CN111560535A - Preparation method of high-strength graphene/copper composite material - Google Patents
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Abstract
The invention provides a preparation method of a high-strength graphene/copper composite material. And then, carrying out copper plating on the graphene oxide/copper composite powder by using an electroless copper plating process to obtain copper-plated graphene oxide/copper composite powder. And secondly, heating and reducing the copper-plated graphene oxide/copper composite powder through a tubular furnace to obtain the copper-plated graphene/copper composite powder. And finally, putting the copper-plated graphene/copper composite powder into a discharge plasma sintering furnace for sintering to obtain the graphene/copper composite powder. The graphene/copper composite material prepared by the invention realizes the uniform dispersion of graphene in a copper matrix, the interface bonding property of graphene and copper is improved, and the mechanical property of the composite material is obviously improved.
Description
Technical Field
The invention relates to the technical field of composite material preparation, in particular to a preparation method of a high-strength graphene/copper composite material.
Background
Copper and copper alloy have been widely used in aerospace, energy and chemical industry, mechanical industry, national defense industry, electrical and electronic fields due to their advantages of good electrical and thermal conductivity, easy formability, etc. With the rapid development of modern science and technology, the traditional copper and copper alloy can not meet the requirements of practical application in comprehensive performance. By adding the second phase particles with high strength into the copper and copper alloy matrix, the copper and copper alloy matrix has more excellent comprehensive performance, and the application range of the copper and copper alloy can be effectively expanded.
Graphene is a compound represented by sp2The hybridized carbon atoms are closely arranged to form the honeycomb-shaped two-dimensional carbon material with the single atomic layer. The graphene has excellent electric conductivity and heat conductivity and ultrahigh strength, and is an ideal copper-based composite material reinforcement. The graphene is added into the copper matrix to play a role in stopping dislocation motion and transferring load, so that the mechanical property of the copper-based composite material is improved. However, due to the difference in density, graphene is difficult to be uniformly dispersed in a copper matrix, and the graphene and the copper matrix have poor wettability and poor interface bonding property, so that the graphene is difficult to fully exert the potential of serving as a reinforcement in a copper-based composite material.
Disclosure of Invention
The invention aims to provide a preparation method of a high-strength graphene/copper composite material, which effectively solves the problems that graphene is difficult to uniformly disperse in a copper matrix and the interface bonding force between the graphene and copper is poor.
In order to achieve the purpose, the invention provides a preparation method of a high-strength graphene/copper composite material, which comprises the following steps:
step 1: preparing a graphene oxide solution;
step 2: sensitizing the graphene oxide solution;
and step 3: activating the graphene oxide solution;
and 4, step 4: preparing flake copper powder;
and 5: uniformly adsorbing the graphene oxide graphene on the surface of the flake copper powder by using a static self-assembly process to prepare graphene oxide/copper composite powder;
step 6: placing the graphene oxide/copper composite powder in a plating solution for plating, and then drying to prepare copper-plated graphene oxide/copper composite powder;
and 7: reducing graphene oxide in the copper-plated graphene oxide/copper composite powder to obtain copper-plated graphene/copper composite powder;
and 8: and placing the copper-plated graphene/copper composite powder in a die for prepressing and forming, and then sintering and forming to obtain the graphene/copper composite material.
Further, in the step 1, 1g of flake graphite, 1g of sodium nitrate and 46mL of concentrated sulfuric acid are mixed into a beaker, and the mixture is magnetically stirred for 1 hour in an ice-water bath; slowly adding 6g of potassium permanganate, stirring for 1h, transferring to a constant-temperature water bath at 35 ℃, and magnetically stirring for 2 h; slowly adding 40mL of distilled water into a beaker, and magnetically stirring for 2 hours at the temperature of 90 ℃ under the water bath condition; taking out the beaker, adding a proper amount of distilled water, adding 6mL of 3 wt% hydrogen peroxide solution, uniformly stirring, standing for a period of time, and pouring out supernatant; and adding a dilute hydrochloric acid solution into the beaker, adding deionized water, and performing centrifugal washing until the solution is neutral to obtain a graphene oxide solution with negative charges.
