CN115074694B - Preparation method of graphene film - Google Patents

Preparation method of graphene film Download PDF

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Publication number
CN115074694B
CN115074694B CN202210768556.XA CN202210768556A CN115074694B CN 115074694 B CN115074694 B CN 115074694B CN 202210768556 A CN202210768556 A CN 202210768556A CN 115074694 B CN115074694 B CN 115074694B
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graphene film
growth substrate
growth
porous carbon
carbon material
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CN115074694A (en
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王炜
沈大勇
谭化兵
瞿研
郭冰
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Jiangsu Jiangnan Elenyl Graphene Technology Co ltd
Changzhou Sixth Element Semiconductor Co ltd
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Jiangsu Jiangnan Elenyl Graphene Technology Co ltd
Changzhou Sixth Element Semiconductor Co ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/186—Preparation by chemical vapour deposition [CVD]
    • 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
    • C23C16/44—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 method of coating
    • C23C16/458—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 method of coating characterised by the method used for supporting substrates in the reaction chamber
    • C23C16/4581—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 method of coating characterised by the method used for supporting substrates in the reaction chamber characterised by material of construction or surface finish of the means for supporting the substrate

Abstract

The scheme discloses a preparation method of a graphene film, which comprises the following steps: placing a growth substrate on a supporting structure and continuously conveying the growth substrate along with the supporting structure into a reaction cavity for performing chemical vapor deposition reaction at a preset speed under the action of a conveying mechanism; in the reaction cavity, the graphene film grows on a growth substrate, and the growth substrate moves in the reaction cavity along with the supporting structure at a preset speed under the action of the conveying mechanism until the growth substrate is conveyed out of the reaction cavity. According to the method, when the graphene film is prepared by the CVD method, continuous preparation of the graphene film is realized, the growth temperature is not required to be reduced, and the high-quality graphene film can be prepared.

Description

Preparation method of graphene film
Technical Field
The invention relates to the technical field of film preparation, in particular to a preparation method of a graphene film.
Background
Graphene is a two-dimensional crystal with only one layer of atomic thickness and is formed by carbon atoms, and is a new material with thinnest natural world and highest strength at present. The graphene film production method is to introduce vapor containing gaseous reactants or liquid reactants forming film elements and other gases required by the reaction into a reaction chamber, and to generate chemical reaction on the surface of a substrate to grow a film, namely a chemical vapor deposition method (called as CVD method hereinafter).
The current common graphene film production equipment is to put a substrate material into the equipment, grow a graphene film on the substrate material, take the graphene film out, put a new substrate material into the equipment, and perform the next graphene film growth. The production mode has low working efficiency, needs to be taken and placed for many times, and because the temperature required by the growth of the graphene film is higher, in order to avoid scalding during taking and placing, the temperature needs to be reduced firstly, and then the temperature is raised after the completion of taking and placing, so that the production working time is further prolonged, the reaction temperature is raised, the energy consumption is high, the production cost is increased, and the continuous growth of the coiled material is a necessary trend of industry development.
In this aspect, there are many researches at present, and the main difficulty is that the metal growth substrate is easy to soften at high temperature, and is easy to stretch, deform and even break during the growth of coiled materials, and adhesion welding and other conditions are easy to occur, so that the temperature can only be reduced for growth. The temperature decrease is accompanied by a decrease in growth quality, and in view of this, various methods such as plasma-assisted enhanced CVD method, changing the horizontal growth structure, and low-temperature cracking of the carbon source have been adopted at present. Although the methods can be used for growth, the growth quality of the method is not comparable to that of a graphene film prepared by a high-temperature thermal CVD method due to the generation of amorphous carbon caused by insufficient temperature, impurities in the growth process, ion bombardment and other reasons, and particularly when continuous single-layer graphene films with better quality are required to be prepared.
Disclosure of Invention
An object of the present invention is to provide a method for preparing a graphene film, which can realize continuous preparation of a graphene film and can prepare a high-quality graphene film without reducing a growth temperature when preparing a graphene film by a CVD method.
