CN114835494B - Preparation method of high-performance graphene heat conducting film - Google Patents
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Abstract
The invention relates to a preparation method of a high-performance graphene heat-conducting film, which comprises the steps of introducing a gaseous carbon source diluted by inert gas into high-temperature molten liquid metal, carrying out bubble growth in the liquid metal to obtain graphene powder, fully mixing the prepared graphene powder with a resin binder solution in a spray and stirring mixing mode, carrying out calendaring molding, graphitizing treatment and controlling the carbon residue formed by the binder resin to be 2-5% of the weight of the second graphene film after graphitizing treatment, and carrying out film densification treatment to obtain the complete high-performance graphene heat-conducting film. The preparation method disclosed by the invention is simple in preparation process, easy to expand production, and excellent in heat conduction performance and heat dissipation performance of the prepared graphene heat conduction film; the method can realize no waste water and waste gas emission in the preparation process of the graphene heat-conducting film, and cannot pollute the environment.
Description
Technical Field
The invention relates to the technical field of graphene, in particular to a preparation method of a high-performance graphene heat conduction film.
Background
With the development of high power electronics, the heat dissipation efficiency of thermal management materials has become a critical issue, which determines the operational reliability and stability of the device. The graphene heat conducting film with high heat conducting performance can effectively spread out local heat, and particularly has a remarkable heat radiating effect in electronic equipment with a complex structure.
In the prior art, graphene oxide is firstly dispersed into slurry in water, then the slurry is coated into a film, the film is heated and dried, and then the graphene thermal conductive film is obtained through low-temperature carbonization reduction and high-temperature graphitization processes and finally calendaring. In the prior art, graphene oxide is used as a raw material, and a large amount of strong acid and strong oxidant are needed in the process of obtaining the graphene oxide, so that a large amount of wastewater discharge is necessarily generated, and serious pollution is caused to the environment. In addition, the graphene oxide preparation process needs to be subjected to a series of procedures, is complex in process and high in energy consumption. Finally, for high-power electronic devices with high integration, graphene heat conduction films are required to have higher heat conduction performance, but the current production process has technical bottlenecks for further improving the heat conduction performance of the graphene heat conduction films, so that the requirements of terminal electronic manufacturers on the graphene heat conduction films with higher heat conduction performance are difficult to meet.
Disclosure of Invention
In order to solve the technical problem that the existing graphene heat conduction film is poor in heat conduction performance, a preparation method of the high-performance graphene heat conduction film is provided. The graphene heat conducting film prepared by the method disclosed by the invention has excellent heat conducting property and quicker heat diffusion.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a preparation method of a high-performance graphene heat conduction film comprises the following steps:
(1) Preparing graphene powder by bubbling growth in liquid metal through a CVD method;
(2) Spraying the collected graphene powder by adopting a resin binder solution, mixing the graphene powder and the resin binder solution at the same time, and uniformly mixing the graphene powder to obtain viscous powder;
the resin binder solution is obtained by diluting aqueous binder resin or oily binder resin with a solvent; the bonding resin is resin with higher carbon residue at high temperature, and is one of polyurethane, epoxy resin, phenolic resin, acrylic resin, amino resin, unsaturated polyester resin and saturated polyester resin;
(3) Feeding the adhesive powder into a calender to carry out first calendering to obtain a first graphene film;
(4) Graphitizing the first graphene film under the protection of inert gas to obtain a second graphene film; controlling the carbon residue amount formed by the bonding resin after graphitization treatment to be 2-5% of the weight of the second graphene film, calculating the dosage of the bonding resin according to the carbon residue amount, and diluting the bonding resin to the solid content which can be used for spraying by adopting a corresponding diluent;
(5) And placing the second graphene film in the calender for secondary calendering to obtain the high-performance graphene heat conducting film.
Further, the specific process of the step (1) is as follows: under the protection of normal pressure and nitrogen, introducing mixed gas of a gaseous carbon source and nitrogen below the liquid level of the molten metal, generating bubbles below the liquid level of the molten metal, growing graphene on the surfaces of the bubbles by the gaseous carbon source under the catalysis of the molten metal, and separating and collecting graphene powder from the molten metal after the bubbles rise above the liquid level of the molten metal due to the difference of surface tension, wherein the proportion of the prepared graphene powder sheet diameter is more than or equal to 85%, and the graphene powder sheet diameter prepared by the method is larger.
