CN108149046B - High-strength and high-conductivity graphene/copper nano composite material and preparation method and application thereof - Google Patents
High-strength and high-conductivity graphene/copper nano composite material and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
- C22C1/081—Casting porous metals into porous preform skeleton without foaming
- C22C1/082—Casting porous metals into porous preform skeleton without foaming with removal of the preform
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0084—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ carbon or graphite as the main non-metallic constituent
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
Abstract
The invention relates to a high-strength and high-conductivity graphene/copper composite material and a preparation method and application thereof. The copper matrix of the composite material is uniformly distributed in a three-dimensional nanoscale manner, and the dimension is 10-100 nm, preferably 30-80 nm; the graphene is in a three-dimensional interconnected network structure in the composite material, and the average layer number is 1-10. The graphene/copper nano composite material obtained by the method has the characteristics of high strength, high modulus and high conductivity, and can be used as various types of conducting materials.
Description
Technical Field
The invention relates to a high-strength and high-conductivity graphene/copper nano composite material as well as a preparation method and application thereof, belonging to the technical field of metal-based composite materials.
Background
Pure copper is one of the metal materials with the lowest resistivity, and is widely applied to the industrial fields of electric power, electronics, machinery and the like. However, pure copper is also difficult to meet the requirements of industrial development due to lower mechanical properties, for example, the ideal performance indexes of the contact line of the electrified high-speed railway are that the tensile strength is more than or equal to 550MPa, the elastic modulus is more than or equal to 140GPa, and the conductivity is more than or equal to 90% IACS. Therefore, copper materials with high strength, high modulus and high conductivity have become the focus of development.
In recent years, research on introduction of carbon material reinforced graphene into metal matrices has been increasingly promoted. The unique structure of the material has high strength (tensile strength-130 GPa), high modulus (elastic modulus-1 TPa) and high conductance (electron mobility-2 x 10)5cm2the/Vs) characteristics provide possibility for the copper-based composite material to realize the performances of high strength (more than or equal to 550MPa), high modulus (more than or equal to 140GPa) and high electric conductivity (more than or equal to 90 percent IACS). The literature search of the prior art finds that a pure Copper sample with High-density nano twin crystals is prepared by a pulse electrodeposition method in literature (1) of ultra High stranded High electric Conductivity in Copper, the average value of twin crystal lamella is 15nm, the scattering capability of the High-density nano twin crystal boundary on electron transportation is very low while dislocation motion is effectively limited, the breaking strength of the nano twin crystal Copper reaches 1068MPa, and the electric Conductivity is 98.4% IACS. However, due to the lack of the introduction of a high-modulus reinforcement, the elastic modulus of the nano twin crystal copper is 110 GPa-120 GPa, so that the use requirement is not met. In the document (2) "Enhanced Mechanical properties of Graphene/Copper Nanocomposites Using a Molecular-Level Mixing Process" (Graphene/Copper Nanocomposites with improved Mechanical properties Using a Molecular-Level Mixing Process), Graphene oxide nanosheets and Copper ions are subjected to Molecular-Level Mixing by electrostatic agent adsorption to obtain Graphene oxide/Copper ions (GO/Cu)2+) And then obtaining a reduced graphene oxide/copper (rGO/Cu) composite material through oxidation, reduction and sintering. The copper matrix in the composite material is in a submicron scale (100 nm-500 nm), and a graphene oxide reinforcement with mechanical and electrical properties reduced due to structural damage is used, the volume fraction of the reinforcement is 2.5%, the tensile strength of the composite material is 335MPa, the elastic modulus is 131GPa, and the electrical conductivity is 50% IACS, so that the composite material can not meet the use requirements. Document (3) "Aligning graphene in bulk hopper with nano-induced architecture coupled with in-situ processing for enhanced mechanical properties and high electrical conductivity" (at blockGraphene was arranged in bulk copper: nano laminated structure inspired by pearl layer and in-situ process leading to improvement of mechanical properties and high conductivity) ball milling commercial spherical copper powder to obtain a flaky shape, coating PMMA on the surface of the flaky copper powder by using an organic solvent, converting PMMA into graphene in situ under the conditions of high temperature and hydrogen atmosphere to obtain graphene/copper sheet composite powder, and finally obtaining the nano laminated graphene/copper composite material by hot-pressing sintering and hot-rolling processes. The thickness of the copper matrix sheet layer in the composite material is submicron (about 660nm), the volume fraction of the reinforcement is 2.5%, the tensile strength of the composite material is 378MPa, the elastic modulus is 135GPa, and the composite material does not meet the use requirement. But the introduction of high quality in-situ grown graphene keeps the composite material high conductivity (93.8% IACS).
