was a tin electrolyte. The tin electrolyte was prepared by mixing stannous chloride dihydrate, potassium hydrogen phosphate trihydrate, and deionized water in a mass ratio of 15:120:1000, with a flow rate of 2 mA / cm 2 , electroplated at 30°C for 10 min, washed with deionized water 5 times, dried at 50°C for 8 h, drawn at 450°C to a diameter of 0.3 mm, annealed at 450°C for 1 h, and cooled to room temperature at 8°C / s to obtain a copper wire.
[0026] Example 5 (1) Copper, magnesium, chromium and titanium were mixed in a mass ratio of 100:13:11:10, melted until liquid, cast into an ingot, forged at 330°C for 10 minutes, then kept at 600°C for 34 minutes, and cooled to room temperature to obtain a copper bar; the copper bar was drawn at 420°C for 25 minutes, kept at this temperature for 35 minutes, annealed at 450°C for 1 hour, and cooled to room temperature at 8°C / s to obtain a pretreated copper wire; (2) The pretreated copper wire was washed twice with anhydrous ethanol, immersed in deionized water 3 times the mass of the pretreated copper wire, ultrasonically cleaned at 600W for 12 minutes, taken out, immersed in 4.2% hydrochloric acid 2.5 times the mass of the pretreated copper wire, and ultrasonically cleaned for 15 minutes. Then, it was washed 6 times with deionized water and alcohol in sequence. The pretreated copper wire was used as the working electrode, the saturated calomel electrode was used as the reference electrode, the platinum sheet was used as the counter electrode, and the electrolyte was aluminum nickel cerium electrolyte. The preparation method of aluminum nickel cerium electrolyte was as follows: aluminum nitrate hexahydrate, nickel nitrate hexahydrate, cerium nitrate hexahydrate, potassium acetate, and high-purity water were mixed in a mass ratio of 1:0.8:0.5:2.8:293, stirred at 150rpm for 1 hour, electroplated at -1.0V for 700s, reacted at 5MPa pressure and 80℃ for 4 hours, and then reacted at 5MPa and 160℃ for 6 hours to obtain the copper wire raw material; (3) The copper wire material was used as the working electrode, the graphite plate was used as the counter electrode, and the electrolyte was a tin electrolyte. The tin electrolyte was prepared by mixing stannous chloride dihydrate, potassium hydrogen phosphate trihydrate, and deionized water in a mass ratio of 15:120:1000, with a flow rate of 3 mA / cm 2 , electroplated at 30 ° C for 10 minutes, washed with deionized water 5 times, dried at 50 ° C for 8 hours, drawn at 440 ° C to a diameter of 0.2 mm, annealed at 450 ° C for 1 hour, and cooled to room temperature at 6~8 ° C / s to obtain copper wire.
[0027] Example 6 (1) Copper, magnesium, chromium and titanium were mixed in a mass ratio of 100:14:14:15, melted until liquid, cast into an ingot, forged at 350°C for 12 minutes, then kept at 620°C for 30 minutes, and cooled to room temperature to obtain a copper bar; the copper bar was drawn at 500°C for 25 minutes, kept at this temperature for 40 minutes, annealed at 430°C for 1 hour, and cooled to room temperature at 6°C / s to obtain a pretreated copper wire; (2) The pretreated copper wire was washed twice with anhydrous ethanol, immersed in deionized water twice the mass of the pretreated copper wire, ultrasonically cleaned at 600W for 10 minutes, taken out, immersed in 4.2% hydrochloric acid twice the mass of the pretreated copper wire, and ultrasonically cleaned for 15 minutes. Then, the pretreated copper wire was washed six times with deionized water and alcohol in sequence. The pretreated copper wire was used as the working electrode, the saturated calomel electrode was used as the reference electrode, the platinum sheet was used as the counter electrode, and the electrolyte was aluminum nickel cerium electrolyte. The preparation method of aluminum nickel cerium electrolyte was as follows: aluminum nitrate hexahydrate, nickel nitrate hexahydrate, cerium nitrate hexahydrate, potassium acetate, and high-purity water were mixed in a mass ratio of 1:0.8:0.5:2.8:293, stirred at 100rpm for 1 hour, electroplated at -1.0V for 500s, reacted at 3MPa pressure and 80℃ for 2 hours, and then reacted at 5MPa and 160℃ for 6 hours to obtain the copper wire raw material; (3) The copper wire material was used as the working electrode, the graphite plate was used as the counter electrode, and the electrolyte was a tin electrolyte. The tin electrolyte was prepared by mixing stannous chloride dihydrate, potassium hydrogen phosphate trihydrate, and deionized water in a mass ratio of 15:120:1000, with a flow rate of 4 mA / cm 2 , electroplated at 30°C for 10 min, washed with deionized water 5 times, dried at 50°C for 8 h, drawn at 500°C to a diameter of 0.2 mm, annealed at 440°C for 1 h, and cooled to room temperature at 7°C / s to obtain a copper wire.