Still further, the temperature of the molten metal is 1050-1600 ℃, which is the temperature at which graphene is grown during the catalytic reaction; the gaseous carbon source is one of methane, ethane, propane, propylene, propyne, ethylene, acetylene, natural gas, liquefied petroleum gas, butane and butene; the flow rate of the gaseous carbon source is 1-15L/min, the flow rate of the nitrogen is 50-300L/min, and the flow rate of the nitrogen is preferably 120-250L/min.
Further, the solvent used for dilution in the step (2) is water and/or an organic solvent, and a corresponding diluting solvent is selected according to the type of the resin, for example, the aqueous binder resin can be directly diluted with water, the oily binder can be diluted and dissolved with an organic solvent, and then sprayed, and the organic solvent can be an alcohol solvent, acetone, benzene, toluene, xylene, an ester organic solvent, an amide organic solvent, and the like, and a good solvent capable of dissolving the corresponding resin is generally selected as the diluted organic solvent; spraying and mixing in the step (2) are performed in a spraying mixer, wherein the spraying pressure is 0.5-2.5MPa, the spraying solution flow is 3-15mL/min, the mixing speed is 800-2200rpm, and the mixing time is 1-3h; preferably, the solid content of the resin binder solution is 10 to 20wt%; preferably, the carbon residue formed by the binding resin after graphitization treatment is controlled to be 2-3.5% of the weight of the second graphene film.
Further, the pressure of the first rolling in the step (3) is 10-20MPa; the pressure of the second calendering in step (5) is 8-25MPa, preferably 10-16MPa, and the second calendering is carried out until the density of the obtained film is more than or equal to 2g/cm 3 The thickness is not less than100μm。
Further, the graphitization treatment in the step (4) is carried out by heating to 500 ℃ at the speed of 2-5 ℃/min, heating to 2800-3200 ℃ at the speed of 5-10 ℃/min, and then preserving heat for 1-3h at 2800-3200 ℃.
The beneficial technical effects are as follows:
the technical scheme for preparing the graphene heat-conducting film can be briefly summarized into graphene powder preparation, resin binder solution addition/spray mixing, roller pressing film preparation, graphitization and film densification, and the preparation method is simple in preparation process, easy to expand production, and excellent in heat-conducting performance and heat-radiating performance of the prepared graphene heat-conducting film; the method can realize no waste water and waste gas emission in the preparation process of the graphene heat-conducting film, and cannot pollute the environment.
According to the method, a spraying and stirring mixing mode is adopted, graphene powder and a small amount of binder can be fully and uniformly mixed, the problem that the heat conduction performance of the final graphene heat conduction film is affected due to excessive binder usage during conventional stirring and mixing, and the graphene film cannot be molded due to the fact that the binder usage is too small is avoided.
The binder disclosed by the invention is a resin binder (or bonding resin) with high-temperature carbon residue, so that the binder plays a role in bonding graphene powder during molding and is convenient for calendaring molding, and meanwhile, in a high-temperature graphitization stage, the bonding interface of graphene micro-plates and micro-plates is fused together through graphitized carbon; in addition, the graphene powder prepared by the CVD method bubbling growth in the molten liquid metal has larger sheet diameter, and after film forming and graphitization, the graphene micro-sheets and micro-sheets have fewer bonding interfaces and low thermal resistance, so that the graphene heat conduction film with higher heat conduction performance is obtained.
According to the invention, the graphene powder prepared by bubbling growth in liquid metal through a CVD method is used as a raw material for preparing the graphene heat conduction film, and no waste water discharge of strong acid and strong oxidant or greenhouse gas is generated in the process of preparing the graphene powder by using the bubbling growth method through the CVD methodBulk CO 2 The emission is carried out, so that the pollution to the environment is avoided;
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The numerical values set forth in these examples do not limit the scope of the present invention unless specifically stated otherwise. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but should be considered part of the specification where appropriate. In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of the exemplary embodiments may have different values.