Therefore, in summary of the features and defects of the prior art, the preparation of the high-strength and high-conductivity graphene/copper composite material with the tensile strength of more than or equal to 550MPa, the elastic modulus of more than or equal to 140GPa and the conductivity of more than or equal to 90% IACS needs to solve the following technical problems: (1) the acquisition of the copper matrix with the internal nano scale (less than 100nm) of the composite material increases the barrier effect of the grain boundary on dislocation motion and improves the strength of the copper matrix; (2) due to the introduction of a high-density graphene/copper interface in the composite material, the barrier effect of the interface on dislocation motion is increased, and the volume fraction of graphene is improved, so that the composite material has high strength and high modulus; (3) due to the introduction of high-quality graphene, the intrinsic properties of two-dimensional high conductivity and high electron mobility of the graphene are exerted, so that the composite material keeps high conductivity.
Disclosure of Invention
In order to solve the technical problems, the high-strength and high-conductivity graphene/copper nanocomposite is obtained by constructing a copper matrix with uniform three-dimensional nanoscale distribution, introducing a carbon source on the basis, and finally sintering.
The invention is realized by the following technical scheme.
A high-strength and high-conductivity graphene/copper composite material is characterized in that a copper matrix is uniformly distributed in a three-dimensional nanoscale, and the dimension is 10-100 nm, preferably 30-80 nm; the graphene is in a three-dimensional interconnected network structure in the composite material, and the average layer number is 1-10.
The tensile strength of the composite material is 580-650MPa, the elastic modulus is 150-220GPa, and the electrical conductivity is 90-97% IACS.
The invention also provides a preparation method of the high-strength and high-conductivity graphene/copper composite material, which comprises the following steps: taking a Cu-Mn binary alloy plate or a Cu-Ni binary alloy plate as an anode, and obtaining nano porous copper by electrochemical etching dealloying; introducing a carbon source, uniformly growing graphene on the surface of the nano-porous copper, and performing hot-pressing sintering densification to obtain the graphene/copper composite material.
Wherein the mass fraction of Mn or Ni in the binary alloy plate is 50-90% (such as 70%, 80%), and the thickness of the alloy plate is 10-1000 μm, preferably 100-500 μm.
In the electrochemical etching step, the electrolyte is an acid water solution, and the potential difference is 0.01-0.30V, preferably 0.05-0.30V; the etching time is 0.5-50 hours. The electrolyte can be HCl aqueous solution, the concentration is 0.01-0.50 mol/L, and the preferable concentration is 0.05-0.50 mol/L; or H2SO4The concentration of the aqueous solution is 0.005-0.25 mol/L, preferably 0.025-0.25 mol/L; or H3PO4The concentration of the aqueous solution is 0.005-0.20 mol/L, preferably 0.02-0.20 mol/L.
The carbon source is selected from a gaseous carbon source and/or a solid carbon source; wherein the gaseous carbon source is methane or acetylene; the solid carbon source is polymethyl methacrylate (PMMA) or Polystyrene (PS). Meanwhile, according to different types of carbon sources, the introduction mode and the graphene growth mode are correspondingly different, and the method comprises the following specific steps:
when the carbon source is a gaseous carbon source, the graphene deposition conditions are as follows: the flow rate of the gaseous carbon source is 1sccm to 10sccm, the flow rate of the hydrogen is 10sccm to 30sccm, the flow rate of the argon is 50sccm to 150sccm, the pressure in the tube is kept less than 1Torr, and the temperature is 600 ℃ to 700 ℃. The specific implementation steps are as follows:
(1) placing the nano porous copper in a tubular furnace, adjusting the flow of a gaseous carbon source to be 1 sccm-10 sccm, the flow of hydrogen to be 10 sccm-30 sccm, the flow of argon to be 50 sccm-150 sccm, and keeping the pressure in the tube to be less than 1 Torr;
(2) carrying out graphene deposition at the temperature of 600-700 ℃, wherein the deposition time is 5-20 minutes;
(3) and stopping introducing the gaseous carbon source, and keeping the pressure in the tube less than 200mTorr until the furnace temperature is cooled to the room temperature to obtain the nano porous graphene/copper.