Further, in step 2, adding the graphene oxide solution prepared in step 1 into a sensitizing solution, sensitizing for 30min, and centrifugally washing with deionized water to neutrality to obtain a sensitized graphene oxide solution; the sensitizing solution is a mixed solution containing 25g/L stannous chloride and 50mL/L hydrochloric acid.
Further, in the step 3, adding the sensitized graphene oxide solution prepared in the step 2 into an activation solution, activating for 30min, and centrifugally washing with deionized water to be neutral to obtain a sensitized and activated graphene oxide solution with the concentration of 1 mg/mL; the activating solution is a mixed solution containing 0.25g/L of palladium chloride and 10mL/L of hydrochloric acid.
Further, in the step 4, 200g of spherical copper powder is added into a ball milling tank, the particle size of the copper powder is 15-20 microns, the purity is more than 99.9%, a stainless steel ball is used as a grinding ball, the ball material ratio is 10:1, 500mL of absolute ethyl alcohol is added as a ball milling medium, 0.5g of stearic acid is added as a process control agent, the rotation speed is 300rpm, and the ball milling tank is put into a vacuum drying box for complete drying after 4 hours of ball milling to obtain the flake copper powder.
Further, in step 5, 20g of the flake copper powder prepared in step 4 is added into 5g/L of cetyl trimethyl ammonium bromide solution, and magnetic stirring is carried out for 1h, so as to obtain flake copper powder slurry with positive charges on the surface. And (3) slowly adding 20-40 mL of sensitized and activated graphene oxide solution prepared in the step (three) into the copper slurry, stirring for 15min, and adsorbing graphene oxide with negative charges on the surface of the flake copper powder with positive charges under the action of electrostatic force to obtain graphene oxide/copper composite powder.
Further, in step 6, transferring the graphene oxide/copper composite powder prepared in step 5 into a plating solution with a pH value of 12, adding 5mL of formaldehyde solution, plating for 15min, centrifugally washing with deionized water to be neutral, and drying in a vacuum drying oven to obtain copper-plated graphene oxide/copper composite powder; the plating solution is a mixed solution containing 15g/L of copper sulfate pentahydrate, 15g/L of disodium ethylene diamine tetraacetate and 14g/L of potassium sodium tartrate.
Further, in step 7, the copper-plated graphene oxide/copper composite powder prepared in step 6 is placed in a tube furnace, argon is introduced to serve as a protective atmosphere, the temperature is increased to 500 ℃, graphene oxide is reduced through heating, the temperature is kept for 2 hours, and then the temperature is reduced along with the furnace, so that the copper-plated graphene/copper composite powder is obtained.
Further, in step 8, adding the copper-plated graphene/copper composite powder prepared in step 7 into a graphite mold, pre-pressing and molding, placing into a discharge plasma sintering furnace, sintering and molding under vacuum conditions, wherein the temperature rise speed is 100 ℃/min, the sintering temperature is 600 ℃, the sintering pressure is 35MPa, and the temperature is kept for 5min and then is reduced along with the furnace to obtain the graphene/copper composite material.
Further, the content of graphene in the high-strength graphene/copper composite material is 0.1 wt% -0.3 wt%, and the balance is copper;
the tensile strength of the graphene/copper composite material is 230-280 MPa, the yield strength is 180-240 MPa, and the elongation is 32-24%.
Compared with the prior art, the invention has the advantages that: according to the preparation method of the high-strength graphene/copper composite material, graphene is uniformly adsorbed on the surface of the flake copper powder through a static self-assembly process, so that the problem that the graphene is difficult to uniformly disperse in a copper matrix is solved, meanwhile, copper plating treatment is performed on the graphene adsorbed on the flake copper powder, copper particles plated on the surface of the graphene are fused with surrounding composite powder in a sintering process, the phenomenon that the graphene is directly and mechanically combined with the surrounding powder is avoided, the interface bonding property of the graphene and the copper matrix is improved, the potential of the graphene as a copper-based composite material reinforcement is improved, and the tensile strength and the yield strength are obviously improved.
