CN110371955B - Preparation method of graphene-metal composite material - Google Patents
Preparation method of graphene-metal composite material Download PDFInfo
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- CN110371955B CN110371955B CN201910660089.7A CN201910660089A CN110371955B CN 110371955 B CN110371955 B CN 110371955B CN 201910660089 A CN201910660089 A CN 201910660089A CN 110371955 B CN110371955 B CN 110371955B
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
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- C01B32/186—Preparation by chemical vapour deposition [CVD]
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1031—Alloys containing non-metals starting from gaseous compounds or vapours of at least one of the constituents
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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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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- 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
- C23C16/02—Pretreatment of the material to be coated
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- 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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- 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
- C23C16/56—After-treatment
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
Abstract
The invention discloses a preparation method of a graphene-metal composite material, which comprises the following steps: (1) taking raw material metal as a substrate, and depositing graphene by adopting a chemical vapor deposition method to obtain a metal raw material with a graphene layer deposited on the surface; (2) an oxidation grinding process: heating the metal raw material deposited with the graphene layer in an oxidizing atmosphere to make the graphene layer uniform, so as to obtain a graphene-metal composite raw material; (3) and stacking or orderly stacking the graphene-metal composite raw materials and then sintering to prepare the graphene-metal composite material. According to the invention, because the graphene film deposited on the metal surface is subjected to oxidation grinding process treatment, graphene 'islands' inevitably generated by deposition of the graphene film by a vapor deposition method are removed, and a complete regular graphene layer is reserved, so that the conductivity of the graphene-metal composite material is improved.
Description
Technical Field
The invention belongs to the field of graphene composite materials, and particularly relates to a preparation method of a graphene-metal composite material.
Background
Graphene is an ideal two-dimensional reinforcing phase in the field of composite materials due to its ultrahigh thermal conductivity (5000W/m), excellent mechanical properties (tensile strength up to 130GPa and Young modulus more than 1.0 TPa) and the like, and the graphene is compounded into base materials such as aluminum, titanium, copper and the like, so that the composite material with light weight, high strength, electric conduction, heat conduction and other functional properties can be expected to be obtained.
In the graphene-metal composite material, generally, a chemical vapor deposition method is adopted to grow graphene on the metal surface, and then a vacuum hot-pressing process is adopted to prepare a graphene-metal material block. The conductivity of the alloy is still to be further improved.
Disclosure of Invention
Aiming at the defects or improvement requirements in the prior art, the invention provides a preparation method of a graphene-metal composite material, which aims to remove 'isolated islands' of a graphene film growing on the surface of a metal through an oxidation grinding process, improve the integrity of a deposited graphite film and further improve the conductivity of the prepared graphene-metal composite material, thereby solving the technical problem that the conductivity of the existing graphene-metal composite material needs to be improved.
In order to achieve the above object, according to an aspect of the present invention, there is provided a method for preparing a graphene-metal composite, including the steps of:
(1) taking raw material metal as a substrate, and depositing graphene by adopting a chemical vapor deposition method to obtain a metal raw material with a graphene layer deposited on the surface;
(2) an oxidation grinding process: heating the metal raw material deposited with the graphene layer obtained in the step (1) in an oxidizing atmosphere to make the graphene layer uniform, so as to obtain a graphene-metal composite raw material;
(3) and (3) stacking or orderly stacking the graphene-metal composite raw materials obtained in the step (2) and then sintering to obtain the graphene-metal composite material.
Preferably, in the preparation method of the graphene-metal composite material, the oxidizing atmosphere is preferably an air atmosphere, the temperature is 150 to 220 ℃, preferably 200 ℃, and the heating time is 1 to 20 min.
Preferably, in the preparation method of the graphene-metal composite material, the raw material metal is a metal foil; the metal species is preferably a simple substance or an alloy of copper or nickel.
Preferably, in the preparation method of the graphene-metal composite material, in the step (1), the graphene is deposited by a chemical vapor deposition method, specifically:
suspending the sheet metal foil in a deposition cavity, and depositing graphene on two sides of the copper foil; or
And (3) enabling the coiled metal foil to pass through the deposition chamber in a continuous roll-to-roll mode, and depositing graphene on the surface of the copper foil.