In addition, the terms "first", "second", etc. are used to define the graphene film in the preparation process, and are merely for convenience of distinguishing the products obtained in each step, and unless otherwise stated, the terms have no special meaning, and therefore should not be construed as limiting the scope of the present invention.
The experimental methods in the following examples, for which specific conditions are not noted, are generally determined according to national standards; if the national standard is not corresponding, the method is carried out according to the general international standard or the standard requirements set by related enterprises. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
Yield of graphene powder = m 2 /m 1 ×100％；
Wherein: m is m 1 Is the mass of carbon atoms in the carbon source gas at the beginning of the reaction;
m 2 the quality of the obtained graphene powder is collected.
Example 1
A preparation method of a high-performance graphene heat conduction film comprises the following steps:
(1) Preparing graphene powder by CVD (chemical vapor deposition) method bubbling growth in liquid metal: under the protection of normal pressure and nitrogen, introducing mixed gas of methane/nitrogen into molten liquid copper at 1285 ℃, wherein the flow rate of the methane is 10L/min, the flow rate of the nitrogen is 150L/min, the mixed gas generates bubbles below the liquid surface of the molten copper, meanwhile, the methane grows graphene on the surface of the bubbles under the catalysis of the molten copper, after the bubbles rise above the liquid surface of the molten copper, the bubbles are broken due to the difference of surface tension, graphene powder is separated from the molten copper, and then the graphene powder enters a collecting device along with air flow for standby;
according to calculation, the yield of the graphene powder is 55wt%, and in addition, the sheet diameter of the graphene powder is more than 100 mu m and accounts for 85wt% by utilizing SEM observation and data statistics;
(2) Placing the graphene powder prepared in the step (1) into a spraying mixer, stirring at a rotating speed of 1500 rpm, spraying the graphene powder in the mixer by using a spray gun through an aqueous polyurethane emulsion with the solid content of 10wt% after being diluted by water, wherein the spraying pressure is 1.5MPa, the flow rate of the aqueous polyurethane emulsion is 5mL/min, stirring and mixing are carried out for 2 hours, so that the graphene powder and the polyurethane emulsion are fully mixed to obtain viscous graphene powder, the adhesive resin is the aqueous polyurethane emulsion, and the using amount of the adhesive resin is calculated according to the proportion that the carbon residue of the adhesive resin after graphitization treatment in the following step (4) is 2% of the weight of the second graphene film;
(3) And (3) performing primary forming of a graphene film: carrying out first rolling on the adhesive graphene powder in the step (2) by adopting a rolling mill, wherein the first rolling is carried out by carrying out rolling twice, and the rolling pressure of the two times is 15MPa, so as to obtain a first graphene film;
(4) Graphitizing: placing the first graphene film in a graphitization furnace, heating the first graphene film from room temperature to 500 ℃ at a speed of 2 ℃/min under the protection of argon, heating the first graphene film from 500 ℃ to 3000 ℃ at a speed of 7 ℃/min, and performing graphitization treatment at 3000 ℃ for 1h to obtain a second graphene film;
(5) Densification treatment of a graphene film: and placing the second graphene film in a calender again for calendering under the pressure of 10MPa, and finally obtaining the compact high-performance graphene heat conducting film.
The thickness of the graphene heat conduction film prepared in the embodiment is measured to be 100 mu m, and the density is measured to be 2.1g/cm 3 The thermal conductivity data are shown in Table 1.