When the type of the carbon source is a solid carbon source, firstly obtaining nano porous PMMA/copper or PS/copper by using a vacuum impregnation method, and then growing graphene; the impregnation conditions are as follows: the impregnation liquid is 0.5-5.0 g/L polymethyl methacrylate or polystyrene anisole or chloroform solution, and the drying temperature is 70-90 ℃; the graphene growth conditions are as follows: the flow rate of hydrogen is 5sccm to 15sccm, the flow rate of argon is 100sccm to 200sccm, the pressure in the tube is kept less than 1Torr, the temperature is 800 ℃ to 1000 ℃, and the time is 1to 2 hours. The specific implementation steps are as follows:
(1) adding 0.5-5.0 g/L polymethyl methacrylate (PMMA) or Polystyrene (PS) into a solvent by using a vacuum impregnation method, uniformly stirring, introducing into a nano porous copper structure, and drying at 70-90 ℃ (such as 80 ℃) to obtain nano porous PMMA/copper or PS/copper; the system is anisole or chloroform;
(2) placing the nano porous PMMA/copper or PS/copper into a tubular furnace, adjusting the hydrogen flow to be 5 sccm-15 sccm, the argon flow to be 100-200 sccm, keeping the pressure in the tube to be less than 1Torr, and growing the graphene at the temperature of 800-1000 ℃ for 1-2 hours;
(3) and keeping the pressure in the tube less than 200mTorr until the furnace temperature is cooled to room temperature, thus obtaining the nano porous graphene/copper.
The hot-pressing sintering can be selected from one of hot-pressing sintering under vacuum or gas protection, hot isostatic pressing sintering, spark plasma sintering and microwave sintering; the sintering temperature is 700-1000 ℃, the pressure is 10-200 MPa, and preferably 50-200 MPa.
The invention also provides application of the graphene/copper composite material in the fields of electric power, electronics and mechanical industry.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with the submicron scale of the existing composite material, the copper matrix in the composite material is uniformly distributed in a three-dimensional nanoscale manner, the matrix grain boundary density and the graphene/copper interface density are obviously improved, the effect of hindering dislocation motion is increased, and the composite material has high strength (more than or equal to 550 MPa).
(2) The existence of the high-density graphene/copper interface improves the volume fraction of the high-modulus reinforcement graphene in the composite material, so that the composite material has high modulus (more than or equal to 140 GPa).
(3) The graphene grows on the surface of the nanometer hole, and the graphene presents a three-dimensional network structure in the composite material; the graphene carbon atoms can obtain doped electrons from surrounding copper atoms, so that the carrier migration speed of a graphene/copper interface is obviously improved; the existence of the high-density and high-conductivity graphene/copper interface enables the composite material to keep high conductivity (more than or equal to 90% IACS).
Drawings
Fig. 1 is a schematic diagram of a preparation method of the high-strength and high-conductivity graphene/copper nanocomposite material of the invention.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
The embodiment provides a preparation method of a graphene/copper composite material, which comprises the following steps:
(1) carrying out electrochemical etching to remove alloying on a Cu-Mn binary alloy plate with the thickness of 100 mu m and the Mn mass fraction of 70%, wherein the electrolyte is 0.25mol/L HCl aqueous solution; the potential difference is 0.10V; the electrochemical etching time is 4 hours; the aperture of the obtained nano-porous copper is 30 nm.