Preferably, in the preparation method of the graphene-metal composite material, in the step (1), the graphene is deposited by a chemical vapor deposition method, specifically:
and (3) enabling the wound copper foil to pass through the deposition chamber in a continuous roll-to-roll mode, and depositing graphene on the surface of the copper foil.
Step (2) heating the metal raw material deposited with the graphene layer obtained in the step (1) in an oxidizing atmosphere, specifically:
and stopping vacuumizing the roll-to-roll equipment, communicating with the atmospheric environment, keeping the furnace temperature at 200 ℃, and slowly passing the copper foil with the graphene through the heating zone at the speed of 15-300 mm/min.
Preferably, in the preparation method of the graphene-metal composite material, the step (1) of depositing graphene comprises: vacuumizing, polishing the copper foil by using plasma, annealing the copper foil, growing graphene, and rapidly cooling.
Preferably, in the preparation method of the graphene-metal composite material, the gas atmosphere in the step of plasma polishing the copper foil is argon and hydrogen, the flow of the argon is 20-400sccm, and the flow of the hydrogen is 20-100 sccm;
the annealing conditions comprise:
gas atmosphere: argon and hydrogen mixed atmosphere, wherein the flow of the argon is 20-400sccm, and the flow of the hydrogen is 20-100 sccm;
annealing temperature: 500 ℃ to 1050 ℃;
annealing time: 2min to 40 min;
the growth conditions comprise:
gas atmosphere: the method comprises the following steps of mixing methane, argon and hydrogen, wherein the flow rate of the methane is 10-100sccm, the flow rate of the hydrogen is 20-100sccm, and the flow rate of the argon is 0-400 sccm;
growth temperature: 600 ℃ to 1050 ℃;
and (3) growth time: 2min to 40 min;
the rapid cooling step is to rapidly draw out the copper foil from the heating zone to a low temperature zone and cool the copper foil in a vacuum environment.
Preferably, the preparation method of the graphene-metal composite material comprises the following specific steps (3):
and orderly stacking the graphene-metal composite raw materials, and sintering to obtain the orthotropic graphene-metal composite material.
Preferably, in the preparation method of the graphene-metal composite material, the sintering process is vacuum hot-pressing sintering or alternating-current induction sintering.
Preferably, in the preparation method of the graphene-metal composite material, the vacuum degree of the vacuum hot-pressing sintering is 1 to 10 Pa; the given pressure of the pressure head is between 30MPa and 50 MPa; the sintering temperature is 850-.
The vacuum degree of the alternating current induction sintering is 1Pa to 10 Pa; the given pressure of the pressure head is between 30MPa and 50 MPa; the sintering temperature is 850-.
Generally speaking, compared with the prior art, the technical scheme of the invention removes the graphene 'isolated island' inevitably generated by depositing the graphene film by the vapor deposition method and retains the complete regular graphene layer because the graphene film deposited on the metal surface is subjected to the oxidation grinding process, thereby improving the conductivity of the graphene-metal composite material.
Drawings
FIG. 1 is a schematic diagram of an oxidative smoothing process of the present invention;
fig. 2 is a report of a resistivity detection result of the graphene-metal composite provided in embodiment 1 of the present invention;
fig. 3 is a report of a resistivity detection result of the graphene-metal composite provided in embodiment 2 of the present invention;
fig. 4 is a report of resistivity detection results of the graphene-metal composite provided by the comparative example.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The preparation method of the graphene metal composite material provided by the invention comprises the following steps:
(1) taking raw material metal as a substrate, and depositing graphene by adopting a chemical vapor deposition method to obtain a metal raw material with a graphene layer deposited on the surface;
the raw material metal is metal foil; the metal species is preferably a simple substance or an alloy of copper or nickel. The copper and nickel metal substrate is more suitable for the growth of graphene, and a chemical vapor deposition method is adopted to deposit a uniform graphene layer.
