A method for preparing a super copper / carbon nanotube composite

Abstract

A kind of preparation method of super copper / carbon nanotube composite material, by the treatment of strong oxidant potassium permanganate and hydrogen peroxide, carbon nanotube is oxidized and peeled off, and high-dispersity oxidized and peeled off carbon nanotube aqueous solution is obtained, copper, the precursor of oxidized and peeled off carbon nanotube composite material is co-deposited using pulse electrodeposition method, and super copper / carbon nanotube composite material is obtained by annealing-rolling-annealing treatment.Oxidized and peeled off carbon nanotube is inserted in copper matrix, and uniform distribution is realized.In addition, pulse electrodeposition process and annealing treatment can effectively reduce the oxygen content of composite material and optimize material structure.Therefore, the super copper / carbon nanotube composite material of the present application is superior to the characteristics of pure copper in electricity, heat and mechanics, and the preparation method is simple and easy to operate, and has good and wide application prospect in the field of electronic power, energy and other related fields.

Description

A method for preparing a super copper / carbon nanotube composite material Technical Field

[0001] This invention relates to a method for preparing a super copper / carbon nanotube composite material. Background Technology

[0002] Copper, with its excellent electrical conductivity and processing properties, is currently the most widely used conductive material. With the rapid development of modern industrial technology, the application of copper in key national development areas such as advanced rail transportation, new energy, agricultural machinery, and power equipment has placed higher demands on its performance. For example, cables used in aerospace need to be lightweight while maintaining constant conductivity, and the windings in the motors of new energy electric vehicles require conductors to maintain low resistivity at high temperatures, necessitating higher conductivity from copper. However, limited by fundamental material properties, the conductivity of copper has only increased by 3% over the past century. Novel carbon nanomaterials, due to their unique properties—low density and excellent mechanical and electrical properties—are often used as reinforcing phases in metal matrix composites to reduce composite density and improve overall performance. Carbon nanotubes are hollow cylindrical nanostructures, seamless cylinders formed by rolling a single layer of atomically thick graphene at specific and discrete angles. Conduction in carbon nanotubes is ballistic, with a large mean free path of electrons, resulting in extremely low resistance that is independent of length. This unique property of carbon nanotubes gives them the potential to significantly improve the performance of copper matrices.

[0003] Currently, common processes for preparing copper / carbon nanotube composites include powder metallurgy, spraying, and hot pressing sintering. However, the strengthening efficiency of the reinforcement in composites prepared using these methods falls significantly short of theoretical values. This is because the nanowire structure and chemical inertness of carbon nanotubes make them prone to aggregation. Furthermore, the poor wettability of carbon nanotubes with the copper matrix makes it difficult for them to disperse uniformly within the matrix, hindering the formation of a strong interfacial bond and resulting in low strengthening efficiency—far below theoretical predictions. Therefore, new research approaches and preparation methods are needed to achieve the fabrication of super copper / carbon nanotube composites. Summary of the Invention

[0004] To address the aforementioned issues, this invention employs oxidized and exfoliated carbon nanotubes as reinforcement. A pulsed electrodeposition method is used to achieve uniform dispersion of carbon nanotubes in a copper matrix, while effectively removing oxygen-containing functional groups from the surface to maintain the structural integrity of the carbon nanotubes. Through heat treatment, rolling, and reheat treatment processes, a super copper / carbon nanotube composite material with excellent comprehensive performance is obtained.

[0005] The present invention adopts the following technical solution:

[0006] 1. A method for preparing a super copper / carbon nanotube composite material, the specific steps of which are as follows:

[0007] (1) Preparation of oxidatively exfoliated carbon nanotube dispersion:

[0008] After adding carbon nanotubes to a mixed acid and stirring until homogeneous, potassium permanganate was added to the mixed acid in batches and stirring continued to obtain a suspension. The suspension was heated at 65-80℃ for 1-10 hours and cooled to room temperature. An ice-water mixture containing hydrogen peroxide was then poured into the suspension. Subsequently, the acid was removed by centrifugation, and the mixture was washed with hydrochloric acid to remove impurities. Finally, the complex was dispersed in deionized water and dialyzed to thoroughly purify it until the pH was neutral, resulting in an oxidized exfoliated carbon nanotube dispersion.

[0009] (2) Preparation of precursors for super copper / carbon nanotube composite materials by pulsed electrochemical deposition:

[0010] A surface-polished Ti plate was selected as the working electrode, a Cu plate as the counter electrode, and a copper sulfate solution with a pH of 1-2 as the electroplating solution. A copper substrate was prepared by pulse electrodeposition at room temperature. Subsequently, an oxide-exfoliated carbon nanotube dispersion was added to the electroplating solution to form a mixed copper sulfate electroplating solution. The electroplating solution was then ultrasonically and magnetically stirred to ensure uniform dispersion of the oxide-exfoliated carbon nanotubes in the solution. Then, using the Ti plate containing the copper substrate as the working electrode, a copper / carbon nanotube composite precursor was prepared by pulse electrodeposition. During the pulse electrodeposition process, the electroplating solution containing the oxide-exfoliated carbon nanotubes needed to be replaced multiple times.

[0011] (3) Processing and annealing of oxide-exfoliated carbon nanotube-reinforced copper-based composite materials:

[0012] The composite precursor obtained in step (2) is placed in an inert protective gas and subjected to a first annealing treatment at 300℃~500℃ (e.g., 300℃, 310℃, 320℃, 330℃, 340℃, 350℃, 360℃, 370℃, 380℃, 390℃, 400℃, 410℃, 420℃, 430℃, 440℃, 450℃, 460℃, 470℃, 480℃, 490℃ or 500℃). After cooling to room temperature, the composite material is rolled, and then a second annealing treatment is performed according to the different rolling amounts to obtain the super copper / carbon nanotube composite material.

[0013] Specifically, this invention provides a method for preparing a super copper / carbon nanotube composite material, the specific steps of which are as follows:

[0014] (1) Preparation of oxidatively exfoliated carbon nanotube dispersion:

[0015] Carbon nanotubes were added to a mixture of concentrated sulfuric acid and phosphoric acid, and stirred until homogeneous. Potassium permanganate was then slowly added to the mixture in batches, and stirring was continued for 30 minutes to obtain a suspension. The suspension was heated at 65-80℃ for 1-10 hours and cooled to room temperature. An ice-water mixture containing hydrogen peroxide was then poured into the suspension. Subsequently, inorganic acids were removed by centrifugation, and the mixture was washed with 5% dilute hydrochloric acid to remove impurities. Finally, the complex was dispersed in deionized water and dialyzed to thoroughly purify it until the pH was neutral, yielding an oxidized exfoliated carbon nanotube dispersion with a concentration of 0.5-2 mg / mL.