In order to achieve the above purpose, the scheme is as follows:
a preparation method of a graphene film comprises the following steps:
placing a growth substrate on a supporting structure and continuously conveying the growth substrate along with the supporting structure into a reaction cavity for performing chemical vapor deposition reaction at a preset speed under the action of a conveying mechanism;
in the reaction cavity, the graphene film grows on a growth substrate, and the growth substrate moves in the reaction cavity along with the supporting structure at a preset speed under the action of the conveying mechanism until the growth substrate is conveyed out of the reaction cavity.
Preferably, the support structure is made of a porous carbon material, and the porosity of the porous carbon material is 10% -95%.
Preferably, the tensile strength of the porous carbon material is 4MPa or more.
Preferably, the thickness of the support structure is 10 μm to 5mm.
Preferably, the growth substrate is coiled material, and the material of the growth substrate comprises one or two of copper, iron, cobalt, ruthenium, iridium, nickel, palladium and gold.
Preferably, the material of the growth substrate is copper, nickel or copper-nickel alloy.
Preferably, the environmental temperature for growing the graphene film in the reaction cavity is 700-1400 ℃; the environmental pressure for growing the graphene film is 0.1 Pa-0.01 MPa.
Preferably, the gas forming the growth environment of the graphene film in the reaction cavity comprises one or two of hydrogen, hydrocarbon gas, nitrogen, argon, ethanol, water vapor and oxygen.
Preferably, the gas forming the graphene film growing environment is a mixed gas of hydrogen and methane.
Preferably, the speed at which the growth substrate moves in the reaction chamber along with the support structure at a predetermined speed under the action of the transfer mechanism is 0.1 m/min to 60 m/min; the temperature of the growth substrate as it is transferred out of the reaction chamber is lower than 400 ℃.
The beneficial effects of this scheme are as follows:
according to the scheme, the porous carbon film is introduced into the growth preparation process of the graphene film, and the excellent chemical stability and mechanical property of the porous carbon film are utilized, so that the metal substrate for growing the graphene film can be conveyed without bearing tensile force at high temperature, deformation at high temperature is avoided, and the situation that the graphene film is stretched and broken or even broken due to stretching of the metal substrate is avoided.
The porous carbon material has excellent air permeability, and when being attached to the surface of the substrate, the porous carbon material can still enable the growth atmosphere to reach the surface of the growth substrate through the porous carbon layer for catalytic cracking growth, so that the growth of graphene on a plurality of surfaces of the substrate can be realized. By selecting porous carbon materials with different porosities, controllable growth of the graphene film can be realized.
The method is simple in implementation mode, can be directly put into use on the basis of the current roll-to-roll growth equipment, is low in application and popularization difficulty, and is beneficial to industrialized growth application.
Drawings
In order to more clearly illustrate the practice of the present solution, the drawings that are required for the description of the embodiments will be briefly described below, it being apparent that the drawings in the following description are only some embodiments of the present solution and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram showing the flow of gases when a porous carbon material supports a growth substrate in example 1;
FIG. 2 is a Raman spectrum of the graphene film prepared in example 1;
FIG. 3 is a Raman spectrum of the graphene film prepared in example 2;
FIG. 4 is a Raman spectrum of the graphene film prepared in example 3;
fig. 5 is a raman spectrum of the graphene film prepared in example 4.
Detailed Description
Embodiments of the present solution are described in further detail below. It is clear that the described embodiments are only some of the embodiments of the present solution, not an exhaustive list of all embodiments. It should be noted that, in the case of no conflict, the embodiments and features in the embodiments in the present solution may be combined with each other.