Example 2
A preparation method of a high-performance graphene heat conduction film comprises the following steps:
(1) Preparing graphene powder by CVD (chemical vapor deposition) method bubbling growth in liquid metal: under the protection of normal pressure and nitrogen, introducing mixed gas of ethane/nitrogen into molten liquid copper-nickel alloy at 1330 ℃, wherein the flow of ethane is 7L/min, the flow of nitrogen is 140L/min, the mixed gas generates bubbles below the liquid surface of the molten copper-nickel alloy, meanwhile, the ethane grows graphene on the surface of the bubbles under the catalysis of the molten copper-nickel alloy, after the bubbles rise above the liquid surface of the molten copper-nickel alloy, the bubbles are broken due to the difference of surface tension, graphene powder is separated from the molten copper-nickel alloy, and then the graphene powder enters a collecting device along with air flow for standby;
according to calculation, the yield of the graphene powder is 52wt%, and in addition, the sheet diameter of the graphene powder is more than 100 mu m and accounts for 85.4wt% by utilizing SEM observation and data statistics;
(2) Placing the graphene powder prepared in the step (1) into a spraying mixer, stirring at a rotation speed of 1200 r/min, spraying the graphene powder in the mixer with a water-based epoxy resin solution with 17wt% of solid content after being diluted by water through a spray gun, wherein the spraying pressure is 2MPa, the flow rate of the water-based epoxy resin solution is 8mL/min, stirring and mixing are carried out for 2.5h, so that the graphene powder and the water-based epoxy resin solution are fully mixed to obtain viscous graphene powder with viscosity, wherein the bonding resin is the water-based epoxy resin, and the consumption of the bonding resin is calculated according to the proportion that the carbon residue of the bonding resin after graphitization treatment in the following step (4) accounts for 2.8% of the weight of the second graphene film;
(3) And (3) performing primary forming of a graphene film: carrying out first rolling on the adhesive graphene powder in the step (2) by adopting a rolling machine, wherein the first rolling is carried out by carrying out rolling twice, and the rolling pressure of the two times is 12MPa, so as to obtain a first graphene film;
(4) Graphitizing: placing the first graphene film in a graphitization furnace, heating the first graphene film from room temperature to 500 ℃ at a speed of 3 ℃/min under the protection of argon, heating the first graphene film from 500 ℃ to 2900 ℃ at a speed of 6 ℃/min, and performing graphitization treatment at the temperature of 2900 ℃ for 2 hours to obtain a second graphene film;
(5) Densification treatment of a graphene film: and placing the second graphene film in a calender again for calendering under the pressure of 13MPa, and finally obtaining the compact high-performance graphene heat conducting film.
The thickness of the graphene heat-conducting film prepared in the embodiment is 120 mu m, and the density is 2.13g/cm 3 The thermal conductivity data are shown in Table 1.
Example 3
A preparation method of a high-performance graphene heat conduction film comprises the following steps:
(1) Preparing graphene powder by CVD (chemical vapor deposition) method bubbling growth in liquid metal: under the protection of normal pressure and nitrogen, introducing mixed gas of natural gas/nitrogen into the molten liquid copper-iron alloy at 1350 ℃, wherein the natural gas flow is 5L/min, the nitrogen flow is 80L/min, the mixed gas generates bubbles below the liquid surface of the molten copper-iron alloy, meanwhile, the natural gas grows graphene on the surface of the bubbles under the catalysis of the molten copper-iron alloy, after the bubbles rise above the liquid surface of the molten copper-iron alloy, the bubbles are broken due to the difference of surface tension, the graphene powder is separated from the molten copper-iron alloy, and then the graphene powder enters a collecting device along with the air flow for standby;
according to calculation, the yield of the graphene powder is 53wt%, and in addition, the sheet diameter of the graphene powder is more than 100 mu m and accounts for 86wt% by utilizing SEM observation and data statistics;
(2) Placing the graphene powder prepared in the step (1) into a spraying mixer, stirring at a rotation speed of 1800 turns/min, spraying the graphene powder in the mixer with a water-based acrylic resin solution with a solid content of 15wt% through a spray gun, wherein the spraying pressure is 2.1MPa, the flow rate of the water-based acrylic resin solution is 5.5mL/min, stirring and mixing are carried out for 1.8 hours, so that the graphene powder and the water-based epoxy resin solution are fully mixed to obtain viscous graphene powder with viscosity, wherein the bonding resin is the water-based acrylic resin, and the consumption of the bonding resin is calculated according to the proportion that the carbon residue of the bonding resin after graphitization treatment in the following step (4) accounts for 5% of the weight of the second graphene film;
(3) And (3) performing primary forming of a graphene film: carrying out first rolling on the adhesive powder in the step (2) by adopting a rolling mill, wherein the first rolling is carried out by carrying out rolling twice, and the rolling pressure of the two times is 10MPa, so as to obtain a first graphene film;
(4) Graphitizing: placing the first graphene film in a graphitization furnace, heating the first graphene film from room temperature to 500 ℃ at a speed of 5 ℃/min under the protection of argon, heating the first graphene film from 500 ℃ to 3050 ℃ at a speed of 8 ℃/min, and performing graphitization treatment for 2.5 hours at the temperature of 3050 ℃ to obtain a second graphene film;
(5) Densification treatment of a graphene film: and placing the second graphene film in a calender again for calendering under the pressure of 15MPa, and finally obtaining the compact high-performance graphene heat conducting film.