Drawings
Fig. 1 is an SEM image of the graphene oxide/copper composite powder obtained in example 2 of the present invention.
Fig. 2 is an SEM image of the copper-plated graphene oxide/copper composite powder obtained in example 2 of the present invention.
Fig. 3 is a TEM image of the graphene/copper composite obtained in example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be further described below.
Example 1
Firstly, preparing graphene oxide: dissolving graphene oxide dry powder in deionized water by utilizing ultrasonic dispersion to obtain a graphene oxide solution with negative charges;
1g of flake graphite, 1g of sodium nitrate and 46mL of concentrated sulfuric acid were mixed and magnetically stirred in an ice-water bath for 1 hour. Slowly adding 6g of potassium permanganate, stirring for 1h, transferring to a constant-temperature water bath at 35 ℃ and magnetically stirring for 2 h. 40mL of distilled water was slowly added to the beaker and magnetically stirred for 2h at 90 ℃ in a water bath. Taking out the beaker, adding a proper amount of distilled water, adding 6mL of 3 wt% hydrogen peroxide solution, stirring uniformly, standing for a period of time, and pouring out the supernatant. Adding a dilute hydrochloric acid solution into the beaker, adding deionized water, and performing centrifugal washing until the solution is neutral to obtain a graphene oxide solution with negative charges;
secondly, sensitizing graphene oxide: and (3) adding the graphene oxide solution prepared in the step one into a sensitizing solution, sensitizing for 30min, and centrifugally washing with deionized water to be neutral to obtain the sensitized graphene oxide solution. The sensitizing solution is a mixed solution containing 25g/L stannous chloride and 50mL/L hydrochloric acid;
thirdly, activating graphene oxide: and D, adding the sensitized graphene oxide solution prepared in the step two into an activation solution, activating for 30min, and centrifugally washing with deionized water to be neutral to obtain the sensitized and activated graphene oxide solution with the concentration of 1 mg/mL. The activating solution is a mixed solution containing 0.25g/L of palladium chloride and 10mL/L of hydrochloric acid;
fourthly, preparing the flake copper powder: adding 200g of spherical copper powder (the particle size is 15-20 microns, the purity is more than 99.9%) into a ball milling tank, adding 500mL of absolute ethyl alcohol as a ball milling medium into a ball milling ball with a ball material ratio of 10:1, adding 0.5g of stearic acid as a process control agent, rotating at 300rpm, and putting the ball milling tank into a vacuum drying oven for complete drying after 4 hours of ball milling to obtain flake copper powder;
fifthly, preparing the graphene oxide/copper composite powder: and adding 20g of the flake copper powder prepared in the fourth step into 5g/L of hexadecyl trimethyl ammonium bromide solution, and magnetically stirring for 1h to obtain flake copper powder slurry with positive charges on the surface. Slowly adding 20mL of sensitized and activated graphene oxide solution prepared in the step three into the copper slurry, stirring for 15min, and adsorbing graphene oxide with negative charges on the surface of flake copper powder with positive charges under the action of electrostatic force to obtain graphene oxide/copper composite powder;
sixthly, preparing copper-plated graphene oxide/copper composite powder: transferring the graphene oxide/copper composite powder prepared in the fifth step into a plating solution with the pH value of 12, adding 5mL of formaldehyde solution, plating for 15min, centrifugally washing with deionized water to be neutral, and drying in a vacuum drying oven to obtain the copper-plated graphene oxide/copper composite powder. The plating solution is a mixed solution containing 15g/L of copper sulfate pentahydrate, 15g/L of disodium ethylene diamine tetraacetate and 14g/L of potassium sodium tartrate;
seventhly, preparing copper-plated graphene/copper composite powder: putting the copper-plated graphene oxide/copper composite powder prepared in the sixth step into a tube furnace, introducing argon gas as protective atmosphere, heating to 500 ℃, reducing graphene oxide by heating, preserving heat for 2 hours, and cooling along with the furnace to obtain the copper-plated graphene oxide/copper composite powder;
eighthly, preparing the graphene/copper composite material: adding the copper-plated graphene/copper composite powder prepared in the seventh step into a graphite mold, placing the graphite mold into a discharge plasma sintering furnace for sintering and molding under a vacuum condition after pre-pressing and molding, wherein the temperature rise speed is 100 ℃/min, the sintering temperature is 600 ℃, the sintering pressure is 35MPa, and the temperature is kept for 5min and then is reduced along with the furnace to obtain a graphene/copper composite material;
tests show that: the tensile strength of the composite material is 250MPa, the yield strength is 200MPa, and the elongation is 32%.