The porous carbon material still maintains good mechanical strength and chemical stability at high temperature of about one thousand DEG C, has no obvious volatile impurities, can bear pressure or tensile force and is not deformed or broken. The main component of the graphene film is carbon, and the graphene film can not be adhered to a metal material, welded and the like at high temperature, and cannot be polluted by impurities. By utilizing the properties, the growth of the graphene film can be realized by supporting the metal substrate for growing the graphene film by the porous carbon material in the continuous production process. In the transmission process at the high temperature of growth, continuous transmission of the growth metal substrate can be realized only by applying push-pull force to the porous carbon material, and the metal substrate can not be subjected to push-pull force, so that the situation of stretching deformation and even fracture can not occur. After the growth is completed, the metal substrate is cooled to a temperature with enough mechanical strength, and can be independently conveyed without stretching deformation or even fracture.
The porous carbon material has excellent porosity, can enable gas to penetrate the material, and can realize that the surface of the porous carbon material is bonded when the metal substrate grows, the growth atmosphere is not blocked, and the metal substrate can still grow normally by utilizing the characteristic. The porous carbon material mainly contains steady-state carbon, does not react with metals such as mutual melting, does not react with the carbon source atmosphere for growth, and does not introduce impurities to pollute the grown graphene film, so that the growth quality of the graphene film can be fully ensured. Also because of this feature, porous carbon materials can be coated on one or both sides of the grown metal substrate, so that the design of the equipment and process can be more flexible, which is advantageous for industrial use.
The porous carbon material is applied to the process of preparing the graphene film by the CVD method, and high-temperature continuous preparation in the process of preparing the graphene film by the CVD method is realized by utilizing good mechanical property and excellent air permeability at high temperature.
A preparation method of a graphene film comprises the following steps:
placing a growth substrate on a supporting structure and continuously conveying the growth substrate along with the supporting structure into a reaction cavity for performing chemical vapor deposition reaction at a preset speed under the action of a conveying mechanism;
in the reaction cavity, the graphene film grows on a growth substrate, and the growth substrate is continuously conveyed out of the reaction cavity along with the supporting structure at a preset speed under the action of the conveying mechanism.
In the reaction cavity, after the graphene film grows on the growth substrate, the temperature of the growth substrate is reduced to below 400 ℃, and then rolling or subsequent processing is carried out.
If the growth substrate is conveyed out of the reaction cavity at a higher temperature, adhesion and wrinkling of the metal substrate can be caused, and the graphene can be possibly damaged due to oxidation caused by contact with oxidizing atmosphere, so that the growth substrate of the grown graphene film is conveyed out of the reaction cavity after the temperature is reduced to below 400 ℃, different environmental temperatures can be realized in the same cavity because the reaction cavity is of a multi-stage temperature control structure, and the conveying mechanism passes through the environments of the reaction cavity at different temperatures, so that control of different temperatures and a cooling process can be realized.
Because the growth substrate is supported by the porous carbon material in the growth environment of the reaction chamber, in the transmission process, the transmission power acts on the support structure, so the growth substrate can not be subjected to tensile force and can not be subjected to tensile deformation in the moving process.
In one embodiment, the growth substrate is a coiled material, and the material of the growth substrate comprises one or two of copper, iron, cobalt, ruthenium, iridium, nickel, palladium and gold; preferably, the material of the growth substrate is copper, nickel or copper-nickel alloy.
In one embodiment, the ambient temperature for growing the graphene film in the reaction chamber is 700-1400 ℃; the environmental pressure for growing the graphene film is 0.1 Pa-0.01 MPa.
In one embodiment, the gas forming the growth environment of the graphene film in the reaction cavity comprises one or two of hydrogen, hydrocarbon gas, nitrogen, argon, ethanol, water vapor and oxygen; preferably, the gas forming the graphene film growth environment is a mixed gas of hydrogen and methane.
In one embodiment, the support structure is made of a porous carbon material, and the porosity of the porous carbon material is 10% -95%.
The porous carbon materials used in the present application are affordable, do not deform, do not chemically react, do not crack and melt at temperatures not less than 1000 ℃, and are not less than the growth ambient temperature.
In one embodiment, the porous carbon material has a tensile strength of 4MPa or greater.
In one embodiment, the thickness of the support structure is 10 μm to 5mm.