The thickness of the graphene heat conduction film prepared in the embodiment is measured to be 150 mu m, and the density is measured to be 2.18g/cm 3 The thermal conductivity data are shown in Table 1.
Example 4
A preparation method of a high-performance graphene heat conduction film comprises the following steps:
(1) Preparing graphene powder by CVD (chemical vapor deposition) method bubbling growth in liquid metal: under the protection of normal pressure and nitrogen, introducing mixed gas of liquefied petroleum gas/nitrogen into molten liquid copper-cobalt alloy at 1250 ℃, wherein the flow rate of the liquefied petroleum gas is 15L/min, the flow rate of the nitrogen is 220L/min, and the mixed gas is prepared by mixing the following components in a certain proportionMelting copper-cobalt alloyBubbles are generated under the liquid level, meanwhile, the liquefied petroleum gas grows graphene on the surface of the bubbles under the catalysis of the molten copper-cobalt alloy, and the bubbles rise to molten copperAfter the liquid surface of the cobalt alloy is above, bubbles are broken due to the difference of surface tension, the graphene powder is separated from the molten copper cobalt alloy, and then the graphene powder enters a collecting device along with air flow for standby;
according to calculation, the yield of the graphene powder is 53.5wt%, and in addition, the sheet diameter of the graphene powder is more than 100 mu m and accounts for 85.7wt% by utilizing SEM observation and data statistics;
(2) Placing the graphene powder prepared in the step (1) into a spraying mixer, stirring at a rotation speed of 1700 r/min, spraying the graphene powder in the mixer by using a water-based phenolic resin solution with a solid content of 16wt% after being diluted by water through a spray gun, wherein the spraying pressure is 1.65MPa, the flow rate of the water-based phenolic resin solution is 6mL/min, stirring and mixing are carried out for 2.3h, so that the graphene powder and the water-based phenolic resin solution are fully mixed to obtain viscous graphene powder with viscosity, wherein the bonding resin is the water-based phenolic resin, and the consumption of the bonding resin is calculated according to the proportion that the carbon residue of the bonding resin accounts for 3.5% of the weight of the second graphene film after graphitization treatment in the following step (4);
(3) And (3) performing primary forming of a graphene film: carrying out first rolling on the adhesive powder in the step (2) by adopting a rolling mill, wherein the first rolling is carried out by carrying out rolling twice, and the rolling pressure of the two times is 13MPa, so as to obtain a first graphene film;
(4) Graphitizing: placing the first graphene film in a graphitization furnace, heating the first graphene film from room temperature to 500 ℃ at a speed of 4 ℃/min under the protection of argon, heating the first graphene film from 500 ℃ to 3100 ℃ at a speed of 10 ℃/min, and performing graphitization treatment at 3100 ℃ for 2.5h to obtain a second graphene film;
(5) Densification treatment of a graphene film: and placing the second graphene film in a calender again for calendering under the pressure of 16MPa, and finally obtaining the compact high-performance graphene heat conducting film.
The thickness of the graphene heat-conducting film prepared in the embodiment is measured to be 130 mu m, and the density is measured to be 2.2g/cm 3 The thermal conductivity data are shown in Table 1.
