CN114959697A - Preparation method of graphene/copper composite material combining physical vapor deposition and chemical vapor deposition - Google Patents

Preparation method of graphene/copper composite material combining physical vapor deposition and chemical vapor deposition Download PDF

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CN114959697A
CN114959697A CN202210531620.2A CN202210531620A CN114959697A CN 114959697 A CN114959697 A CN 114959697A CN 202210531620 A CN202210531620 A CN 202210531620A CN 114959697 A CN114959697 A CN 114959697A
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copper
graphene
vapor deposition
composite material
preparing
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梁俊才
章潇慧
裴中正
柳柏杉
王雅伦
李要君
杨为三
陈强
陈朝中
李明高
赵明元
龚明
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CRRC Industry Institute Co Ltd
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CRRC Academy Co Ltd
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    • 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
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • 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
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention belongs to the technical field of materials, and particularly relates to a preparation method of a graphene/copper composite material combining physical vapor deposition and chemical vapor deposition. The method comprises the steps of depositing a layer of graphene material on the surface of a copper foil by CVD, depositing a layer of copper material on the surface of the graphene material by PVD, depositing the graphene material on the surface of the deposited copper material by CVD, and repeatedly depositing in the way to obtain the graphene/copper composite material with the multilayer structure. The material is compounded by using two materials of pure copper and graphene, and the tensile strength of the compounded material is more than or equal to 200MPa and is at the same level as that of the pure copper; the conductivity of the copper is more than or equal to 110% IACS, and is improved by more than 10% compared with the conductivity of pure copper; compared with pure copper, the skin depth is improved by 30 percent. The material can replace the traditional copper material or silver material, is applied to a super capacitor or a motor driving device, and plays the roles of improving efficiency, reducing temperature rise and the like.

Description

Preparation method of graphene/copper composite material combining physical vapor deposition and chemical vapor deposition
Technical Field
The invention belongs to the technical field of materials, and relates to a preparation method of a graphene/copper composite material combining physical vapor deposition and chemical vapor deposition.
Background
The graphene/copper composite material is applied to the field of power electronic transmission due to the ultrahigh electric conductivity, good mechanical property and good heat conductivity, and particularly replaces the application of the traditional copper material in the fields of high-efficiency traction motors, energy-saving transformers, 5G communication, new energy automobiles and the like, so that the effects of reducing copper loss, reducing temperature rise and improving efficiency can be achieved.
Copper has the advantages of high electrical conductivity, high thermal conductivity and the like, and is the most important conductive material in the current power system. However, the current purification and single crystallization techniques have approached the physical limits of copper materials, and it is difficult to further reduce the heat-induced electrical losses.
Graphene as a novel two-dimensional planar material has excellent mechanical properties and ultrahigh carrier mobility. Graphene is used as a reinforcing phase and is embedded into metal copper to form the graphene/copper composite material, so that comprehensive performances of copper conductivity, mechanics and the like can be remarkably improved.
In recent years, many researches on graphene/copper composite materials at home and abroad are carried out, and mainly the graphene film is deposited on the surface of copper powder by in-situ growth, and then the graphene film is pressed and formed by using a powder metallurgy process. The powder metallurgy method mainly improves the strength of the composite material, but the graphene is in a disordered state in the distribution of a copper matrix, so that the high electron transfer capacity of the graphene cannot be exerted, and the improvement on the conductivity is limited.
Disclosure of Invention
The invention provides a preparation method of a graphene/copper composite material, wherein the graphene/copper composite material prepared by the method has the tensile strength of more than or equal to 200MPa and is at the same level with pure copper; the conductivity of the copper is more than or equal to 110% IACS, and is improved by more than 10% compared with the conductivity of pure copper; compared with pure copper, the skin depth is improved by 30%.
A preparation method of a graphene/copper composite material comprises the following steps:
1) providing a rolled copper foil; preparing a graphene film on the surface of the rolled copper foil by adopting a Chemical Vapor Deposition (CVD) process to prepare a copper/graphene material;
2) depositing a copper film on the surface of the copper/graphene material by using a high-purity sputtering copper target material as a material and adopting a Physical Vapor Deposition (PVD) process to prepare a Cu/C/Cu material;
3) preparing a graphene film on the surface of the Cu/C/Cu material by adopting a chemical vapor deposition process to prepare a Cu/C/Cu/C composite material;
4) depositing a copper film on the surface of the Cu/C/Cu/C composite material by using a high-purity sputtering copper target material as a material and adopting a Physical Vapor Deposition (PVD) process to obtain the Cu/C/Cu/C/Cu composite material;
5) and continuously repeating the step 3) and the step 4) to prepare the graphene/copper composite material with the multilayer structure.