In one embodiment, the speed of movement of the growth substrate is between 0.1 meters/minute and 60 meters/minute.
The porous carbon material has better flexibility, can serve as a conveying and supporting structure layer to play a role of conveying a belt sample, and the method can solve the problem that when a graphene film grows on a metal substrate at a high temperature, the metal substrate is easy to stretch and deform or break by restricting the tensile strength of the porous carbon material to meet the requirement of being stretched and used by introducing the porous carbon material, and meanwhile, the problem that graphene cannot effectively grow on the surface of the substrate after being covered is avoided by virtue of the porosity property, so that the growth of a multilayer structure can be realized.
The present application will be described with reference to specific examples.
Example 1
As shown in fig. 1, the porous carbon material 206 supports the growth substrate 205 on one surface, and the gas 201 may directly reach the surface of the growth substrate 205 or may directly reach the surface of the growth substrate 205 through the porous carbon material 206. Before the reaction starts, the growth substrate 205 is placed on the porous carbon material 206 and is transferred into a reaction chamber where a chemical vapor deposition reaction is performed along with the porous carbon material 206 by a transfer mechanism;
in the reaction cavity, the growth substrate continuously moves along with the porous carbon material at a preset speed under the action of the conveying mechanism, and the longer the growth substrate stays in the reaction cavity, the thicker the graphene film growing on the growth substrate; the growth substrate 205 is transferred out of the reaction chamber along with the porous carbon material 206 into the reaction chamber for a period of time at a predetermined transfer rate. The temperature outside the reaction cavity is lower than 250 ℃, the growth substrate and the porous carbon material are cooled outside the reaction cavity, and the growth substrate is rolled or processed later after the temperature is reduced.
In this embodiment, the temperature of the growth environment in the reaction chamber is 850 ℃, the pressure is 400Pa, the gas forming the growth environment in the reaction chamber is a mixed gas of methane and hydrogen, the volume ratio of methane to hydrogen is 1:4, and the temperature outside the reaction chamber is lower than 250 ℃. The material of the growth substrate used for the reaction is continuous rolled copper-nickel alloy foil, the mass ratio of copper to nickel in the alloy is 9:1, the thickness of the growth substrate is 25 microns, the porosity of the porous carbon material used as a supporting structure is 30% -40%, the tensile strength is not lower than 4.5MPa, the porous carbon material is free from deformation and chemical reaction, the temperature of cracking and melting is 1300 ℃, and the thickness of the porous carbon material is 0.6mm.
In this embodiment, the growth substrate is supported by the porous carbon material, the power of the conveying mechanism acts on the porous carbon material, the growth substrate is conveyed into the reaction chamber at a speed of 0.3m/min along with the porous carbon material under the action of the conveying mechanism to perform a chemical vapor deposition reaction, the residence time of the growth substrate in the reaction chamber is 10min, and then the growth substrate is conveyed out of the reaction chamber at a speed of 0.3m/min along with the porous carbon material under the action of the conveying mechanism.
After the preparation of the graphene film on the growth substrate is completed, the growth substrate is separated from the porous carbon material along with the fact that the temperature of the porous carbon material outside the reaction cavity is reduced to be not more than 250 ℃, and the growth substrate is subjected to subsequent rolling or processing.
The range of sheet resistance of the graphene film after growth is 300 to 500 ohm/sq in the intrinsic state after transfer, and the full spectrum light transmittance of the visible light wave band is 92 to 96 percent after the influence of the transfer substrate is eliminated. The Raman spectrum instrument shows that the growth quality is good, the number of graphene film layers is 2-5, and the Raman spectrum is shown in figure 2.