Example 2
Firstly, preparing graphene oxide: dissolving graphene oxide dry powder in deionized water by utilizing ultrasonic dispersion to obtain a graphene oxide solution with negative charges;
1g of flake graphite, 1g of sodium nitrate and 46mL of concentrated sulfuric acid were mixed and magnetically stirred in an ice-water bath for 1 hour. Slowly adding 6g of potassium permanganate, stirring for 1h, transferring to a constant-temperature water bath at 35 ℃ and magnetically stirring for 2 h. 40mL of distilled water was slowly added to the beaker and magnetically stirred for 2h at 90 ℃ in a water bath. Taking out the beaker, adding a proper amount of distilled water, adding 6mL of 3 wt% hydrogen peroxide solution, stirring uniformly, standing for a period of time, and pouring out the supernatant. Adding a dilute hydrochloric acid solution into the beaker, adding deionized water, and performing centrifugal washing until the solution is neutral to obtain a graphene oxide solution with negative charges;
secondly, sensitizing graphene oxide: and (3) adding the graphene oxide solution prepared in the step one into a sensitizing solution, sensitizing for 30min, and centrifugally washing with deionized water to be neutral to obtain the sensitized graphene oxide solution. The sensitizing solution is a mixed solution containing 25g/L stannous chloride and 50mL/L hydrochloric acid;
thirdly, activating graphene oxide: and D, adding the sensitized graphene oxide solution prepared in the step two into an activation solution, activating for 30min, and centrifugally washing with deionized water to be neutral to obtain the sensitized and activated graphene oxide solution with the concentration of 1 mg/mL. The activating solution is a mixed solution containing 0.25g/L of palladium chloride and 10mL/L of hydrochloric acid;
fourthly, preparing the flake copper powder: adding 200g of spherical copper powder (the particle size is 15-20 microns, the purity is more than 99.9%) into a ball milling tank, adding 500mL of absolute ethyl alcohol as a ball milling medium into a ball milling ball with a ball material ratio of 10:1, adding 0.5g of stearic acid as a process control agent, rotating at 300rpm, and putting the ball milling tank into a vacuum drying oven for complete drying after 4 hours of ball milling to obtain flake copper powder;
fifthly, preparing the graphene oxide/copper composite powder: and adding 20g of the flake copper powder prepared in the fourth step into 5g/L of hexadecyl trimethyl ammonium bromide solution, and magnetically stirring for 1h to obtain flake copper powder slurry with positive charges on the surface. Slowly adding 30mL of sensitized and activated graphene oxide solution prepared in the third step into the copper slurry, stirring for 15min, and adsorbing graphene oxide with negative charges on the surface of flake copper powder with positive charges under the action of electrostatic force to obtain graphene oxide/copper composite powder;
sixthly, preparing copper-plated graphene oxide/copper composite powder: transferring the graphene oxide/copper composite powder prepared in the fifth step into a plating solution with the pH value of 12, adding 5mL of formaldehyde solution, plating for 15min, centrifugally washing with deionized water to be neutral, and drying in a vacuum drying oven to obtain the copper-plated graphene oxide/copper composite powder. The plating solution is a mixed solution containing 15g/L of copper sulfate pentahydrate, 15g/L of disodium ethylene diamine tetraacetate and 14g/L of potassium sodium tartrate;
seventhly, preparing copper-plated graphene/copper composite powder: putting the copper-plated graphene oxide/copper composite powder prepared in the sixth step into a tube furnace, introducing argon gas as protective atmosphere, heating to 500 ℃, reducing graphene oxide by heating, preserving heat for 2 hours, and cooling along with the furnace to obtain the copper-plated graphene oxide/copper composite powder;
eighthly, preparing the graphene/copper composite material: adding the copper-plated graphene/copper composite powder prepared in the seventh step into a graphite mold, placing the graphite mold into a discharge plasma sintering furnace for sintering and molding under a vacuum condition after pre-pressing and molding, wherein the temperature rise speed is 100 ℃/min, the sintering temperature is 600 ℃, the sintering pressure is 35MPa, and the temperature is kept for 5min and then is reduced along with the furnace to obtain a graphene/copper composite material;
tests show that: the tensile strength of the composite material is 280MPa, the yield strength is 240MPa, and the elongation is 28%.