[0028] Comparative Example 1 The difference between Comparative Example 1 and Example 2 lies in step (1), which is modified as follows: copper, magnesium, chromium, and titanium are mixed in a mass ratio of 100:12:12:12, melted until liquid, cast to obtain an ingot, forged at 325°C for 13 minutes, then kept at 600°C for 38 minutes, and cooled to room temperature to obtain a pretreated copper wire. The remaining steps are the same as those in Example 2.
[0029] Comparative Example 2 The difference between Comparative Example 2 and Example 2 is that there is no step (2), and step (3) is changed to: using the pretreated copper wire as the working electrode and the graphite plate as the counter electrode, 3mA / cm 2The copper wire was then electrodeposited at 30°C for 10 minutes, washed five times with deionized water, dried at 50°C for 8 hours, and then drawn at 450°C to a diameter of 0.2 mm. The wire was annealed at 440°C for 1 hour and cooled to room temperature at a rate of 7°C / s to obtain a copper wire. The electrolyte used in the electrodeposition was a tin electrolyte prepared by mixing stannous chloride dihydrate, potassium hydrogen phosphate trihydrate, and deionized water in a mass ratio of 15:120:1000. The remaining steps were the same as in Example 2.
[0030] Comparative Example 3 The difference between Comparative Example 3 and Example 2 is that step (3) is omitted, and the remaining steps are the same as those in Example 2.
[0031] Effect Examples Table 1 below shows the performance analysis results of the high-strength tinned copper wires of Examples 1 to 6 of the present invention and Comparative Examples 1 to 3.
[0032] Table 1 The present invention successfully constructs a copper-based conductor with a gradient composite structure through the synergistic effects of a secondary stretching annealing process, a secondary deposition process, and a pressurized heat treatment. This structure and its preparation process significantly improve the comprehensive performance of copper wire in the harsh environment of new energy applications. By optimizing the composition of the copper bar alloy (copper, magnesium, chromium, and titanium) and conducting a secondary stretching annealing process, the present invention achieves grain refinement and optimized atomic arrangement, significantly improving the mechanical strength of the copper wire. The present invention performs a first deposition process, using nickel nitrate, aluminum nitrate, and cerium nitrate as raw materials, which are electrodeposited on the surface of the copper bar. After pressurized heat treatment, a strong metallurgical bond is formed with the substrate, forming a dense, high-temperature antioxidant barrier that effectively resists high-temperature oxidation and corrosive media erosion within new energy equipment. A second deposition process, electroplating tin onto the intermediate layer, not only fills the surface micropores, improving surface density and smoothness, but more importantly, forms an excellent corrosion-resistant layer. Its layered structure design greatly enhances the bonding strength with the core copper layer and the outer protective layer, effectively isolating it from the penetration of corrosive media.
[0033] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be encompassed therein. Any reference in a claim should not be construed as limiting the claim to which it relates.