[0016] (2) Preparation of precursors for super copper / carbon nanotube composite materials by pulsed electrochemical deposition:

[0017] A Ti plate with a polished surface was selected as the working electrode, a Cu plate of the same size was selected as the counter electrode, and a 1 mol / L copper sulfate solution with a pH of 1-2 was selected as the electroplating solution. A copper substrate was prepared by pulse electrodeposition at room temperature for 10 minutes. Then, an oxide-exfoliated carbon nanotube dispersion was added to the electroplating solution, and the electroplating solution was ultrasonically and magnetically stirred to ensure that the oxide-exfoliated carbon nanotubes were uniformly dispersed in the solution. Subsequently, a copper / carbon nanotube composite precursor was prepared by pulse electrodeposition using the copper substrate as the working electrode.

[0018] (3) Processing and annealing of oxide-exfoliated carbon nanotube-reinforced copper-based composite materials:

[0019] The composite precursor obtained in step (2) was placed in an inert protective gas and annealed at 450°C for 1 hour. After cooling to room temperature, the surface of the composite material was polished and then rolled. The appropriate annealing temperature was selected according to the rolling amount to obtain the super copper / carbon nanotube composite material.

[0020] In this invention, concentrated sulfuric acid is an aqueous solution of sulfuric acid with a mass fraction greater than or equal to 70%.

[0021] In step (1), the mixed acid is composed of concentrated sulfuric acid and phosphoric acid.

[0022] In step (1), the carbon nanotubes are added to concentrated sulfuric acid at a mass-to-volume ratio of 1:100 to 500 g / mL (for example, carbon nanotubes are added to concentrated sulfuric acid at mass-to-volume ratios of 1:100, 1:120, 1:140, 1:160, 1:180, 1:200, 1:220, 1:240, 1:260, 1:300, 1:350, 1:400, 1:450, 1:499, or 1:500 g / mL). Potassium permanganate is added at a mass-to-volume ratio of 1:100 g / mL to 1:500 g / mL to concentrate. The carbon nanotubes are added at a mass ratio of 1:2 to 10 (for example, the mass ratio of carbon nanotubes to potassium permanganate is 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, or 1:10). Concentrated phosphoric acid is added at a volume ratio of concentrated sulfuric acid to phosphoric acid of 1:0.1 to 0.2. Hydrogen peroxide is added at a mass-volume ratio of carbon nanotubes to hydrogen peroxide of 1:2 to 10 g / mL.

[0023] The oxidized and exfoliated carbon nanotube dispersion described in step (1) is composed of one or more of graphene oxide nanoribbons, semi-exfoliated carbon nanotubes, and surface-oxidized carbon nanotubes.

[0024] The area of ​​the working electrode mentioned in step (2) is 20-100 cm². 2 For example, the area of ​​the working electrode is 20 cm². 2 25cm 2 30cm 2 35cm 2 40cm 2 45cm 2 50cm 2 55cm 2 60cm 2 65cm 2 70cm 2 75cm 2 80cm 2 85cm 2 9095cm 2 Or 100cm 2 .

[0025] In step (2), the concentration of oxidized stripped carbon nanotubes in the mixed copper sulfate electroplating solution is 4 mg / mL, 6 mg / mL, 8 mg / mL, 10 mg / mL, 12 mg / mL, 14 mg / mL, 16 mg / mL, 18 mg / mL, 20 mg / mL, 22 mg / mL, 24 mg / mL, 26 mg / mL, 28 mg / mL, 30 mg / mL, 32 mg / mL, 34 mg / mL, 36 mg / mL, 38 mg / mL, 40 mg / mL, 42 mg / mL, 44 mg / mL, 46 mg / mL, 48 mg / mL, 50 mg / mL, 52 mg / mL, 54 mg / mL, or 55 mg / mL.

[0026] In step (2), the parameters for pulse electrodeposition include a forward current density of 50–500 mA / cm². 2 (For example, a forward current density of 50 mA / cm²) 2 60mA / cm 2 70mA / cm 2 80mA / cm 2 90mA / cm 2 100mA / cm 2 110mA / cm 2 120mA / cm 2 130mA / cm 2 140mA / cm 2 150mA / cm 2 160mA / cm 2 170mA / cm 2 180mA / cm 2 190mA / cm 2 200mA / cm 2 210mA / cm 2 220mA / cm 2 230mA / cm 2 240mA / cm 2 250mA / cm 2 260mA / cm 2 270mA / cm 2 280mA / cm 2 290mA / cm 2 300mA / cm 2 310mA / cm 2 320mA / cm 2 330mA / cm 2 340mA / cm 2 350mA / cm2 360mA / cm 2 370mA / cm 2 380mA / cm 2 390mA / cm 2 400mA / cm 2 410mA / cm 2 420mA / cm 2 430mA / cm 2 440mA / cm 2 450mA / cm 2 460mA / cm 2 470mA / cm 2 480mA / cm 2 490mA / cm 2 Or 500mA / cm 2 ), pulse width 1000~5000μs (pulse width is 1000μs, 1100μs, 1200μs, 1300μs, 1400μs, 1500μs, 1600μs, 1700μs, 1800μs, 1900μs, 2000μs, 2100μs, 2300μs, 2500 μs, 2700μs, 2900μs, 3100μs, 3300μs, 3500μs, 3700μs, 3900μs, 4100μs, 4300μs, 4500μs, 4700μs, 4900μs or 5000μs), reverse current density -0.1~-20mA / cm 2 (Reverse current density is -0.1 mA / cm) 2 -0.3mA / cm 2 -0.5mA / cm 2 -0.7mA / cm 2 -0.9mA / cm 2 -1mA / cm 2 -3mA / cm 2 -5mA / cm 2 -7mA / cm 2 -9mA / cm 2 -11mA / cm 2 -13mA / cm 2 -15mA / cm 2 -17mA / cm 2 -19mA / cm 2 or -20mA / cm 2), pulse width 0.1~2000μs (pulse width is 0.1μs, 1μs, 5μs, 10μs, 20μs, 30μs, 40μs, 50μs, 60μs, 70μs, 80μs, 90μs, 100μs, 200μs 1 600μs, 1700μs, 1800μs, 1900μs or 2000μs), duty cycle 5-20% (duty cycle 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%), deposition time 5-18h (deposition time 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h or 18h).