The chemical vapor deposition method for depositing the graphene specifically comprises the following steps:
suspending the sheet metal foil in a deposition cavity, and depositing graphene on two sides of the copper foil; or
And (3) enabling the coiled metal foil to pass through the deposition chamber in a continuous roll-to-roll mode, and depositing graphene on the surface of the copper foil.
The graphene deposition process comprises the following steps: vacuumizing, polishing the copper foil by using plasma, annealing the copper foil, growing graphene, and rapidly cooling.
The gas atmosphere of the working procedure of the plasma polishing copper foil is argon and hydrogen, the flow of the argon is 20-400sccm, and the flow of the hydrogen is 20-100 sccm. And (3) polishing by using a radio frequency coil in a chemical vapor deposition device, wherein the radio frequency power is 30-100W, and preferably about 50W.
The annealing conditions comprise:
gas atmosphere: argon and hydrogen mixed atmosphere, wherein the flow of the argon is 20-400sccm, and the flow of the hydrogen is 20-100 sccm;
annealing temperature: 600 ℃ to 1050 ℃;
annealing time: 2min to 40 min;
the growth conditions comprise:
gas atmosphere: the method comprises the following steps of mixing methane, argon and hydrogen, wherein the flow rate of the methane is 10-100sccm, the flow rate of the hydrogen is 20-100sccm, and the flow rate of the argon is 0-400 sccm;
growth temperature: 600 ℃ to 1050 ℃;
and (3) growth time: 2min to 40 min;
the rapid cooling step is to rapidly draw out the copper foil from the heating zone to a low temperature zone and cool the copper foil in a vacuum environment.
The copper foil passes through the deposition cavity in a continuous roll-to-roll mode, the deposition cavity is a vacuum quartz tube and is respectively connected with the feeding end and the discharging end, and the copper foil passes through the quartz tube from the feeding end to reach the discharging end. The quartz tube is about 1.5m long, the radio frequency coil is installed at the front end (close to the feeding end), the tube furnace is arranged at the middle section and is a heating area, and the cooling area is arranged at the rear end (close to the discharging end). The annealing, the growth and the cooling of the graphene are completed in one step in a vacuum cavity of the equipment, so that the annealing, the growth and the cooling of the graphene are in an assembly line process at each stage and are synchronous in time; the time for annealing, growth and cooling depends on the speed of the copper foil from the feed end to the discharge end. Therefore, the continuous roll-to-roll growth of the graphene can greatly improve the preparation yield of the graphene and reduce the cost.
(2) An oxidation grinding process: heating the metal raw material deposited with the graphene layer obtained in the step (1) in an oxidizing atmosphere to make the graphene layer uniform, so as to obtain a graphene-metal composite raw material;
the oxidizing atmosphere is preferably an air atmosphere, the temperature is 150-220 ℃, preferably 200 ℃, and the heating time is 1-20 min. The specific operation is preferably as follows:
and stopping vacuumizing the roll-to-roll equipment, communicating with the atmospheric environment, keeping the furnace temperature at 200 ℃, slowly passing the copper foil with the graphene through the heating area at the speed of about 15-300mm/min, and keeping the copper foil in the heating area for 1-20 min.
In the graphene layer deposited on the surface of the metal raw material in the step (2), due to the randomness of deposition, multiple isolated island-shaped free graphene fragments inevitably occur, as shown in fig. 1, the thickness of the graphene layer is not uniform due to the free graphene fragments, so that the property of the graphene layer is not consistent, and the conductivity after the graphene layer is compounded with copper is affected. We find that the free graphene fragments are easily oxidized, and heated in 150 to 220 ℃ air atmosphere, the incomplete isolated graphene layer is oxidized, and the regular deposited graphene layer is not easily oxidized due to the formation of a stable structure under the oxidation atmosphere and conditions, so that the free graphene isolated graphene layer is oxidized and ground flat by accurately controlling the oxidation conditions, and the complete regular graphene layer is remained, thereby improving the conductivity of the graphene-metal composite material.
(3) And (3) stacking or orderly stacking the graphene-metal composite raw materials obtained in the step (2) and then sintering to obtain the graphene-metal composite material.
And orderly stacking the graphene-metal composite raw materials, and sintering to obtain the orthotropic graphene-metal composite material.