Fig. 1 is an SEM photograph of the graphene oxide/copper composite powder prepared in step five, in which black spots are graphene oxide and are uniformly adsorbed on the surface of the flake copper powder.
Fig. 2 is an SEM photograph of the copper-plated graphene oxide/copper composite powder obtained in step six, and it can be seen from the drawing that graphene oxide adsorbed by the flake-shaped copper powder is uniformly plated with a layer of nano-copper particles.
Fig. 3 is a TEM photograph of the graphene/copper composite material obtained in step eight, in which the interface between graphene and copper is well bonded, and no gap is formed.
Example 3
Firstly, preparing graphene oxide: dissolving graphene oxide dry powder in deionized water by utilizing ultrasonic dispersion to obtain a graphene oxide solution with negative charges;
1g of flake graphite, 1g of sodium nitrate and 46mL of concentrated sulfuric acid were mixed and magnetically stirred in an ice-water bath for 1 hour. Slowly adding 6g of potassium permanganate, stirring for 1h, transferring to a constant-temperature water bath at 35 ℃ and magnetically stirring for 2 h. 40mL of distilled water was slowly added to the beaker and magnetically stirred for 2h at 90 ℃ in a water bath. Taking out the beaker, adding a proper amount of distilled water, adding 6mL of 3 wt% hydrogen peroxide solution, stirring uniformly, standing for a period of time, and pouring out the supernatant. Adding a dilute hydrochloric acid solution into the beaker, adding deionized water, and performing centrifugal washing until the solution is neutral to obtain a graphene oxide solution with negative charges;
secondly, sensitizing graphene oxide: and (3) adding the graphene oxide solution prepared in the step one into a sensitizing solution, sensitizing for 30min, and centrifugally washing with deionized water to be neutral to obtain the sensitized graphene oxide solution. The sensitizing solution is a mixed solution containing 25g/L stannous chloride and 50mL/L hydrochloric acid;
thirdly, activating graphene oxide: and D, adding the sensitized graphene oxide solution prepared in the step two into an activation solution, activating for 30min, and centrifugally washing with deionized water to be neutral to obtain the sensitized and activated graphene oxide solution with the concentration of 1 mg/mL. The activating solution is a mixed solution containing 0.25g/L of palladium chloride and 10mL/L of hydrochloric acid;
fourthly, preparing the flake copper powder: adding 200g of spherical copper powder (the particle size is 15-20 microns, the purity is more than 99.9%) into a ball milling tank, adding 500mL of absolute ethyl alcohol as a ball milling medium into a ball milling ball with a ball material ratio of 10:1, adding 0.5g of stearic acid as a process control agent, rotating at 300rpm, and putting the ball milling tank into a vacuum drying oven for complete drying after 4 hours of ball milling to obtain flake copper powder;
fifthly, preparing the graphene oxide/copper composite powder: and adding 20g of the flake copper powder prepared in the fourth step into 5g/L of hexadecyl trimethyl ammonium bromide solution, and magnetically stirring for 1h to obtain flake copper powder slurry with positive charges on the surface. Slowly adding 40mL of sensitized and activated graphene oxide solution prepared in the third step into the copper slurry, stirring for 15min, and adsorbing graphene oxide with negative charges on the surface of flake copper powder with positive charges under the action of electrostatic force to obtain graphene oxide/copper composite powder;