[0027] In step (2), the electroplating solution containing oxidized carbon nanotubes is updated once every 0.5-2 hours during the pulse electrodeposition process.

[0028] In step (3), the rolling weight of the oxide-exfoliated carbon nanotube reinforced copper matrix composite material is 15%-80%. For example, the rolling weight of the oxide-exfoliated carbon nanotube reinforced copper matrix composite material is 15%, 16%, 17%, 18%, 19%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, or 80%.

[0029] In step (3), the secondary annealing temperature of the oxide-exfoliated carbon nanotube reinforced copper matrix composite material is 400℃-800℃. For example, the secondary annealing temperature of the oxide-exfoliated carbon nanotube reinforced copper matrix composite material is 400℃, 410℃, 420℃, 430℃, 440℃, 450℃, 460℃, 470℃, 480℃, 490℃, 500℃, 510℃, 520℃, 530℃, 540℃, 560℃, 580℃, 600℃, 620℃, 640℃, 660℃, 680℃, 700℃, 720℃, 740℃, 760℃, 780℃, or 800℃.

[0030] The super copper / carbon nanotube composite material exhibits exceptional properties, with electrical conductivity reaching 100%-120% (e.g., 100%, 105%, 110%, 115%, or 120%), meeting the International Association of Advanced Materials for Annealed Copper (IACS). At a high temperature of 180°C, its electrical conductivity is 1%-20% higher than that of pure copper (e.g., increases of 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%). 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%); thermal conductivity 400-450 W / (m·K) (thermal conductivity 400 W / (m·K), 405 W / (m·K), 410 W / (m·K), 415 W / (m·K), 420 W / (m·K), 425 W / (m·K), 430 W / (m·K), 43 5W / (m·K), 440W / (m·K), 445W / (m·K) or 450W / (m·K), with tensile strength of 150-350MPa (tensile strengths of 150MPa, 155MPa, 160MPa, 165MPa, 170MPa, 175MPa, 180MPa, 185MPa, 190MPa, 200MPa, 210MPa, 220MPa). MPa, 230MPa, 240MPa, 250MPa, 260MPa, 270MPa, 280MPa, 290MPa, 300MPa, 310MPa, 320MPa, 330MPa, 340MPa or 350MPa), with an elongation of 10%-45% (elongation of 10%, 15%, 20%, 25%, 30%, 35%, 40% or 45%).

[0031] This invention utilizes an oxidation reaction to partially open the walls of carbon nanotubes, obtaining a composite containing graphene oxide nanoribbons, semi-exfoliated carbon nanotubes, and carbon oxide nanotubes. First, the exfoliated outer wall provides oxygen-containing functional groups, resulting in excellent dispersion in aqueous systems, while the unexfoliated inner wall provides the inherent properties of the carbon nanotubes. The fully exfoliated graphene oxide nanoribbons have a larger aspect ratio, providing sufficient length to withstand greater load transfer during load transfer. Oxidative exfoliation exposes the inner walls of the carbon nanotubes, effectively overcoming the limitation that only the outer structure of the carbon nanotube is functional. Furthermore, pulsed electrodeposition has a reducing effect on the carbon nanotube composite, effectively eliminating oxygen-containing functional groups in the copper matrix, ensuring structural integrity, and further facilitating electron transport.

[0032] The beneficial effects of this invention are:

[0033] This invention utilizes novel oxidized exfoliated carbon nanotubes as a reinforcement and employs a pulsed electrodeposition method in a liquid phase system. This not only ensures uniform dispersion of the carbon nanotubes within the matrix, effectively increasing the contact area with the copper matrix, but also maintains the integrity of the carbon nanotube structure. After annealing-rolling-annealing processing, the structure is optimized, resulting in a composite material with superior mechanical, electrical, and thermal properties compared to existing pure copper, exhibiting exceptional overall performance. Therefore, this preparation method is novel in design, features a more rational reinforcement structure, and is simple and easy to implement, making it an important method for obtaining copper-based composite materials with superior comprehensive performance. Attached Figure Description

[0034] Figure 1. Photograph of the carbon nanotube dispersion of an embodiment of the present invention;

[0035] Figure 2 is a scanning electron microscope image of the composite material in step (2) of Embodiment 1 of the present invention;

[0036] Figure 3 is a transmission electron microscope image of the composite material in step (2) of Embodiment 1 of the present invention;

[0037] Figure 4 shows the electrical conductivity, tensile strength, and thermal conductivity of the composite material in Example 1 of this invention. Detailed Implementation

[0038] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0039] In the following embodiments of the present invention, concentrated sulfuric acid (wt%: 95%) was used;

[0040] Carbon nanotubes (XFM34, 95% purity, 0.5-2 micrometers in length, 50 nm in diameter, multi-walled carbon nanotubes);

[0041] Hydrogen peroxide (30 wt%); dilute hydrochloric acid (5 wt%)

[0042] Example 1

[0043] 0.4 g of carbon nanotubes were added to a mixture of 100 mL of concentrated sulfuric acid and 12 mL of phosphoric acid, and stirred in an ice-water bath for 30 min. 1.6 g of potassium permanganate was then slowly added to the mixed acid in batches, and stirring was continued for another 30 min. The resulting suspension was heated at 70 °C for 2 h and cooled to room temperature. 80 mL of an ice-water mixture containing 4 mL of hydrogen peroxide (30 wt%) was poured into the suspension. Subsequently, inorganic acids were removed by centrifugation, and the mixture was washed with dilute hydrochloric acid to remove impurities. Finally, the complex was dispersed in deionized water and dialyzed to thoroughly purify it until the pH was neutral, resulting in an oxidized exfoliated carbon nanotube dispersion with a concentration of 1 mg / mL. The dispersion remained uniformly dispersed for several months (Figure 1).