Further, the thickness of the rolled copper foil in the step 1) is between 8 and 25 μm.
Further, before depositing the graphene film, the rolled copper foil needs to be subjected to hydrogen reduction treatment to remove gas adsorbed on the surface and an oxide layer.
Furthermore, the purity of the copper material is more than or equal to 99.9%, such as 99.9% -99.9999%, specifically such as 99.9%, 99.99%, 99.999%, 99.9999%. Preferably, the purity of the copper material is more than or equal to 99.99 percent. Researches find that the corresponding raw material cost of the copper block is exponentially increased along with the improvement of the purity of the copper block, and in order to meet the actual production requirement, the purity of the copper block is 99.99 percent. The performance of the graphene/copper-based composite material prepared from the copper block with the purity of 99.99% is at the same level as that of the copper block with the purity of 99.999%.
Further, carbon sources used for chemical vapor deposition are methane, ethylene, acetylene, and the like.
Further, the temperature of the chemical vapor deposition is 950-.
Further, the number of layers of the graphene thin film prepared by each chemical vapor deposition is 1-5, such as 1, 2, 3, 4, 5. Due to the preparation technology, the number of layers of the graphene material is smaller, the requirements on the preparation technology and equipment are higher, and the corresponding cost is higher. The number of the graphite layers is less than 5, and the graphite still has different electronic structures of three-dimensional graphite. The single-layer graphene has excellent performance but can generate folds which can destroy a hexagonal symmetrical lattice structure of the graphene and generate a long-range scattering potential barrier to increase resistance, so that the preparation process is very important for regulating and controlling the number of graphene layers. The preparation method is characterized in that the number of graphene layers is divided into single-layer graphene (1 layer), double-layer graphene (2 layers) and multi-layer graphene (3 layers, 4 layers and 5 layers).
Further, the copper thin film prepared by each physical vapor deposition has a thickness of 1-15 μm, optionally 3-10 μm, such as 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 12 μm, 15 μm.
Further, each time the vacuum of the background of the physical vapor deposition reaches 5.5 multiplied by 10 -3 Pa or above, and/or target power densityAt 1-10W/cm 2 E.g. 1W/cm 2 、2W/cm 2 、3W/cm 2 、4W/cm 2 、5W/cm 2 、6W/cm 2 、7W/cm 2 、8W/cm 2 、9W/cm 2 、10W/cm 2 。
Further, the target current of the physical vapor deposition is 5-20A.
Further, the temperature of the physical vapor deposition is 500 ℃ or lower.
According to the embodiment of the present invention, the total number of layers of the graphene/copper composite material having a multilayer structure is 10 to 1000, specifically, for example, 10, 50, 100, 200, 300, 400, 500, 600, 800, 900, 1000 layers. The thickness of the application target product determines the total layer number of the graphene/copper composite material. Because the number of layers is different, the proportion of graphene is different, according to the test result of electrical properties, when the number of graphene layers is 10, 50 and 100, the conductivity is increased by a small margin and is increased from 108% IACS to 112% IACS, and when the total number of layers is more than 200, the conductivity tends to be consistent with the change of the number of layers. The total number of layers refers to the number of layers of all copper thin films and the number of layers of graphene thin films.
Further, the operation of preparing the copper film and the operation of preparing the graphene film in the preparation method are performed in the same chamber. Therefore, the introduction of impurity elements and the damage of mechanical stress in the transfer process of the graphene film can be avoided, and the integrity and uniformity of the graphene film in the copper matrix are ensured.
Further, the method also comprises a step 6) of further processing the prepared graphene/copper composite material with the multilayer structure. The finished product meeting the requirements of the required size and surface quality can be processed by utilizing mechanical processing equipment.
The invention also discloses the graphene/copper composite material with the multilayer structure prepared by the method. The material can replace the traditional copper material or silver material, is applied to a super capacitor or a motor driving device, and plays the roles of improving efficiency, reducing temperature rise and the like.