The sintering process is vacuum hot-pressing sintering or alternating current induction sintering;
the vacuum degree of the vacuum hot-pressing sintering is 1Pa to 10 Pa; the given pressure of the pressure head is between 30MPa and 50 MPa; the sintering temperature is 850-.
The vacuum degree of the alternating current induction sintering is 1Pa to 10 Pa; the given pressure of the pressure head is between 30MPa and 50 MPa; the sintering temperature is 850-.
The sintering process is preferably alternating current induction sintering, and the bulk graphene-metal composite material can be rapidly sintered.
The following are examples:
example 1
A preparation method of a graphene metal composite material comprises the following steps:
(1) taking raw material metal as a substrate, and depositing graphene by adopting a chemical vapor deposition method to obtain a metal raw material with a graphene layer deposited on the surface;
the raw material metal is a rolled copper foil;
the chemical vapor deposition method for depositing the graphene specifically comprises the following steps:
and (3) enabling the wound copper foil to pass through the deposition chamber in a continuous roll-to-roll mode, and depositing graphene on the surface of the copper foil.
The graphene deposition process comprises the following steps: vacuumizing, polishing the copper foil by using plasma, annealing the copper foil, growing graphene, and cooling. The whole process flow is synchronously completed in a same cavity in a production line mode, the copper foil penetrates through the cavity at the speed of about 150mm/min, and the time of the copper foil in a heating area is about 2 min.
The gas atmosphere of the copper foil plasma polishing process is argon and hydrogen, the argon flow is 400sccm, and the hydrogen flow is 100 sccm. And (3) polishing by adopting a radio frequency coil in chemical vapor deposition equipment, wherein the radio frequency power is 100W.
The annealing conditions comprise:
gas atmosphere: argon and hydrogen mixed atmosphere, wherein the flow of the argon is 400sccm, and the flow of the hydrogen is 100 sccm;
annealing temperature: 1050 ℃; for a period of 2min
The growth conditions comprise:
gas atmosphere: the method comprises the following steps of mixing methane, argon and hydrogen, wherein the flow rate of methane is 100sccm, the flow rate of hydrogen is 100sccm, and the flow rate of argon is 400 sccm;
growth temperature: 1050 ℃;
the cooling step is to draw out the copper foil from the heating zone to a low temperature zone and cool the copper foil in a vacuum environment.
(2) An oxidation grinding process: heating the metal raw material deposited with the graphene layer obtained in the step (1) in an oxidizing atmosphere to make the graphene layer uniform, so as to obtain a graphene-metal composite raw material;
the oxidation atmosphere is carried out in an air atmosphere at a temperature of 220 ℃. The specific operation is as follows:
and stopping vacuumizing the roll-to-roll equipment, communicating with the atmospheric environment, keeping the furnace temperature at 220 ℃, slowly passing the copper foil with the graphene through the heating zone for 300mm at the speed of about 15mm/min, and passing the copper foil through the heating zone for about 20 min.
(3) Cutting the rolled graphene-metal composite raw material obtained in the step (2) into round pieces with the same inner diameter as that of a hot-pressing die, and sintering after stacking or orderly stacking to obtain the graphene-metal composite material.
And orderly stacking the graphene-metal composite raw materials, and sintering to obtain the orthotropic graphene-metal composite material.
The sintering process is vacuum hot-pressing sintering; pumping to 10Pa in vacuum degree; the pressure head set pressure is between 30 MPa; heating to 1050 deg.C, maintaining the temperature for 120min, and cooling with pressure head.
Example 2
A preparation method of a graphene metal composite material comprises the following steps:
(1) taking raw material metal as a substrate, and depositing graphene by adopting a chemical vapor deposition method to obtain a metal raw material with a graphene layer deposited on the surface;
the raw material metal is a rolled copper foil;
the chemical vapor deposition method for depositing the graphene specifically comprises the following steps:
and (3) enabling the wound copper foil to pass through the deposition chamber in a continuous roll-to-roll mode, and depositing graphene on the surface of the copper foil.