[0044] Selected with a surface polishing treatment and an area of ​​20cm² 2A Ti plate was used as the working electrode, a Cu plate of the same size as the counter electrode, and a 1 mol / L copper sulfate solution with a pH of 1-2 was used as the electroplating solution. A copper substrate was prepared by pulse electrodeposition at room temperature for 10 minutes. The electrodeposition parameters were a forward current density of 200 mA / cm². 2 The pulse width is 4000μs, and the reverse current density is -20mA / cm². 2 A copper-plated Ti plate was obtained using a pulse width of 2000 μs and a duty cycle of 20%. Subsequently, an oxide-exfoliated carbon nanotube dispersion was added to the electroplating solution to form a mixed copper sulfate electroplating solution. The concentration of oxide-exfoliated carbon nanotubes in the mixed copper sulfate electroplating solution was 5 mg / L. The electroplating solution was then subjected to ultrasonic and magnetic stirring to ensure uniform dispersion of the oxide-exfoliated carbon nanotubes in the solution. Using the copper-plated Ti plate as the working electrode, a copper / carbon nanotube composite precursor was prepared by pulse electrodeposition with a forward current density of 200 mA / cm². 2 The pulse width is 4000μs, and the reverse current density is -20mA / cm². 2 The pulse width was 2000 μs and the duty cycle was 20%. The electroplating solution containing the oxidized exfoliated carbon nanotube dispersion was replaced every 1 hour (the composition of the new electroplating solution was the same as that of the mixed copper sulfate electroplating solution). After a total deposition of 13 hours, the precursor of the super copper / carbon nanotube composite material was obtained. SEM and TEM showed that the oxidized exfoliated carbon nanotubes were uniformly interspersed in the copper matrix (Figures 2 and 3).

[0045] The precursor of the super copper / carbon nanotube composite material was placed in an Ar protective gas, heated to 450°C, and held at that temperature for 1 hour for annealing. After cooling to room temperature, it was rolled with a rolling amount of 38%, and then annealed at 400°C for 1 hour to obtain a super copper / carbon nanotube composite material with a uniform and dense structure. The composite material is denoted as Cu-GCNT.

[0046] The electrical conductivity of the composite material was measured using a Keithley voltmeter via the voltmeter-ammeter method, and was 105% IACS. At a high temperature of 180°C, the conductivity was 8% higher than that of pure copper. The thermal conductivity of the composite conductor was tested using the flash method, and the thermal diffusivity was 109.93 mm². 2 Its specific heat capacity is 0.425 J / (g·K), and its density is 8.89 g / cm³. 3 According to the formula K=ραCp, the thermal conductivity of the composite material is 415W / (m·K); the tensile strength is 251MPa and the elongation is 40% (Figure 4).

[0047] Example 2

[0048] 0.8 g of carbon nanotubes were added to a mixture of 80 mL concentrated sulfuric acid and 8 mL phosphoric acid, and stirred in an ice-water bath for 30 min. 1.6 g of potassium permanganate was then slowly added to the mixed acid in batches, and stirring was continued for another 30 min. The resulting suspension was heated at 65 °C for 2 h, cooled to room temperature, and 80 mL of an ice-water mixture containing 4 mL of hydrogen peroxide was poured into the suspension. Subsequently, inorganic acids were removed by centrifugation, and the mixture was washed with 5 wt% dilute hydrochloric acid to remove impurities. Finally, the complex was dispersed in deionized water and dialyzed to thoroughly purify it until the pH was neutral, yielding an oxidized exfoliated carbon nanotube dispersion with a concentration of 2 mg / mL.

[0049] Selected with a surface polishing treatment and an area of ​​30cm² 2 A Ti plate was used as the working electrode, a Cu plate of the same size as the counter electrode, and a 1 mol / L copper sulfate solution with a pH of 1-2 was used as the electroplating solution. A copper substrate was prepared by pulse electrodeposition at room temperature for 10 minutes. The electrodeposition parameters were a forward current density of 100 mA / cm². 2 The pulse width is 5000μs, and the reverse current density is -10mA / cm. 2 A Ti plate with copper plating was obtained by using a pulse width of 2000 μs and a duty cycle of 15%. Subsequently, an oxide-exfoliated carbon nanotube dispersion was added to the electroplating solution to form a mixed copper sulfate electroplating solution. The concentration of oxide-exfoliated carbon nanotubes in the mixed copper sulfate electroplating solution was [missing information].

[0050] The electroplating solution was prepared at a concentration of 15 mg / L, and ultrasonic and magnetic stirring were used to uniformly disperse the oxidized and exfoliated carbon nanotubes in the solution. A copper-plated Ti plate was then used as the working electrode for pulse electrodeposition to prepare a copper / carbon nanotube composite precursor. The electrodeposition parameters were a forward current density of 200 mA / cm². 2 The pulse width is 4000μs, and the reverse current density is -20mA / cm². 2 The pulse width was 2000 μs and the duty cycle was 20%. The electroplating solution containing the oxidized exfoliated carbon nanotube dispersion was replaced every 2 hours (the composition of the new electroplating solution was the same as that of the mixed copper sulfate electroplating solution). The super copper / carbon nanotube composite precursor was obtained after a total deposition time of 10 hours.

[0051] The precursor of the super copper / carbon nanotube composite material was placed in Ar protective gas, heated to 450℃, and held at that temperature for 1 hour for annealing. After cooling to room temperature, it was rolled with a rolling amount of 38%, and then annealed at 400℃ for 1 hour to obtain a super copper / carbon nanotube composite material with a uniform and dense structure.

[0052] The electrical conductivity of the composite material was measured using a Keithley power supply voltmeter by the voltmeter-ammeter method. The conductivity was 100% IACS. At a high temperature of 180°C, the conductivity was 1% higher than that of pure copper. The thermal conductivity was 400 W / (m·K), the tensile strength was 325 MPa, and the elongation was 10%.

[0053] Example 3

[0054] 0.2 g of carbon nanotubes were added to a mixture of 100 mL of concentrated sulfuric acid and 20 mL of phosphoric acid, and stirred in an ice-water bath for 30 min. 1.0 g of potassium permanganate was then slowly added to the mixed acid in batches, and stirring was continued for another 30 min. The resulting suspension was heated at 80 °C for 1 h, cooled to room temperature, and 40 mL of an ice-water mixture containing 2 mL of hydrogen peroxide was poured into the suspension. Subsequently, inorganic acids were removed by centrifugation, and the mixture was washed with 5% dilute hydrochloric acid to remove impurities. Finally, the complex was dispersed in deionized water and dialyzed to thoroughly purify it until the pH was neutral, yielding an oxidized exfoliated carbon nanotube dispersion with a concentration of 0.5 mg / mL.