(2) Introducing 2.5g/L of polymethyl methacrylate anisole solution into the nano-porous copper structure by using a vacuum impregnation method, and drying at 80 ℃ to obtain the nano-porous PMMA/copper. The nano porous PMMA/copper is placed in a tubular furnace, the hydrogen flow is adjusted to be 10sccm, the argon flow is adjusted to be 150sccm, and the pressure in the tube is kept to be less than 1 Torr. And (3) carrying out graphene growth at the temperature of 900 ℃ for 1 hour. Keeping the pressure in the tube less than 200mTorr until the furnace temperature is cooled to room temperature, and obtaining the nano porous graphene/copper, wherein the number of graphene layers is 5-6.
(3) And carrying out hot-pressing sintering on the nano porous graphene/copper under the protection of argon atmosphere at the temperature of 900 ℃ and the pressure of 50MPa for 60 minutes to obtain the graphene/copper-based composite material.
The obtained composite material has tensile strength of 633MPa, elastic modulus of 209.6GPa and electric conductivity of 92.1% IACS, and meets the use requirements.
Example 2
The embodiment provides a preparation method of a graphene/copper composite material, which comprises the following steps:
(1) carrying out electrochemical etching dealloying on a Cu-Ni binary alloy plate with the thickness of 500 mu m and the mass fraction of Ni of 80 percent, wherein the electrolyte is H of 0.05Mol/L2SO4An aqueous solution; the potential difference is 0.20V; the electrochemical etching time is 12 hours; the aperture of the obtained nano-porous copper is 50 nm.
(2) Introducing 0.50g/L chloroform solution of polymethyl methacrylate into the nano-porous copper structure by using a vacuum impregnation method, and drying at 80 ℃ to obtain the nano-porous PMMA/copper. The nano porous PMMA/copper is placed in a tubular furnace, the hydrogen flow is adjusted to be 15sccm, the argon flow is adjusted to be 200sccm, and the pressure in the tube is kept to be less than 1 Torr. And (3) carrying out graphene growth at the temperature of 1000 ℃ for 1 hour. Keeping the pressure in the tube less than 200mTorr until the furnace temperature is cooled to room temperature, and obtaining the nano porous graphene/copper, wherein the number of graphene layers is 2-3.
(3) And (3) carrying out discharge plasma hot-pressing sintering on the nano porous graphene/copper under the conditions that the temperature is 800 ℃ and the pressure is 100MPa, and keeping the pressure for 10 minutes to obtain the graphene/copper-based composite material.
The obtained composite material has the tensile strength of 587MPa, the elastic modulus of 154.5GPa and the electrical conductivity of 94.6 percent IACS, and meets the use requirements.
Example 3
The embodiment provides a preparation method of a graphene/copper composite material, which comprises the following steps:
(1) carrying out electrochemical etching to remove alloying on a Cu-Mn binary alloy plate with the thickness of 1000 mu m and the Mn mass fraction of 90%, wherein the electrolyte is 0.50Mol/L HCl aqueous solution; the potential difference is 0.30V; the electrochemical etching time is 20 hours; the aperture of the obtained nano-porous copper is 75 nm.
(2) 5.0g/L of anisole solution of polystyrene is introduced into the nano-porous copper structure by a vacuum impregnation method, and then the nano-porous PS/copper is obtained by drying at 80 ℃. The nano-porous PS/copper is placed in a tubular furnace, the hydrogen flow is adjusted to be 5sccm, the argon flow is adjusted to be 100sccm, and the pressure in the tube is kept to be less than 1 Torr. And carrying out graphene growth at the temperature of 800 ℃ for 2 hours. Keeping the pressure in the tube less than 200mTorr until the furnace temperature is cooled to room temperature, and obtaining the nano porous graphene/copper, wherein the number of graphene layers is 8-9.
(3) And (3) carrying out vacuum hot-pressing sintering on the nano porous graphene/copper under the conditions that the temperature is 700 ℃ and the pressure is 200MPa, and keeping the pressure for 60 minutes to obtain the graphene/copper-based composite material.
The obtained composite material has the tensile strength of 617MPa, the elastic modulus of 186.4GPa and the electrical conductivity of 91.7 percent IACS, and meets the use requirements.