sixthly, preparing copper-plated graphene oxide/copper composite powder: transferring the graphene oxide/copper composite powder prepared in the fifth step into a plating solution with the pH value of 12, adding 5mL of formaldehyde solution, plating for 15min, centrifugally washing with deionized water to be neutral, and drying in a vacuum drying oven to obtain the copper-plated graphene oxide/copper composite powder. The plating solution is a mixed solution containing 15g/L of copper sulfate pentahydrate, 15g/L of disodium ethylene diamine tetraacetate and 14g/L of potassium sodium tartrate;
seventhly, preparing copper-plated graphene/copper composite powder: putting the copper-plated graphene oxide/copper composite powder prepared in the sixth step into a tube furnace, introducing argon gas as protective atmosphere, heating to 500 ℃, reducing graphene oxide by heating, preserving heat for 2 hours, and cooling along with the furnace to obtain the copper-plated graphene oxide/copper composite powder;
eighthly, preparing the graphene/copper composite material: adding the copper-plated graphene/copper composite powder prepared in the seventh step into a graphite mold, placing the graphite mold into a discharge plasma sintering furnace for sintering and molding under a vacuum condition after pre-pressing and molding, wherein the temperature rise speed is 100 ℃/min, the sintering temperature is 600 ℃, the sintering pressure is 35MPa, and the temperature is kept for 5min and then is reduced along with the furnace to obtain a graphene/copper composite material;
tests show that: the tensile strength of the composite material is 230MPa, the yield strength is 180MPa, and the elongation is 24%.
While the embodiments of the present invention have been described in detail, it should be understood that the invention is not limited to the embodiments, but is intended to cover modifications and substitutions within the spirit and scope of the present invention
The above description is only a preferred embodiment of the present invention, and does not limit the present invention in any way. It will be understood by those skilled in the art that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a high-strength graphene/copper composite material is characterized by comprising the following steps:
step 1: preparing a graphene oxide solution;
step 2: sensitizing the graphene oxide solution;
and step 3: activating the graphene oxide solution;
and 4, step 4: preparing flake copper powder;
and 5: uniformly adsorbing the graphene oxide graphene on the surface of the flake copper powder by using a static self-assembly process to prepare graphene oxide/copper composite powder;
step 6: placing the graphene oxide/copper composite powder in a plating solution for plating, and then drying to prepare copper-plated graphene oxide/copper composite powder;
and 7: reducing graphene oxide in the copper-plated graphene oxide/copper composite powder to obtain copper-plated graphene/copper composite powder;
and 8: and placing the copper-plated graphene/copper composite powder in a die for prepressing and forming, and then sintering and forming to obtain the graphene/copper composite material.
2. The preparation method of the high-strength graphene/copper composite material according to claim 1, wherein in step 1, 1g of crystalline flake graphite, 1g of sodium nitrate and 46mL of concentrated sulfuric acid are mixed in a beaker and magnetically stirred in an ice-water bath for 1 hour; slowly adding 6g of potassium permanganate, stirring for 1h, transferring to a constant-temperature water bath at 35 ℃, and magnetically stirring for 2 h; slowly adding 40mL of distilled water into a beaker, and magnetically stirring for 2 hours at the temperature of 90 ℃ under the water bath condition; taking out the beaker, adding a proper amount of distilled water, adding 6mL of 3 wt% hydrogen peroxide solution, uniformly stirring, standing for a period of time, and pouring out supernatant; and adding a dilute hydrochloric acid solution into the beaker, adding deionized water, and performing centrifugal washing until the solution is neutral to obtain a graphene oxide solution with negative charges.