[0055] Selected with a surface polishing treatment and an area of ​​100cm² 2 A Ti plate was used as the working electrode, a Cu plate of the same size as the counter electrode, and a 1 mol / L copper sulfate solution with a pH of 1-2 was used as the electroplating solution. A copper substrate was prepared by pulse electrodeposition at room temperature for 10 minutes. The electrodeposition parameters were a forward current density of 500 mA / cm². 2 The pulse width is 1000 μs, and the reverse current density is -0.1 mA / cm². 2 A copper-plated Ti plate was obtained using a pulse width of 0.1 μs and a duty cycle of 5%. Subsequently, an oxide-exfoliated carbon nanotube dispersion was added to the electroplating solution to form a mixed copper sulfate electroplating solution. The concentration of oxide-exfoliated carbon nanotubes in the mixed copper sulfate electroplating solution was 10 mg / L. The electroplating solution was then subjected to ultrasonic and magnetic stirring to ensure uniform dispersion of the oxide-exfoliated carbon nanotubes in the solution. Using the copper-plated Ti plate as the working electrode, a copper / carbon nanotube composite precursor was prepared by pulse electrodeposition with a forward current density of 500 mA / cm². 2 The pulse width is 1000 μs, and the reverse current density is -0.1 mA / cm². 2 The pulse width was 0.1 μs and the duty cycle was 5%. The electroplating solution containing the oxidized exfoliated carbon nanotube dispersion was replaced every 0.5 h (the composition of the new electroplating solution was the same as that of the mixed copper sulfate electroplating solution). The super copper / carbon nanotube composite precursor was obtained after a total deposition time of 8 h.

[0056] The precursor of the super copper / carbon nanotube composite material was placed in Ar protective gas, heated to 450℃, and held at that temperature for 1 hour for annealing. After cooling to room temperature, it was rolled with a rolling amount of 60%, and then annealed at 600℃ for 1 hour to obtain a super copper / carbon nanotube composite material with a uniform and dense structure.

[0057] Measured using a Keithley voltmeter by the voltmeter-ammeter method, the electrical conductivity of the composite material is 110% IACS, and at a high temperature of 180°C, the electrical conductivity is 15% higher than that of pure copper; the thermal conductivity is 450 W / (m·K), the tensile strength is 200 MPa, and the elongation is 45%.

[0058] Example 4

[0059] 0.4 g of carbon nanotubes were added to a mixture of 100 mL concentrated sulfuric acid and 12 mL phosphoric acid, and stirred in an ice-water bath for 30 min. 1.6 g of potassium permanganate was then slowly added to the mixed acid in batches, and stirring was continued for another 30 min. The resulting suspension was heated at 70 °C for 10 h and cooled to room temperature. 80 mL of an ice-water mixture containing 4 mL of hydrogen peroxide was poured into the suspension. Subsequently, inorganic acids were removed by centrifugation, and the mixture was washed with dilute hydrochloric acid to remove impurities. Finally, the complex was dispersed in deionized water and dialyzed to thoroughly purify it until the pH was neutral, yielding an oxidized exfoliated carbon nanotube dispersion with a concentration of 0.8 mg / mL.

[0060] Selected with a surface polishing treatment and an area of ​​80cm² 2 A Ti plate was used as the working electrode, a Cu plate of the same size as the counter electrode, and a 1 mol / L copper sulfate solution with a pH of 1-2 was used as the electroplating solution. A copper substrate was prepared by pulse electrodeposition at room temperature for 10 minutes. The electrodeposition parameters were a forward current density of 400 mA / cm². 2 The pulse width is 1000 μs, and the reverse current density is -0.1 mA / cm². 2 A copper-plated Ti plate was obtained using a pulse width of 0.1 μs and a duty cycle of 5%. Subsequently, a dispersion of 0.8 mg / mL oxidized exfoliated carbon nanotubes was added to the electroplating solution to form a mixed copper sulfate electroplating solution. The concentration of oxidized exfoliated carbon nanotubes in the mixed copper sulfate electroplating solution was 10 mg / L. The electroplating solution was then subjected to ultrasonic and magnetic stirring to ensure uniform dispersion of the oxidized exfoliated carbon nanotubes in the solution. Using the copper-plated Ti plate as the working electrode, a copper / carbon nanotube composite precursor was prepared by pulse electrodeposition with a forward current density of 300 mA / cm². 2 Pulse width 1000μs, reverse current density -10mA / cm 2 The pulse width was 1000 μs and the duty cycle was 10%. The electroplating solution containing the oxidized exfoliated carbon nanotube dispersion was replaced every 1 hour (the composition of the new electroplating solution was the same as that of the mixed copper sulfate electroplating solution). The super copper / carbon nanotube composite precursor was obtained after a total deposition time of 5 hours.

[0061] The precursor of the super copper / carbon nanotube composite material was placed in Ar protective gas, heated to 450℃, and held at that temperature for 1 hour for annealing. After cooling to room temperature, it was rolled with a rolling amount of 15%, and then annealed at 400℃ for 1 hour to obtain a super copper / carbon nanotube composite material with a uniform and dense structure.

[0062] Measured using a Keithley voltmeter by the voltmeter-ammeter method, the electrical conductivity of the composite material is 118% IACS, which is 20% higher than that of pure copper at a high temperature of 180°C; the thermal conductivity is 440 W / (m·K), the tensile strength is 250 MPa, and the elongation is 25%.

[0063] Example 5

[0064] 0.8 g of carbon nanotubes were added to a mixture of 200 mL concentrated sulfuric acid and 24 mL phosphoric acid, and stirred in an ice-water bath for 30 min. Then, 24 mL of phosphoric acid was added, and 3.2 g of potassium permanganate was slowly added to the mixed acid in batches while stirring for another 30 min. The resulting suspension was heated at 80 °C for 5 h and cooled to room temperature. 160 mL of an ice-water mixture containing 8 mL of hydrogen peroxide was poured into the suspension. Subsequently, inorganic acids were removed by centrifugation, and the mixture was washed with dilute hydrochloric acid to remove impurities. Finally, the complex was dispersed in deionized water and dialyzed to thoroughly purify it until the pH was neutral, resulting in an oxidized exfoliated carbon nanotube dispersion with a concentration of 1.5 mg / mL.