The graphene deposition process comprises the following steps: vacuumizing, polishing the copper foil by using plasma, annealing the copper foil, growing graphene, and cooling. The whole process flow is synchronously completed in a same cavity in a production line mode, the copper foil penetrates through the cavity at the speed of about 80mm/min, and the time of the copper foil in a heating area is about 20 min.
The gas atmosphere of the copper foil plasma polishing process is argon and hydrogen, the argon flow is 200sccm, and the hydrogen flow is 40 sccm. And (3) polishing by adopting a radio frequency coil in chemical vapor deposition equipment, wherein the radio frequency power is 50W.
The annealing conditions comprise:
gas atmosphere: argon and hydrogen mixed atmosphere, wherein the flow of the argon is 200sccm, and the flow of the hydrogen is 40 sccm;
annealing temperature: 900 ℃;
the growth conditions comprise:
gas atmosphere: the method comprises the following steps of mixing methane, argon and hydrogen, wherein the flow rate of methane is 40sccm, the flow rate of hydrogen is 40sccm, and the flow rate of argon is 200 sccm;
growth temperature: 900 ℃;
the cooling step is to draw out the copper foil from the heating zone to a low temperature zone and cool the copper foil in a vacuum environment.
(2) An oxidation grinding process: heating the metal raw material deposited with the graphene layer obtained in the step (1) in an oxidizing atmosphere to make the graphene layer uniform, so as to obtain a graphene-metal composite raw material;
the oxidation atmosphere is carried out in an air atmosphere at a temperature of 200 ℃. The specific operation is as follows:
and stopping vacuumizing the roll-to-roll equipment, communicating with the atmospheric environment, keeping the furnace temperature at 200 ℃, slowly passing the copper foil with the graphene through the heating zone for 300mm at the speed of about 50mm/min, and passing the copper foil through the heating zone for about 6 min.
(3) Cutting the rolled graphene-metal composite raw material obtained in the step (2) into round pieces with the same inner diameter as that of a hot-pressing die, and sintering after stacking or orderly stacking to obtain the graphene-metal composite material.
And orderly stacking the graphene-metal composite raw materials, and sintering to obtain the orthotropic graphene-metal composite material.
The sintering process is vacuum hot-pressing sintering; pumping to 10Pa in vacuum degree; the pressure head set pressure is between 30 MPa; heating to 1050 deg.C, maintaining the temperature for 120min, and cooling with pressure head.
Example 3
A preparation method of a graphene metal composite material comprises the following steps:
(1) taking raw material metal as a substrate, and depositing graphene by adopting a chemical vapor deposition method to obtain a metal raw material with a graphene layer deposited on the surface;
the raw material metal is a sheet copper foil;
the chemical vapor deposition method for depositing the graphene specifically comprises the following steps:
the sheet copper foil is suspended in a deposition chamber, and graphene is deposited on both sides of the copper foil.
The graphene deposition process comprises the following steps: vacuumizing, polishing the copper foil by using plasma, annealing the copper foil, growing graphene, and rapidly cooling. The whole process flow is sequentially completed in the same cavity.
The working procedure gas atmosphere of the plasma polished copper foil is argon and hydrogen, the argon flow is 20sccm, and the hydrogen flow is 20 sccm. And (3) polishing by using a radio frequency coil in chemical vapor deposition equipment, wherein the radio frequency power is 30W.
The annealing conditions comprise:
gas atmosphere: argon and hydrogen mixed atmosphere, wherein the flow of the argon is 20sccm, and the flow of the hydrogen is 20 sccm;
annealing temperature: 600 ℃;
annealing time: 40 min;
the growth conditions comprise:
gas atmosphere: the method comprises the following steps of mixing methane, argon and hydrogen, wherein the flow rate of methane is 10sccm, the flow rate of hydrogen is 20sccm, and the flow rate of argon is 0 sccm;
growth temperature: 600 ℃;
and (3) growth time: 40 min;
the rapid cooling step is to rapidly draw out the copper foil from the heating zone to a low temperature zone and cool the copper foil in a vacuum environment.