Example 4
The embodiment provides a preparation method of a graphene/copper composite material, which comprises the following steps:
(1) carrying out electrochemical etching dealloying on a Cu-Ni binary alloy plate with the thickness of 500 mu m and the mass fraction of Ni of 70 percent, wherein the electrolyte is H of 0.05Mol/L3PO4An aqueous solution; the potential difference is 0.05V; the electrochemical etching time is 40 hours; the aperture of the obtained nano-porous copper is 30 nm.
(2) The nanoporous copper is placed in a tubular furnace, the flow of gaseous carbon source acetylene is regulated to be 5sccm, the flow of hydrogen is regulated to be 20sccm, the flow of argon is regulated to be 100sccm, and the pressure in the tube is kept to be less than 1 Torr. Graphene deposition was carried out at a temperature of 650 ℃ for a deposition time of 10 minutes. And then stopping introducing the gaseous carbon source, keeping the pressure in the tube less than 200mTorr until the furnace temperature is cooled to the room temperature, and obtaining the nano porous graphene/copper, wherein the number of layers of the graphene is 1-2.
(3) And carrying out hot-pressing sintering on the nano porous graphene/copper under the protection of argon atmosphere at the temperature of 900 ℃ and the pressure of 50MPa for 60 minutes to obtain the graphene/copper-based composite material.
The obtained composite material has the tensile strength of 595MPa, the elastic modulus of 158.2GPa and the electrical conductivity of 96.8 percent IACS, and meets the use requirements.
The above are some preferred embodiments of the present invention, and it should be understood that there are other embodiments of the present invention, such as changing the composition and thickness parameters of the Cu-Mn or Cu-Ni binary alloy plate in the above embodiments, the electrolyte, potential difference and etching time parameters in the electrochemical etching dealloying process, the carbon source concentration during the graphene growth process, the temperature, atmosphere and time parameters, and the temperature, pressure and time parameters in the densification process, which are easily implemented by those skilled in the art.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (17)
1. A high-strength and high-conductivity graphene/copper composite material is characterized in that a copper matrix is uniformly distributed in a three-dimensional nanoscale, and the dimension of the copper matrix is 10-100 nm; the graphene is in a three-dimensional interconnected network structure in the composite material, and the average number of layers is 1-10;
the preparation method of the composite material comprises the following steps:
taking a Cu-Mn binary alloy plate or a Cu-Ni binary alloy plate as an anode, and obtaining nano porous copper by electrochemical etching dealloying; introducing a carbon source, uniformly growing graphene on the surface of the nano-porous copper, and performing hot-pressing sintering densification to obtain a graphene/copper composite material;
wherein the carbon source is selected from a gaseous carbon source and/or a solid carbon source;
when the carbon source is a gaseous carbon source, the graphene deposition conditions are as follows: the flow rate of the gaseous carbon source is 1sccm to 10sccm, the flow rate of the hydrogen is 10sccm to 30sccm, the flow rate of the argon is 50sccm to 150sccm, the pressure in the tube is kept less than 1Torr, and the temperature is 600 ℃ to 700 ℃;
when the type of the carbon source is a solid carbon source, firstly obtaining nano porous PMMA/copper or PS/copper by using a vacuum impregnation method, and then growing graphene; the graphene growth conditions are as follows: the flow rate of hydrogen is 5sccm to 15sccm, the flow rate of argon is 100sccm to 200sccm, the pressure in the tube is kept less than 1Torr, and the temperature is 800 ℃ to 1000 ℃.
2. The composite material according to claim 1, characterized in that the nanoscale is between 30nm and 80 nm.
3. The composite material according to claim 1 or 2, characterized in that the composite material has a tensile strength of 580-650MPa, an elastic modulus of 150-220GPa and an electrical conductivity of 90-97% IACS.
4. A method for preparing the high-strength high-conductivity graphene/copper composite material according to any one of claims 1to 3, comprising: taking a Cu-Mn binary alloy plate or a Cu-Ni binary alloy plate as an anode, and obtaining nano porous copper by electrochemical etching dealloying; introducing a carbon source, uniformly growing graphene on the surface of the nano-porous copper, and performing hot-pressing sintering densification to obtain the graphene/copper composite material.
5. The production method according to claim 4, wherein the binary alloy sheet contains 50 to 90 mass% of Mn or Ni, and the thickness of the alloy sheet is 10 to 1000 μm.