[0065] Selected with a surface polishing treatment and an area of ​​40cm² 2 A Ti plate was used as the working electrode, a Cu plate of the same size as the counter electrode, and a 1 mol / L copper sulfate solution with a pH of 1-2 was used as the electroplating solution. A copper substrate was prepared by pulse electrodeposition at room temperature for 10 minutes. The electrodeposition parameters were a forward current density of 200 mA / cm². 2 The pulse width is 4000μs, and the reverse current density is -20mA / cm². 2 A copper-plated Ti plate was obtained using a pulse width of 2000 μs and a duty cycle of 20%. Subsequently, a 1.5 mg / mL dispersion of oxidized exfoliated carbon nanotubes was added to the electroplating solution to form a mixed copper sulfate electroplating solution. The concentration of oxidized exfoliated carbon nanotubes in the mixed copper sulfate electroplating solution was 30 mg / L. The electroplating solution was then subjected to ultrasonic and magnetic stirring to ensure uniform dispersion of the oxidized exfoliated carbon nanotubes in the solution. Using the copper-plated Ti plate as the working electrode, a copper / carbon nanotube composite precursor was prepared by pulse electrodeposition with a forward current density of 200 mA / cm². 2 The pulse width is 4000μs, and the reverse current density is -20mA / cm². 2The pulse width was 2000 μs and the duty cycle was 20%. The electroplating solution containing the oxidized exfoliated carbon nanotube dispersion was replaced every 1.5 h (the composition of the new electroplating solution was the same as that of the mixed copper sulfate electroplating solution). The super copper / carbon nanotube composite precursor was obtained after a total deposition time of 9 h.

[0066] The precursor of the super copper / carbon nanotube composite material was placed in Ar protective gas, heated to 450℃, and held at that temperature for 1 hour for annealing. After cooling to room temperature, it was rolled with a rolling amount of 80%, and then annealed at 800℃ for 1 hour to obtain a super copper / carbon nanotube composite material with a uniform and dense structure.

[0067] The electrical conductivity of the composite material was measured using a Keithley voltmeter by the voltmeter-ammeter method. The conductivity was 108% IACS, and at a high temperature of 180°C, the conductivity was 8% higher than that of pure copper. The thermal conductivity was 413 W / (m·K), the tensile strength was 200 MPa, and the elongation was 30%.

[0068] Example 6

[0069] 0.4 g of carbon nanotubes were added to a mixture of 100 mL of concentrated sulfuric acid and 12 mL of phosphoric acid, and stirred in an ice-water bath for 30 min. 1.6 g of potassium permanganate was then slowly added to the mixed acid in batches, and stirring was continued for another 30 min. The resulting suspension was heated at 70 °C for 2 h and cooled to room temperature. 80 mL of an ice-water mixture containing 4 mL of hydrogen peroxide was poured into the suspension. Subsequently, inorganic acids were removed by centrifugation, and the mixture was washed with dilute hydrochloric acid to remove impurities. Finally, the complex was dispersed in deionized water and dialyzed to thoroughly purify it until the pH was neutral, yielding an oxidized exfoliated carbon nanotube dispersion with a concentration of 1 mg / mL.

[0070] Selected with a surface polishing treatment and an area of ​​30cm² 2 A Ti plate was used as the working electrode, a Cu plate of the same size as the counter electrode, and a 1 mol / L copper sulfate solution with a pH of 1-2 was used as the electroplating solution. A copper substrate was prepared by pulse electrodeposition at room temperature for 10 minutes. The electrodeposition parameters were a forward current density of 200 mA / cm². 2 The pulse width is 4000μs, and the reverse current density is -20mA / cm². 2 A copper-plated Ti plate was obtained using a pulse width of 2000 μs and a duty cycle of 20%. Subsequently, a 1 mg / mL dispersion of oxidized exfoliated carbon nanotubes was added to the electroplating solution to form a mixed copper sulfate electroplating solution. The concentration of oxidized exfoliated carbon nanotubes in the mixed copper sulfate electroplating solution was 25 mg / L. The electroplating solution was then subjected to ultrasonic and magnetic stirring to ensure uniform dispersion of the oxidized exfoliated carbon nanotubes in the solution. Using the copper-plated Ti plate as the working electrode, a copper / carbon nanotube composite precursor was prepared by pulse electrodeposition with a forward current density of 200 mA / cm². 2The pulse width is 4000μs, and the reverse current density is -20mA / cm². 2 The pulse width was 2000 μs and the duty cycle was 20%. The electroplating solution containing the oxidized exfoliated carbon nanotube dispersion was replaced every 1 hour (the composition of the new electroplating solution was the same as that of the mixed copper sulfate electroplating solution). The super copper / carbon nanotube composite precursor was obtained after a total deposition time of 13 hours.

[0071] The precursor of the super copper / carbon nanotube composite material was placed in Ar protective gas, heated to 450℃, and held at that temperature for 1 hour for annealing. After cooling to room temperature, it was rolled with a rolling amount of 15%, and then annealed at 400℃ for 1 hour to obtain a super copper / carbon nanotube composite material with a uniform and dense structure.

[0072] Measured using a Keithley voltmeter by the voltmeter-ammeter method, the electrical conductivity of the composite material is 120% IACS, and at a high temperature of 180°C, the electrical conductivity is 17% higher than that of pure copper; the thermal conductivity is 409 W / (m·K), the tensile strength is 300 MPa, and the elongation is 28%.

[0073] Example 7

[0074] 0.4 g of carbon nanotubes were added to a mixture of 100 mL concentrated sulfuric acid and 12 mL phosphoric acid, and stirred in an ice-water bath for 30 min. 1.6 g of potassium permanganate was then slowly added to the mixed acid in batches, and stirring was continued for another 30 min. The resulting suspension was heated at 70 °C for 2 h and cooled to room temperature. 80 mL of an ice-water mixture containing 8 mL of hydrogen peroxide was poured into the suspension. Subsequently, inorganic acids were removed by centrifugation, and the mixture was washed with dilute hydrochloric acid to remove impurities. Finally, the complex was dispersed in deionized water and dialyzed to thoroughly purify it until the pH was neutral, yielding an oxidized exfoliated carbon nanotube dispersion with a concentration of 0.9 mg / mL.