Claims
1. An antioxidant-strengthened gradient composite structure copper wire for new energy, the copper wire being produced through secondary stretching annealing, secondary deposition, and pressurized heat treatment; The first deposition treatment is to use aluminum nitrate hexahydrate, nickel nitrate hexahydrate, cerium nitrate hexahydrate, potassium acetate, and high-purity water as electrolytes, and electroplating the copper wire raw material for a period of time, and then pressurizing and heat treating the copper wire raw material; the second deposition treatment is to use stannous chloride dihydrate, potassium hydrogen phosphate trihydrate, and deionized water as electrolytes, and electroplating the copper wire raw material.
2. A method for preparing an antioxidant-strengthened gradient composite structure copper wire for new energy, characterized in that: The method comprises the following preparation steps: (1) After drawing the copper strip for 15-25 minutes, keeping it warm for 30-40 minutes, annealing it for 1 hour, and cooling it to room temperature to obtain the pretreated copper wire; (2) The pretreated copper wire was washed twice with anhydrous ethanol, immersed in deionized water 2 to 3 times the mass of the pretreated copper wire, ultrasonically cleaned at 600W for 8 to 12 minutes, taken out, immersed in hydrochloric acid 2 to 3 times the mass of the pretreated copper wire, and ultrasonically cleaned for 15 minutes. Then, the pretreated copper wire was washed 6 times with deionized water and alcohol in sequence. The pretreated copper wire was used as the working electrode, the saturated calomel electrode was used as the reference electrode, and the platinum sheet was used as the counter electrode. After electroplating at -1.0V for 500 to 700s, the copper wire was reacted at 3 to 5MPa pressure and 80℃ for 2 to 4h, and then reacted at 5 to 10MPa and 160℃ for 6h to obtain the copper wire raw material. (3) Use copper wire as working electrode and graphite plate as counter electrode, 1~4mA / cm 2 , electroplated at 30°C for 10 min, washed with deionized water 5 times, dried at 50°C for 8 h, drawn at 400~500°C to a diameter of 0.1~0.3 mm, annealed at 430~450°C for 1 h, and cooled to room temperature at 6~8°C / s to obtain copper wire.
3. The method for preparing an antioxidant-strengthened gradient composite structure copper wire for new energy according to claim 2, characterized in that: The copper bar preparation method in step (1) is as follows: copper, magnesium, chromium and titanium are mixed in a mass ratio of 100:10:10:10 to 100:15:15:15, melted until liquid, cast to obtain an ingot, forged at 300-350° C. for 10-15 minutes, then kept at 580-620° C. for 30-45 minutes, and cooled to room temperature.
4. The method for preparing an antioxidant-strengthened gradient composite structure copper wire for new energy according to claim 2, characterized in that: In step (1), the drawing temperature is controlled at 400-500°C.
5. The method for preparing an antioxidant-strengthened gradient composite structure copper wire for new energy according to claim 2, characterized in that: In step (1), the annealing temperature is controlled at 430-450°C.
6. The method for preparing an antioxidant-strengthened gradient composite structure copper wire for new energy according to claim 2, characterized in that: In step (1), the cooling temperature is controlled at 6~8℃ / s.
7. The method for preparing an antioxidant-strengthened gradient composite structure copper wire for new energy according to claim 2, characterized in that: The mass fraction of hydrochloric acid in step (2) is 4.2%.
8. The method for preparing an antioxidant-strengthened gradient composite structure copper wire for new energy use according to claim 2, characterized in that: The electrolyte used for the electrodeposition in step (2) is an aluminum-nickel-cerium electrolyte. The aluminum-nickel-cerium electrolyte is prepared by mixing aluminum nitrate hexahydrate, nickel nitrate hexahydrate, cerium nitrate hexahydrate, potassium acetate, and high-purity water in a mass ratio of 1:0.8:0.5:2.8:293, and stirring at 100-150 rpm for 1 hour.
9. The method for preparing an antioxidant-strengthened gradient composite structure copper wire for new energy according to claim 2, characterized in that: The electrolyte used for the electrodeposition in step (3) is a tin electrolyte, and the tin electrolyte is prepared by mixing stannous chloride dihydrate, potassium hydrogen phosphate trihydrate, and deionized water in a mass ratio of 15:120:1000.