6. The method as claimed in claim 5, wherein the thickness of the alloy plate is 100-500 μm.
7. The preparation method according to claim 4, wherein the electrolyte used in the electrochemical etching is an aqueous acid solution, and the potential difference is 0.01-0.30V.
8. The production method according to claim 7, wherein the potential difference is 0.05 to 0.30V.
9. The method of claim 7, wherein the electrolyte is aqueous HCl, H2SO4Aqueous solution or H3PO4An aqueous solution.
10. The method according to any one of claims 4 to 9, wherein the carbon source is selected from a gaseous carbon source and/or a solid carbon source.
11. The method of claim 10, wherein the gaseous carbon source is methane or acetylene.
12. The method according to claim 10, wherein the solid carbon source is polymethyl methacrylate or polystyrene.
13. The method according to claim 11, wherein when the carbon source is a gaseous carbon source, the graphene deposition conditions are: the flow rate of the gaseous carbon source is 1sccm to 10sccm, the flow rate of the hydrogen is 10sccm to 30sccm, the flow rate of the argon is 50sccm to 150sccm, the pressure in the tube is kept less than 1Torr, and the temperature is 600 ℃ to 700 ℃.
14. The preparation method of claim 12, wherein when the carbon source is a solid carbon source, the nano-porous PMMA/copper or PS/copper is obtained by a vacuum impregnation method, and then graphene growth is performed;
the impregnation conditions are as follows: the impregnation liquid is 0.5-5.0 g/L polymethyl methacrylate or polystyrene anisole or chloroform solution, and the drying temperature is 70-90 ℃;
the graphene growth conditions are as follows: the flow rate of hydrogen is 5sccm to 15sccm, the flow rate of argon is 100sccm to 200sccm, the pressure in the tube is kept less than 1Torr, and the temperature is 800 ℃ to 1000 ℃.
15. The preparation method according to claim 4, wherein the hot-pressing sintering mode is one selected from vacuum or gas protection hot-pressing sintering, hot isostatic pressing sintering, spark plasma sintering or microwave sintering; the sintering temperature is 700-1000 ℃, and the pressure is 10-200 MPa.
16. The method of claim 15, wherein the pressure is 50 to 200 MPa.
17. Use of the graphene/copper composite material according to any one of claims 1to 3 in the fields of electric power, electronics and mechanical industry.
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| CN109440145B (en) * | 2018-12-30 | 2020-02-14 | 苏州碳素集电新材料有限公司 | Graphene/copper composite conductive material and preparation method thereof |
| CN109735826B (en) * | 2019-02-14 | 2021-08-27 | 中车工业研究院有限公司 | Graphene/copper composite material and preparation method and application thereof |
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| CN105217618A (en) * | 2015-10-22 | 2016-01-06 | 天津大学 | A kind of preparation method of three-D nano-porous Graphene |
| CN105386003A (en) * | 2015-12-02 | 2016-03-09 | 哈尔滨工业大学 | Preparation method for three-dimensional structure graphene reinforced copper matrix composite material |
| CN105502359A (en) * | 2015-12-22 | 2016-04-20 | 福州大学 | Preparation method of low-cost porous graphene |
| CN106521204A (en) * | 2016-12-16 | 2017-03-22 | 天津大学 | Preparation method of in-situ grown graphene reinforced metal-based composite material |
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| CN104625283A (en) * | 2014-12-26 | 2015-05-20 | 哈尔滨工业大学 | Auxiliary brazing method for grapheme composite middle layer of three-dimensional structure |
| CN105217618A (en) * | 2015-10-22 | 2016-01-06 | 天津大学 | A kind of preparation method of three-D nano-porous Graphene |
| CN105386003A (en) * | 2015-12-02 | 2016-03-09 | 哈尔滨工业大学 | Preparation method for three-dimensional structure graphene reinforced copper matrix composite material |
| CN105502359A (en) * | 2015-12-22 | 2016-04-20 | 福州大学 | Preparation method of low-cost porous graphene |
| CN106521204A (en) * | 2016-12-16 | 2017-03-22 | 天津大学 | Preparation method of in-situ grown graphene reinforced metal-based composite material |
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