[0075] Selected with a surface polishing treatment and an area of ​​20cm² 2 A Ti plate was used as the working electrode, a Cu plate of the same size as the counter electrode, and a 1 mol / L copper sulfate solution with a pH of 1-2 was used as the electroplating solution. A copper substrate was prepared by pulse electrodeposition at room temperature for 10 minutes. The electrodeposition parameters were a forward current density of 200 mA / cm². 2 The pulse width is 4000μs, and the reverse current density is -20mA / cm². 2A copper-plated Ti plate was obtained using a pulse width of 2000 μs and a duty cycle of 20%. Subsequently, a 0.9 mg / mL dispersion of oxidized exfoliated carbon nanotubes was added to the electroplating solution to form a mixed copper sulfate electroplating solution. The concentration of oxidized exfoliated carbon nanotubes in the mixed copper sulfate electroplating solution was 50 mg / L. The electroplating solution was then subjected to ultrasonic and magnetic stirring to ensure uniform dispersion of the oxidized exfoliated carbon nanotubes in the solution. Using the copper-plated Ti plate as the working electrode, a copper / carbon nanotube composite precursor was prepared by pulse electrodeposition with a forward current density of 200 mA / cm². 2 The pulse width is 4000μs, and the reverse current density is -20mA / cm². 2 The pulse width was 2000 μs and the duty cycle was 20%. The electroplating solution containing the oxidized exfoliated carbon nanotube dispersion was replaced every 1 hour (the composition of the new electroplating solution was the same as that of the mixed copper sulfate electroplating solution). The super copper / carbon nanotube composite precursor was obtained after a total deposition time of 13 hours.

[0076] The precursor of the super copper / carbon nanotube composite material was placed in Ar protective gas, heated to 450℃, and held at that temperature for 1 hour for annealing. After cooling to room temperature, it was rolled with a rolling amount of 20%, and then annealed at 400℃ for 1 hour to obtain a super copper / carbon nanotube composite material with a uniform and dense structure.

[0077] The electrical conductivity of the composite material was measured using a Keithley voltmeter by the voltmeter-ammeter method. The conductivity was 115% IACS, and at a high temperature of 180°C, the conductivity was 10% higher than that of pure copper. The thermal conductivity was 405 W / (m·K), the tensile strength was 150 MPa, and the elongation was 45%.

[0078] Example 8

[0079] 0.4 g of carbon nanotubes were added to a mixture of 100 mL of concentrated sulfuric acid and 12 mL of phosphoric acid, and stirred in an ice-water bath for 30 min. 1.6 g of potassium permanganate was then slowly added to the mixed acid in batches, and stirring was continued for another 30 min. The resulting suspension was heated at 70 °C for 2 h and cooled to room temperature. 80 mL of an ice-water mixture containing 4 mL of hydrogen peroxide was poured into the suspension. Subsequently, inorganic acids were removed by centrifugation, and the mixture was washed with dilute hydrochloric acid to remove impurities. Finally, the complex was dispersed in deionized water and dialyzed to thoroughly purify it until the pH was neutral, yielding an oxidized exfoliated carbon nanotube dispersion with a concentration of 1 mg / mL.

[0080] Selected with a surface polishing treatment and an area of ​​20cm² 2 A Ti plate was used as the working electrode, a Cu plate of the same size as the counter electrode, and a 1 mol / L copper sulfate solution with a pH of 1-2 was used as the electroplating solution. A copper substrate was prepared by pulse electrodeposition at room temperature for 10 minutes. The electrodeposition parameters were a forward current density of 200 mA / cm². 2The pulse width is 4000μs, and the reverse current density is -20mA / cm². 2 A copper-plated Ti plate was obtained using a pulse width of 2000 μs and a duty cycle of 20%. Subsequently, a 1 mg / mL dispersion of oxidized exfoliated carbon nanotubes was added to the electroplating solution to form a mixed copper sulfate electroplating solution. The concentration of oxidized exfoliated carbon nanotubes in the mixed copper sulfate electroplating solution was 50 mg / L. The electroplating solution was then subjected to ultrasonic and magnetic stirring to ensure uniform dispersion of the oxidized exfoliated carbon nanotubes in the solution. Using the copper-plated Ti plate as the working electrode, a copper / carbon nanotube composite precursor was prepared by pulse electrodeposition with a forward current density of 200 mA / cm². 2 The pulse width is 4000μs, and the reverse current density is -20mA / cm². 2 The pulse width was 2000 μs and the duty cycle was 20%. The electroplating solution containing the oxidative stripping carbon nanotube dispersion was replaced every 0.5 h, and the super copper / carbon nanotube composite precursor was obtained after a total deposition time of 18 h.

[0081] The precursor of the super copper / carbon nanotube composite material was placed in Ar protective gas, heated to 450℃, and held at that temperature for 1 hour for annealing. After cooling to room temperature, it was rolled with a rolling amount of 25%, and then annealed at 400℃ for 1 hour to obtain a super copper / carbon nanotube composite material with a uniform and dense structure.

[0082] Measured using a Keithley voltmeter by the voltmeter-ammeter method, the electrical conductivity of the composite material is 117% IACS, which is 20% higher than that of pure copper at a high temperature of 180°C; the thermal conductivity is 450 W / (m·K), the tensile strength is 350 MPa, and the elongation is 12%.

[0083] Example 9

[0084] 0.4 g of carbon nanotubes were added to 100 mL of concentrated sulfuric acid and stirred in an ice-water bath for 30 min. Then, 12 mL of phosphoric acid was added, and 1.6 g of potassium permanganate was slowly added in batches to the mixed acid while stirring for another 30 min. The resulting suspension was heated at 70 °C for 2 h and cooled to room temperature. 80 mL of an ice-water mixture containing 4 mL of hydrogen peroxide was poured into the suspension. Subsequently, inorganic acids were removed by centrifugation, and the mixture was washed with dilute hydrochloric acid to remove impurities. Finally, the complex was dispersed in deionized water and dialyzed to thoroughly purify it until the pH was neutral, resulting in a 1 mg / mL oxygen-oxidized exfoliated carbon nanotube dispersion.

[0085] Selected with a surface polishing treatment and an area of ​​100cm² 2A Ti plate was used as the working electrode, a Cu plate of the same size as the counter electrode, and a 1 mol / L copper sulfate solution with a pH of 1-2 was used as the electroplating solution. A copper substrate was prepared by pulse electrodeposition at room temperature for 10 minutes. The electrodeposition parameters were a forward current density of 200 mA / cm². 2 The pulse width is 4000μs, and the reverse current density is -20mA / cm². 2 A copper-plated Ti plate was obtained using a pulse width of 2000 μs and a duty cycle of 20%. Subsequently, a 1 mg / mL dispersion of oxidized exfoliated carbon nanotubes was added to the electroplating solution to form a mixed copper sulfate electroplating solution. The concentration of oxidized exfoliated carbon nanotubes in the mixed copper sulfate electroplating solution was 30 mg / L. The electroplating solution was then subjected to ultrasonic and magnetic stirring to ensure uniform dispersion of the oxidized exfoliated carbon nanotubes in the solution. Using the copper-plated Ti plate as the working electrode, a copper / carbon nanotube composite precursor was prepared by pulse electrodeposition with a forward current density of 200 mA / cm². 2 The pulse width is 4000μs, and the reverse current density is -20mA / cm². 2 The pulse width was 2000 μs and the duty cycle was 20%. The electroplating solution containing the oxidative stripping carbon nanotube dispersion was replaced every 2 hours, and the super copper / carbon nanotube composite precursor was obtained after a total deposition time of 5 hours.