The invention also provides equipment for preparing the graphene/copper composite material, which is used for preparing the graphene/copper composite material and specifically comprises a CVD (chemical vapor deposition) deposition system and a PVD (physical vapor deposition) deposition system;
preparing a graphene film on the surface of the rolled copper foil by adopting a Chemical Vapor Deposition (CVD) process in a CVD deposition system to prepare a copper/graphene material;
in a PVD (physical vapor deposition) deposition system, a high-purity sputtering copper target material is used as a material, and a copper film is deposited on the surface of the copper/graphene material by adopting a Physical Vapor Deposition (PVD) process to prepare a Cu/C/Cu material;
then preparing a graphene film on the surface of the Cu/C/Cu material by adopting a chemical vapor deposition process in a CVD deposition system to prepare a Cu/C/Cu/C composite material;
in a PVD (physical vapor deposition) deposition system, a high-purity sputtering copper target material is used as a material, and a copper film is deposited on the surface of the Cu/C/Cu/C composite material by adopting a Physical Vapor Deposition (PVD) process to obtain the Cu/C/Cu/C/Cu composite material;
the above Chemical Vapor Deposition (CVD) process and Physical Vapor Deposition (PVD) process are repeated until the graphene/copper composite material having a multi-layered structure is manufactured.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the invention, the preparation process is simple in process and good in repeatability, and is beneficial to industrial large-scale production. Through the experiments of different layers, the graphene/copper composite material with good interface combination effect is obtained, the conductivity of the material is improved, the temperature rise is reduced in the application process of the flat-plate transformer, and the efficiency is improved.
(2) According to the invention, the two materials are subjected to composite deposition in the same chamber, so that the introduction of impurity elements and the damage of mechanical stress in the transfer process of the graphene film are avoided, and the integrity and uniformity of the graphene film in a copper matrix are ensured.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus for preparing a graphene/copper composite material according to an embodiment of the present invention.
In fig. 1, 1: a CVD deposition system; 2: a PVD deposition system; 3: a discharge system; 4: a graphene film deposition zone; 5: a material transfer guide rail; 6: high-purity copper target material; 7: a copper thin film deposition area; 8: graphene/copper composite.
Fig. 2 is a photograph of a graphene/copper composite prepared in example 6 of the present invention.
Fig. 3 is a microstructure photograph of a graphene/copper composite prepared in example 6 of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the following examples.
Referring to fig. 1, an embodiment of the invention provides an apparatus for preparing a graphene/copper composite material, including a CVD deposition system 1 and a PVD deposition system 2; preparing a graphene film on the surface of the rolled copper foil by adopting a chemical vapor deposition process in a CVD (chemical vapor deposition) deposition system 1 to prepare a copper/graphene material; in a PVD (physical vapor deposition) system 2, a high-purity sputtering copper target material is used as a material, and a copper film is deposited on the surface of the copper/graphene material by adopting a physical vapor deposition process to prepare a Cu/C/Cu material; then preparing a graphene film on the surface of the Cu/C/Cu material by adopting a chemical vapor deposition process in a CVD deposition system 2 to prepare a Cu/C/Cu/C composite material; in a PVD (physical vapor deposition) deposition system, a high-purity sputtering copper target material is used as a material, and a copper film is deposited on the surface of the Cu/C/Cu/C composite material by adopting a physical vapor deposition process to obtain the Cu/C/Cu/C/Cu composite material; the above chemical vapor deposition process and physical vapor deposition process are repeated until the graphene/copper composite material 8 having a multilayer structure is manufactured.
Further, the CVD deposition system 1 includes a graphene thin film deposition area 4, and chemical vapor deposition is performed by using a chemical vapor deposition process.
Further, the PVD deposition system 2 comprises a copper thin film deposition zone 7 for depositing a copper thin film by using a physical vapor deposition process with a high-purity sputtering copper target 6 as a material.
Further, the above apparatus further includes a discharging system 3 for transporting out the prepared graphene/copper composite material having a multilayer structure.
Further, the above apparatus further includes a material transfer guide 5 for transferring materials (copper/graphene material, Cu/C/Cu/C composite material, Cu/C/Cu composite material, etc.) between the CVD deposition system 1 and the PVD deposition system 2, and transporting the manufactured graphene/copper composite material 8 having a multilayer structure to the discharge system 3, or further from the discharge system 3.
Further, the CVD deposition system 1 and the PVD deposition system 2 are in the same chamber. Therefore, the introduction of impurity elements and the damage of mechanical stress in the transfer process of the graphene film can be avoided, and the integrity and uniformity of the graphene film in the copper matrix are ensured.
The following examples graphene/copper composites may be prepared using the apparatus shown in fig. 1.
The preparation method of the graphene/copper composite material of the following embodiment is as follows:
the following rolled copper foil is pretreated in advance to remove an oxide layer, so that the cleanliness of the surface of the copper foil is ensured.