Example 2
In this embodiment, the temperature of the growth environment in the reaction chamber is 900 ℃, the pressure is 400Pa, the gas forming the growth environment in the reaction chamber is a mixed gas of ethylene and hydrogen, the volume ratio of ethylene and hydrogen is 1:8, the temperature outside the reaction chamber is lower than 350 ℃,504 is a schematic drawing of the growth substrate in transmission, the material of the growth substrate used in the reaction is a continuous rolled copper foil with the purity of not lower than 99%, the thickness of the growth substrate is 50 micrometers, the porosity of the porous carbon material used as a supporting structure is 30% -40%, the tensile strength is not lower than 4.5MPa, the porous carbon material is bearable and does not deform, the chemical reaction does not occur, the temperature of not cracking and melting is 1300 ℃, and the thickness of the porous carbon material is 0.5mm.
In this embodiment, the growth substrate is supported by the porous carbon material, the power of the conveying mechanism acts on the porous carbon material, the growth substrate is conveyed into the reaction chamber at a speed of 0.5m/min along with the porous carbon material under the action of the conveying mechanism to perform a chemical vapor deposition reaction, the residence time of the growth substrate in the reaction chamber is 6min, and then the growth substrate is conveyed out of the reaction chamber at a speed of 0.5m/min along with the porous carbon material under the action of the conveying mechanism.
After the preparation of the graphene film on the growth substrate is completed, the growth substrate is separated from the porous carbon material along with the fact that the temperature of the porous carbon material outside the reaction cavity is reduced to be not more than 350 ℃, and the growth substrate is subjected to subsequent rolling or processing.
The range of sheet resistance of the graphene film after growth is 400 to 600 ohm/sq in the intrinsic state after transfer, and the visible light wave band full spectrum light transmittance is 95 to 97.5 percent after the influence of the transfer substrate is eliminated. The Raman spectrum instrument shows that the growth quality is good, the number of graphene film layers is 1-3, and the Raman spectrum is shown in figure 3.
Example 3
In this embodiment, the temperature of the growth environment in the reaction chamber is 950 ℃ and the pressure is 300Pa, and the gas forming the growth environment in the reaction chamber is a mixed gas of methane and hydrogen, wherein the volume ratio of methane to hydrogen is 1:5, and the temperature outside the reaction chamber is lower than 300 ℃. The material of the growth substrate used in the reaction is a continuous coiled copper foil with the purity not lower than 99.9%, the thickness of the growth substrate is 30 microns, the porosity of the porous carbon material used as a supporting structure is 20% -30%, the tensile strength is not lower than 4.8MPa, the porous carbon material is bearable and does not deform, does not undergo chemical reaction, the temperature of cracking and melting is 1400 ℃, and the thickness of the porous carbon material is 0.6mm.
In this embodiment, the growth substrate is supported by the porous carbon material, the power of the conveying mechanism acts on the porous carbon material, the growth substrate is conveyed into the reaction chamber at a speed of 0.2m/min along with the porous carbon material under the action of the conveying mechanism to perform a chemical vapor deposition reaction, the residence time of the growth substrate in the reaction chamber is 10min, and then the growth substrate is conveyed out of the reaction chamber at a speed of 0.2m/min along with the porous carbon material under the action of the conveying mechanism.
After the preparation of the graphene film on the growth substrate is completed, the growth substrate is separated from the porous carbon material along with the fact that the temperature of the porous carbon material outside the reaction cavity is reduced to be not more than 300 ℃, and the growth substrate is subjected to subsequent rolling or processing.
The range of sheet resistance of the graphene film after growth is 350 to 450 ohm/sq after transfer in the intrinsic state, and the full spectrum light transmittance of the visible light wave band is 96 to 97.5 percent after the influence of the transfer substrate is eliminated. The Raman spectrum instrument shows that the growth quality is good, the number of graphene film layers is 1-2, and the Raman spectrum is shown in figure 4.
Example 4
In this embodiment, the temperature of the growth environment in the reaction chamber is 1000 ℃, the pressure is 300Pa, the gas forming the growth environment in the reaction chamber is a mixed gas of methane and hydrogen, wherein the volume ratio of methane to hydrogen is 1:6, and the temperature outside the reaction chamber is lower than 350 ℃. The material of the growth substrate used in the reaction is a continuous coiled copper foil with the purity not lower than 99.9%, the thickness of the growth substrate is 25 microns, the porosity of the porous carbon material used as a supporting structure is 50% -70%, the tensile strength is not lower than 4.3MPa, the porous carbon material can bear no deformation and no chemical reaction, the temperature of no cracking and melting is 1200 ℃, and the thickness of the porous carbon material is 0.3mm.