(2) An oxidation grinding process: heating the metal raw material deposited with the graphene layer obtained in the step (1) in an oxidizing atmosphere to make the graphene layer uniform, so as to obtain a graphene-metal composite raw material;
the oxidizing atmosphere is preferably carried out in an air atmosphere at a temperature of 150 ℃ for 15 min. The specific operation is as follows:
and stopping vacuumizing the roll-to-roll equipment, communicating with the atmospheric environment, keeping the furnace temperature at 150 ℃, placing the sheet copper foil with the graphene grown in the heating area for 15min, then drawing out to a low-temperature area, cooling to room temperature, and taking out.
(3) And (3) cutting the flaky graphene-metal composite raw material obtained in the step (2) into round pieces with the same inner diameter as that of a hot-pressing die, and sintering after stacking or orderly stacking to obtain the graphene-metal composite material.
And orderly stacking the graphene-metal composite raw materials, and sintering to obtain the orthotropic graphene-metal composite material.
Pumping to 5Pa in vacuum degree; the pressure head set pressure is 50 MPa; heating to 1000 deg.C, maintaining the temperature for 120min, and cooling with pressure head.
Comparative example
A preparation method of a graphene metal composite material comprises the following steps:
(1) taking raw material metal as a substrate, and depositing graphene by adopting a chemical vapor deposition method to obtain a metal raw material with a graphene layer deposited on the surface;
the raw material metal is a rolled copper foil;
the chemical vapor deposition method for depositing the graphene specifically comprises the following steps:
and (3) enabling the wound copper foil to pass through the deposition chamber in a continuous roll-to-roll mode, and depositing graphene on the surface of the copper foil.
The graphene deposition process comprises the following steps: vacuumizing, polishing the copper foil by using plasma, annealing the copper foil, growing graphene, and cooling. The whole process flow is synchronously completed in a same cavity in a production line mode, the copper foil penetrates through the cavity at the speed of about 80mm/min, and the time of the copper foil in a heating area is about 20 min.
The gas atmosphere of the copper foil plasma polishing process is argon and hydrogen, the argon flow is 400sccm, and the hydrogen flow is 40 sccm. And (3) polishing by adopting a radio frequency coil in chemical vapor deposition equipment, wherein the radio frequency power is 50W.
The annealing conditions comprise:
gas atmosphere: argon and hydrogen mixed atmosphere, wherein the flow of the argon is 400sccm, and the flow of the hydrogen is 40 sccm;
annealing temperature: 1000 ℃;
the growth conditions comprise:
gas atmosphere: the method comprises the following steps of mixing methane, argon and hydrogen, wherein the flow rate of methane is 40sccm, the flow rate of hydrogen is 40sccm, and the flow rate of argon is 400 sccm;
growth temperature: 1000 ℃;
the cooling step is to draw out the copper foil from the heating zone to a low temperature zone and cool the copper foil in a vacuum environment.
(2) Cutting the rolled graphene-metal composite raw material obtained in the step (1) into round pieces with the same inner diameter as that of a hot-pressing die, and sintering after stacking or orderly stacking to obtain the graphene-metal composite material.
And orderly stacking the graphene-metal composite raw materials, and sintering to obtain the orthotropic graphene-metal composite material.
The sintering process is vacuum hot-pressing sintering; pumping to 10Pa in vacuum degree; the pressure head set pressure is 30 MPa; heating to 1050 deg.C, maintaining the temperature for 120min, and cooling with pressure head.
The graphene-copper prepared in examples 1 and 2 and comparative example meets the test results of the resistivity of the material according to the entrusted watson monitoring, and the test reports are shown in the following tables:
the detection result shows that the resistivity of the graphene-copper composite material prepared by the preparation method is obviously improved compared with that of the graphene-copper composite material prepared by the oxidation grinding process.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (13)
1. A preparation method of a graphene-metal composite material is characterized by comprising the following steps:
(1) taking raw material metal as a substrate, and depositing graphene by adopting a chemical vapor deposition method to obtain a metal raw material with a graphene layer deposited on the surface;
(2) an oxidation grinding process: heating the metal raw material deposited with the graphene layer obtained in the step (1) in an oxidizing atmosphere at the temperature of 150-220 ℃ to make the graphene layer uniform, so as to obtain a graphene-metal composite raw material;
(3) and (3) stacking and sintering the graphene-metal composite raw materials obtained in the step (2) to obtain the graphene-metal composite material.