Step A: preparing a graphene film on the surface of a copper foil by taking a rolled copper foil (the thickness of the copper foil is 10 microns) and methane as a carbon source and adopting a CVD (chemical vapor deposition) process to obtain a copper/graphene material; see table 1 for specific processes;
and B: taking a high-purity sputtering copper target material, and depositing a copper film on the surface of the copper/graphene material prepared in the step A by adopting a PVD (physical vapor deposition) process, wherein the thickness and the target power density of the copper film are shown in the following table 1; obtaining a Cu/C/Cu/composite material;
and C: repeating the CVD process in the step A, and depositing a graphene film on the surface of the Cu/C/Cu material prepared in the step B to obtain a Cu/C/Cu/C composite material;
step D: c, repeating the PVD process in the step B, and depositing a copper film on the surface of the Cu/C/Cu/C material prepared in the step C to obtain a Cu/C/Cu/C/Cu composite material;
step E: and repeating the PVD and CVD processes to finally obtain the graphene/copper composite material with the multilayer structure.
Further processing to obtain a product with a length of 100 mm × 100 (width) mm × 2 (height) mm
Table 1 lists the process parameters and the article property parameters for examples 1-13.
Fig. 2 is a photograph of graphene/copper composite materials prepared in examples 6 and 7.
Fig. 3 is a microstructure photograph of the graphene/copper composite prepared in example 6.
Examples of the experiments
The prepared graphene/copper composite material is applied to a flat-plate transformer, and the test results are shown in table 1.
The results of the embodiment 1 and the embodiment 3 can show that the electrical property of the copper-based composite material is improved from 100% IACS to 108IACS after the graphene is added, and the application verification result shows that the temperature rise is reduced and the efficiency is improved.
The comparison between example 3 and example 13 shows that when the number of graphene layers exceeds 5, the properties of graphene change, and the graphene exists in the copper matrix in the form of free carbon, which is equivalent to the presence of impurity elements, and thus lattice defects are generated, which rather inhibit the increase of the electrical conductivity.
The comparative results of examples 9, 10 and 11 show that the electrical properties improve with increasing purity of the starting material;
the results of examples 5, 6 and 7 show that the improvement of the target power can improve the compactness of the sputtered copper film and improve the composite effect of copper and graphene, the strength and the mechanical property of the copper-based composite material are improved, and the influence on the electrical property is small.
The thermal conductivity test is carried out according to GB/T22588-2008; tensile strength testing was performed according to GB/T228.1-2010; the conductivity test was performed as T/CSTM 00591-2022; the efficiency test is carried out according to the energy efficiency limit value and the energy efficiency grade of the GB/18613 and 2016 small and medium three-phase asynchronous motor; skin depth test conditions: 100KHz, copper surface temperature 20 ℃.
Test results show that compared with pure copper, the efficiency is improved by 3.4%, and the skin depth is improved by 30%.
Figure BDA0003643726880000071
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 (10)

1. A preparation method of a graphene/copper composite material is characterized by comprising the following steps:
1) providing a rolled copper foil; preparing a graphene film on the surface of the rolled copper foil by adopting a chemical vapor deposition process to prepare a copper/graphene material;
2) depositing a copper film on the surface of the copper/graphene material by using a physical vapor deposition process by taking a high-purity sputtering copper target material as a material to prepare a Cu/C/Cu material;
3) preparing a graphene film on the surface of the Cu/C/Cu material by adopting a chemical vapor deposition process to prepare a Cu/C/Cu/C composite material;
4) depositing a copper film on the surface of the Cu/C/Cu/C composite material by using a high-purity sputtering copper target as a material and adopting a physical vapor deposition process to obtain the Cu/C/Cu/C/Cu composite material;
5) and continuously repeating the step 3) and the step 4) to prepare the graphene/copper composite material with the multilayer structure.
2. The method of preparing the graphene/copper composite according to claim 1, wherein the thickness of the rolled copper foil in step 1) is between 8 to 25 μm; and/or the purity of the copper material is more than or equal to 99.9 percent, and can be selected from 99.9 to 99.9999 percent.
3. The method for preparing the graphene/copper composite material according to claim 1 or 2, wherein the carbon source used for the chemical vapor deposition is methane, ethylene, acetylene; and/or the temperature of the chemical vapor deposition is 950-1000 ℃.
4. The method of preparing the graphene/copper composite material according to any one of claims 1 to 3, wherein the number of graphene thin films prepared by chemical vapor deposition is 1 to 5.