In this embodiment, the growth substrate is supported by the porous carbon material, the power of the conveying mechanism acts on the porous carbon material, the growth substrate is conveyed into the reaction chamber at a speed of 1m/min along with the porous carbon material under the action of the conveying mechanism to perform a chemical vapor deposition reaction, the residence time of the growth substrate in the reaction chamber is 10min, and then the growth substrate is conveyed out of the reaction chamber at a speed of 1m/min along with the porous carbon material under the action of the conveying mechanism.
After the preparation of the graphene film on the growth substrate is completed, the growth substrate is separated from the porous carbon material along with the fact that the temperature of the porous carbon material outside the reaction cavity is reduced to be not more than 350 ℃, and the growth substrate is subjected to subsequent rolling or processing.
The range of sheet resistance of the graphene film after growth is 350 to 500 ohm/sq in the intrinsic state after transfer, and the visible light band full spectrum light transmittance is 95.5 to 97.5 percent after the influence of a transfer substrate is eliminated. The Raman spectrum instrument shows that the growth quality is good, the number of graphene film layers is 1-2, and the Raman spectrum is shown in figure 5.
In the method, a metallic growth substrate in a coil form is unreeled and then enters a reaction cavity from normal temperature, and is supported by a porous carbon material in the reaction cavity. The porous carbon material is conveyed along with the surface of the porous carbon material under the action of the conveying mechanism, and the growth substrate made of metal materials is not subjected to transverse stretching force in the conveying process. After the growth is completed, the growth substrate is cooled to a proper temperature along with the porous carbon material, separated from the porous carbon material, and independently conveyed for rolling or subsequent processing.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.

Claims (9)

1. The preparation method of the graphene film is characterized by comprising the following steps of:
placing a growth substrate on a supporting structure and continuously conveying the growth substrate along with the supporting structure into a reaction cavity for performing chemical vapor deposition reaction at a preset speed under the action of a conveying mechanism;
in the reaction cavity, the graphene film grows on a growth substrate, and the growth substrate moves in the reaction cavity along with a supporting structure at a preset speed under the action of a conveying mechanism until the growth substrate is conveyed out of the reaction cavity;
the support structure is made of porous carbon material, and the porosity of the porous carbon material is 10% -95%.
2. The method for producing a graphene film according to claim 1, wherein the tensile strength of the porous carbon material is 4MPa or more.
3. The method for preparing a graphene film according to claim 1, wherein the thickness of the support structure is 10 μm to 5mm.
4. The method for preparing a graphene film according to claim 1, wherein the growth substrate is a coiled material, and the material of the growth substrate comprises one or two of copper, iron, cobalt, ruthenium, iridium, nickel, palladium and gold.
5. The method for preparing a graphene film according to claim 4, wherein the growth substrate is made of copper, nickel or copper-nickel alloy.
6. The method for preparing the graphene film according to claim 1, wherein the environmental temperature for growing the graphene film in the reaction chamber is 700-1400 ℃; the environmental pressure for growing the graphene film is 0.1 Pa-0.01 MPa.
7. The method of claim 1, wherein the gas forming the growth environment of the graphene film in the reaction chamber comprises one or two of hydrogen, hydrocarbon gas, nitrogen, argon, ethanol, water vapor and oxygen.
8. The method for preparing a graphene film according to claim 7, wherein the gas forming the growth environment of the graphene film is a mixed gas of hydrogen and methane.
9. The method for preparing a graphene film according to claim 1, wherein the speed at which the growth substrate moves along with the support structure at a predetermined speed in the reaction chamber under the action of the transfer mechanism is 0.1 m/min to 60 m/min; the temperature of the growth substrate as it is transferred out of the reaction chamber is lower than 400 ℃.
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