[0086] The precursor of the super copper / carbon nanotube composite material was placed in Ar protective gas, heated to 450℃, and held at that temperature for 1 hour for annealing. After cooling to room temperature, it was rolled with a rolling amount of 80%, and then annealed at 400℃ for 1 hour to obtain a super copper / carbon nanotube composite material with a uniform and dense structure.

[0087] The electrical conductivity of the composite material was measured using a Keithley voltmeter by the voltmeter-ammeter method. The conductivity was 100% IACS. At a high temperature of 180°C, the conductivity was 2% higher than that of pure copper. The thermal conductivity was 400 W / (m·K), the tensile strength was 350 MPa, and the elongation was 20%.

[0088] The parts of this invention not described in detail are well-known to those skilled in the art. The embodiments described above are merely preferred embodiments of the invention, and do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Various modifications and improvements to the technical solutions of this invention made by those skilled in the art without departing from the spirit of the invention should fall within the protection scope defined by the claims of this invention.

Claims

1. A method for preparing a super copper / carbon nanotube composite material, characterized in that, The specific steps are as follows: (1) Preparation of carbon nanotube dispersion by oxidative stripping: After adding carbon nanotubes to the mixed acid and stirring evenly, potassium permanganate is added to the mixed acid in batches and stirred continuously to obtain a suspension; the suspension is heated at 65-80 ℃ for 1-10 h, cooled to room temperature, and a mixture of ice and water containing hydrogen peroxide is poured into the suspension. Subsequently, the acid was removed by centrifugation, and then the impurities were removed by washing with hydrochloric acid. Finally, the composite was dispersed in deionized water and dialyzed to be thoroughly purified until the pH was neutral to obtain an oxidized exfoliated carbon nanotube dispersion. The mixed acid consisted of concentrated sulfuric acid and phosphoric acid. The mass-volume ratio of carbon nanotubes to concentrated sulfuric acid (g:mL) was 1:100~500, the mass ratio of carbon nanotubes to potassium permanganate was 1:2~5, the volume ratio of concentrated sulfuric acid to phosphoric acid was 1:0.1~0.2, and the mass-volume ratio of carbon nanotubes to hydrogen peroxide (g:mL) was 1:5-20. (2) Preparation of super copper / carbon nanotube composite material precursor by pulsed electrochemical deposition: a surface-polished Ti plate was selected as the working electrode. A Cu plate is used as the counter electrode, and a copper sulfate solution with a pH of 1-2 is used as the electroplating solution. A copper substrate is prepared by pulse electrodeposition at room temperature. Subsequently, an oxide-exfoliated carbon nanotube dispersion is added to the electroplating solution to form a mixed copper sulfate electroplating solution. The electroplating solution is then ultrasonically and magnetically stirred to ensure uniform dispersion of the oxide-exfoliated carbon nanotubes in the solution. A Ti plate containing the copper substrate is then used as the working electrode, and a copper / carbon nanotube composite precursor is prepared by pulse electrodeposition. The electroplating solution containing the oxide-exfoliated carbon nanotubes needs to be replenished multiple times during the pulse electrodeposition process. The pulse electrodeposition parameters for preparing the copper substrate at room temperature include a forward current density of 50-500 mA / cm², a pulse width of 1000-5000 μs, a reverse current density of -0.1 to -20 mA / cm², a pulse width of 0.1-2000 μs, a duty cycle of 5-20%, and a deposition time of 0.1-18 h. The concentration of oxide-exfoliated carbon nanotubes in the mixed copper sulfate electroplating solution is 4-55%. mg / mL; (3) Processing and annealing of oxidized stripped carbon nanotube reinforced copper composite material: The composite material precursor obtained in step (2) is placed in an inert protective gas and annealed at 300~500 °C for the first time. After cooling to room temperature, the composite material is rolled and then annealed again at a different rolling temperature to obtain super copper / carbon nanotube composite material.

2. The preparation method of the super copper / carbon nanotube composite material as described in claim 1, characterized in that, The mass-to-volume ratio of carbon nanotubes to concentrated sulfuric acid (g:mL) is 1:250, the mass-to-volume ratio of carbon nanotubes to potassium permanganate is 1:4, the volume-to-volume ratio of concentrated sulfuric acid to phosphoric acid is 1:0.12, and the mass-to-volume ratio of carbon nanotubes to hydrogen peroxide (g:mL) is 1:

10.

3. The preparation method of the super copper / carbon nanotube composite material as described in claim 1, characterized in that, In step (1), the oxidized exfoliated carbon nanotube dispersion is composed of one or more of the following: graphene oxide nanoribbons, semi-exfoliated carbon nanotubes, and surface-oxidized carbon nanotubes.

4. The method for preparing the super copper / carbon nanotube composite material as described in claim 1, characterized in that, The area of ​​the working electrode in step (2) is 20-100 cm². 2 .

5. The method for preparing the super copper / carbon nanotube composite material as described in claim 1, characterized in that, The parameters for pulse electrodeposition include a forward current density of 200 mA / cm². 2 Pulse width 4000 μs, reverse current density -20 mA / cm² 2 Pulse width 2000 μs, duty cycle 20%.

6. The method for preparing the super copper / carbon nanotube composite material as described in claim 1, characterized in that, In step (2), the electroplating solution containing oxidized exfoliated carbon nanotubes is updated every 0.5-2 h during the pulse electrodeposition process in the preparation of the copper / carbon nanotube composite precursor.

7. The preparation method of the super copper / carbon nanotube composite material as described in claim 1, characterized in that, The rolling amount of the super copper / carbon nanotube composite material in step (3) is 15%-80%.

8. The method for preparing the super copper / carbon nanotube composite material as described in claim 1, characterized in that, In step (3), the first annealing temperature of the super copper / carbon nanotube composite material is 400-800 ℃.

Images