2. The method for preparing the graphene-metal composite material according to claim 1, wherein the graphene-metal composite material is prepared by orderly stacking and sintering the graphene-metal composite raw materials obtained in the step (2) in the step (3).
3. The method of preparing a graphene-metal composite according to claim 1, wherein the oxidizing atmosphere is an air atmosphere.
4. The method of preparing a graphene-metal composite according to claim 1, wherein the heating temperature in the step (2) is 200 ℃ and the heating time is 1 to 20 min.
5. The method of preparing a graphene-metal composite according to claim 1, wherein the raw material metal is a metal foil.
6. The method of preparing a graphene-metal composite according to claim 5, wherein the metal species is a simple substance or an alloy of copper or nickel.
7. The method for preparing the graphene-metal composite material according to claim 1, wherein the step (1) of depositing the graphene by a chemical vapor deposition method specifically comprises:
suspending a sheet metal foil in a deposition cavity, and depositing graphene on two sides of the metal foil; or
And (3) passing the rolled metal foil through the deposition chamber in a continuous roll-to-roll mode, and depositing graphene on the surface of the metal foil.
8. The method for preparing the graphene-metal composite material according to claim 7, wherein the step (1) of depositing the graphene by a chemical vapor deposition method specifically comprises:
enabling the rolled copper foil to pass through a deposition cavity in a continuous roll-to-roll mode, and depositing graphene on the surface of the copper foil;
step (2) heating the metal raw material deposited with the graphene layer obtained in the step (1) in an oxidizing atmosphere, specifically:
and stopping vacuumizing the roll-to-roll equipment, communicating with the atmospheric environment, keeping the furnace temperature at 200 ℃, and slowly passing the copper foil with the graphene through the heating zone at the speed of 15-300 mm/min.
9. The method for preparing a graphene-metal composite material according to claim 1, wherein the step (1) of depositing graphene comprises: vacuumizing, polishing the copper foil by using plasma, annealing the copper foil, growing graphene, and rapidly cooling.
10. The method of preparing a graphene-metal composite according to claim 9, wherein the gas atmosphere in the step of plasma polishing the copper foil is argon gas and hydrogen gas, the flow rate of the argon gas is 20 to 400sccm, and the flow rate of the hydrogen gas is 20 to 100 sccm;
the annealing conditions comprise:
gas atmosphere: argon and hydrogen mixed atmosphere, wherein the flow of the argon is 20-400sccm, and the flow of the hydrogen is 20-100 sccm;
annealing temperature: 600 ℃ to 1050 ℃;
annealing time: 2min to 40 min;
the growth conditions comprise:
gas atmosphere: the method comprises the following steps of mixing methane, argon and hydrogen, wherein the flow rate of the methane is 10-100sccm, the flow rate of the hydrogen is 20-100sccm, and the flow rate of the argon is 0-400 sccm;
growth temperature: 600 ℃ to 1050 ℃;
and (3) growth time: 2min to 40 min;
the rapid cooling step is to rapidly draw out the copper foil from the heating zone to a low temperature zone and cool the copper foil in a vacuum environment.
11. The method for preparing the graphene-metal composite material according to claim 1, wherein the step (3) is specifically:
and orderly stacking the graphene-metal composite raw materials, and sintering to obtain the orthotropic graphene-metal composite material.
12. The method of preparing a graphene-metal composite according to claim 11, wherein the sintering process is vacuum hot-press sintering or ac induction sintering.
13. The method of preparing a graphene-metal composite according to claim 12, wherein the vacuum hot press sintering is performed in a vacuum degree of 1Pa to 10 Pa; the given pressure of the pressure head is between 30MPa and 50 MPa; the sintering temperature is 850-;
the vacuum degree of the alternating current induction sintering is 1Pa to 10 Pa; the given pressure of the pressure head is between 30MPa and 50 MPa; the sintering temperature is 850-.
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