5. The method for preparing the graphene/copper composite material according to any one of claims 1 to 4, wherein the thickness of the copper thin film prepared by each physical vapor deposition is 1 to 15 μm; and/or the presence of a gas in the gas,
the background vacuum of each physical vapor deposition reaches 5.5 multiplied by 10 -3 Pa or above, and/or target power density of 1-10W/cm 2 (ii) a And/or the presence of a gas in the gas,
the target current of the physical vapor deposition is 5-20A; and/or the presence of a gas in the gas,
the temperature of the physical vapor deposition is below 500 ℃.
6. The method for preparing the graphene/copper composite material according to any one of claims 1 to 5, wherein the total number of layers of the graphene/copper composite material having a multi-layer structure is 10 to 1000.
7. The method for preparing the graphene/copper composite material according to any one of claims 1 to 6, wherein the operation of preparing the copper thin film and the operation of preparing the graphene thin film are performed in the same chamber.
8. A graphene/copper composite material having a multilayer structure, which is prepared by the method according to any one of claims 1 to 7.
9. The equipment for preparing the graphene/copper composite material is characterized by comprising a CVD (chemical vapor deposition) deposition system and a PVD (physical vapor deposition) deposition system;
preparing a graphene film on the surface of the rolled copper foil by adopting a chemical vapor deposition process in the CVD deposition system to prepare a copper/graphene material;
in the PVD deposition system, a high-purity sputtering copper target material is used as a material, and a physical vapor deposition process is adopted to deposit a copper film on the surface of the copper/graphene material to prepare a Cu/C/Cu material;
then preparing a graphene film on the surface of the Cu/C/Cu material in the CVD deposition system by adopting a chemical vapor deposition process to prepare a Cu/C/Cu/C composite material;
in the PVD deposition system, a high-purity sputtering copper target material is used as a material, and a physical vapor deposition process is adopted to deposit a copper film on the surface of the Cu/C/Cu/C composite material to obtain a Cu/C/Cu/C/Cu composite material;
and repeating the chemical vapor deposition process and the physical vapor deposition process until the graphene/copper composite material with the multilayer structure is prepared.
10. The apparatus of claim 9, wherein the CVD and PVD deposition systems are in the same chamber; and/or the presence of a gas in the atmosphere,
the equipment also comprises a discharging system for conveying the prepared graphene/copper composite material with the multilayer structure out.
CN202210531620.2A 2022-05-13 2022-05-13 Preparation method of graphene/copper composite material combining physical vapor deposition and chemical vapor deposition Pending CN114959697A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105984179A (en) * 2015-03-06 2016-10-05 兰州空间技术物理研究所 Heat sink material and preparation method thereof
CN106584976A (en) * 2016-08-10 2017-04-26 上海交通大学 High-conductivity graphene/copper-based layered composite material and preparation method thereof
CN109735826A (en) * 2019-02-14 2019-05-10 中车工业研究院有限公司 A kind of graphene/copper composite material and its preparation method and application
CN113873750A (en) * 2021-08-31 2021-12-31 华为技术有限公司 Composite copper foil structure, preparation method thereof, copper-clad laminate and printed circuit board

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013176680A1 (en) * 2012-05-25 2013-11-28 Empire Technology Development, Llc Copper substrate for deposition of graphene
US10501845B2 (en) * 2015-11-20 2019-12-10 Fourté International, Sdn. Bhd Thin metal coating methods for high conductivity graphane-metal composites and methods of manufacture
US11127509B2 (en) * 2016-10-11 2021-09-21 Ultraconductive Copper Company Inc. Graphene-copper composite structure and manufacturing method
US10828869B2 (en) * 2017-08-30 2020-11-10 Ultra Conductive Copper Company, Inc. Graphene-copper structure and manufacturing method
US20200294684A1 (en) * 2019-03-12 2020-09-17 TE Connectivity Services Gmbh Enhanced performance ultraconductive copper and process of making
CN112962099A (en) * 2021-02-01 2021-06-15 西南交通大学 High-conductivity copper/graphene/copper composite material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105984179A (en) * 2015-03-06 2016-10-05 兰州空间技术物理研究所 Heat sink material and preparation method thereof
CN106584976A (en) * 2016-08-10 2017-04-26 上海交通大学 High-conductivity graphene/copper-based layered composite material and preparation method thereof
CN109735826A (en) * 2019-02-14 2019-05-10 中车工业研究院有限公司 A kind of graphene/copper composite material and its preparation method and application
CN113873750A (en) * 2021-08-31 2021-12-31 华为技术有限公司 Composite copper foil structure, preparation method thereof, copper-clad laminate and printed circuit board

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