3. The preparation method of the high-strength graphene/copper composite material according to claim 1, wherein in the step 2, the graphene oxide solution prepared in the step 1 is added into a sensitizing solution, sensitized for 30min, and centrifugally washed by deionized water to be neutral to obtain a sensitized graphene oxide solution; the sensitizing solution is a mixed solution containing 25g/L stannous chloride and 50mL/L hydrochloric acid.
4. The preparation method of the high-strength graphene/copper composite material according to claim 1, wherein in step 3, the sensitized graphene oxide solution prepared in step 2 is added into an activation solution, activated for 30min, and centrifugally washed with deionized water to be neutral, so as to obtain a sensitized and activated graphene oxide solution with a concentration of 1 mg/mL; the activating solution is a mixed solution containing 0.25g/L of palladium chloride and 10mL/L of hydrochloric acid.
5. The preparation method of the high-strength graphene/copper composite material according to claim 1, wherein in step 4, 200g of spherical copper powder is added into a ball milling tank, the particle size of the copper powder is 15-20 μm, the purity is greater than 99.9%, a stainless steel ball is used as a grinding ball, the ball-to-material ratio is 10:1, 500mL of absolute ethyl alcohol is added as a ball milling medium, 0.5g of stearic acid is added as a process control agent, the rotation speed is 300rpm, and the mixture is put into a vacuum drying oven for complete drying after ball milling for 4 hours, so that flake-shaped copper powder is obtained.
6. The method for preparing a high-strength graphene/copper composite material according to claim 1, wherein in step 5, 20g of the flake copper powder prepared in step 4 is added into 5g/L cetyl trimethyl ammonium bromide solution, and magnetic stirring is carried out for 1h to obtain flake copper powder slurry with positive charges on the surface. And (3) slowly adding 20-40 mL of sensitized and activated graphene oxide solution prepared in the step (three) into the copper slurry, stirring for 15min, and adsorbing graphene oxide with negative charges on the surface of the flake copper powder with positive charges under the action of electrostatic force to obtain graphene oxide/copper composite powder.
7. The preparation method of the high-strength graphene/copper composite material according to claim 1, wherein in step 6, the graphene oxide/copper composite powder prepared in step 5 is transferred to a plating solution with a pH value of 12, 5mL of formaldehyde solution is added, plating is performed for 15min, deionized water is used for centrifugal washing to be neutral, and the mixture is placed into a vacuum drying oven for drying to obtain copper-plated graphene oxide/copper composite powder; the plating solution is a mixed solution containing 15g/L of copper sulfate pentahydrate, 15g/L of disodium ethylene diamine tetraacetate and 14g/L of potassium sodium tartrate.
8. The preparation method of the high-strength graphene/copper composite material according to claim 1, wherein in step 7, the copper-plated graphene oxide/copper composite powder prepared in step 6 is placed in a tube furnace, argon is introduced as a protective atmosphere, the temperature is increased to 500 ℃, graphene oxide is reduced by heating, and the temperature is reduced along with the furnace after 2 hours of heat preservation to obtain the copper-plated graphene/copper composite powder.
9. The preparation method of the high-strength graphene/copper composite material according to claim 1, wherein in step 8, the copper-plated graphene/copper composite powder obtained in step 7 is added into a graphite mold, pre-pressed and molded, then placed into a spark plasma sintering furnace to be sintered and molded under vacuum conditions, the temperature rise speed is 100 ℃/min, the sintering temperature is 600 ℃, the sintering pressure is 35MPa, and the temperature is kept for 5min, and then the temperature is reduced along with the furnace to obtain the graphene/copper composite material.
10. The method of claim 1, wherein the high-strength graphene/copper composite has a graphene content of 0.1 wt% to 0.3 wt%, and the balance copper;
the tensile strength of the graphene/copper composite material is 230-280 MPa, the yield strength is 180-240 MPa, and the elongation is 32-24%.
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