Example 5
The preparation process of the graphene film of this example is the same as that of example 1, except that the resin-based binder solution is an aqueous melamine formaldehyde resin (one of aqueous amino resins) diluted with water to a solid content of 20wt%, wherein the binder resin is an aqueous melamine formaldehyde resin, and the amount of the binder resin is calculated according to the proportion of the carbon residue amount of the binder resin after graphitization treatment to 3% of the weight of the second graphene film.
The thickness of the graphene heat conduction film prepared in the example is measured to be 130 mu m, and the density is measured to be 2.21g/cm 3 The thermal conductivity data are shown in Table 1.
Example 6
The preparation process of the graphene film of this embodiment is the same as that of embodiment 1, except that the resin binder solution is an aqueous saturated polyester resin, and the binder solution diluted with water to a solid content of 20wt% is used, wherein the binder resin is an aqueous saturated polyester resin, and the amount of the binder resin is calculated according to the proportion of the carbon residue amount of the binder resin after graphitization treatment to 4% of the weight of the second graphene film.
The thickness of the graphene heat conduction film prepared in the embodiment is measured to be 150 mu m, and the density is measured to be 2.16g/cm 3 The thermal conductivity data are shown in Table 1.
Example 7
The preparation process of the graphene film of this example is the same as that of example 3, except that the resin binder solution is an oily binder resin, and organic solvents are used to dissolve and dilute polyurethane, epoxy resin, phenolic resin, acrylic resin, amino resin, unsaturated polyester resin, and saturated polyester resin to a solid content of 15wt%, respectively, and the organic solvents are selected as good solvents capable of dissolving the corresponding resins; wherein the amount of each oily binding resin is calculated according to the proportion that the carbon residue of the binding resin after graphitization treatment accounts for 4.5% of the weight of the second graphene film.
The thickness of the graphene heat-conducting film prepared in the embodiment is 120 mu m, and the density is 2.22g/cm 3 The thermal conductivity data are shown in Table 1.
Comparative example 1
The preparation method of the graphene heat-conducting film of the comparative example is different from that of example 3 in that an aqueous acrylic resin solution with 15wt% of solid content after dilution with water is added into the graphene powder prepared in step (1), mixed and stirred, then coated on a substrate for forming and dried; the amount of the aqueous acrylic resin of the bonding resin is calculated according to the proportion that carbon residue of the bonding resin accounts for 5% of the weight of the graphene film after graphitization treatment.
The graphene powder prepared by bubbling growth in liquid metal has almost no oxygen-containing groups on the surface, and the content of the binding resin is low, so that the dried graphene film cannot be completely separated from the base material, and the subsequent process cannot be performed. If the amount of the binder resin is increased, the amount of carbon residue formed after graphitization is increased, and only a part of the carbon residue is converted into sp having anisotropy 3 The graphite structure is hybridized, so that the heat conduction performance of the whole graphene film is reduced after the carbon residue amount is increased.
The thickness of the graphene heat-conducting film prepared in the comparative example is measured to be 150 mu m, and the density is measured to be 1.8g/cm 3 The thermal conductivity data are shown in Table 1.
Table 1 thermal conductivity data for graphene films of examples and comparative examples
As can be seen from Table 1, the method of the invention can be used to prepare a complete graphene heat conduction film, and the graphene heat conduction film has excellent heat conduction performance and heat dissipation performance, the heat conductivity can reach more than 1700W/m.K, and the heat diffusion can reach 950mm 2 And/s.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (6)
1. The preparation method of the high-performance graphene heat conduction film is characterized by comprising the following steps of:
(1) Preparing graphene powder by using a CVD method to carry out bubbling growth in liquid metal, wherein the obtained graphene powder has a sheet diameter of more than 100 mu m and accounts for more than 85wt%;
(2) Spraying the collected graphene powder by adopting a resin binder solution, mixing the graphene powder and the resin binder solution at the same time, and uniformly mixing the graphene powder to obtain viscous powder;
the resin binder solution is obtained by diluting aqueous binder resin or oily binder resin with solvent, wherein the binder resin is one of polyurethane, epoxy resin, phenolic resin, acrylic resin, amino resin, unsaturated polyester resin and saturated polyester resin;
(3) Feeding the adhesive powder into a calender to carry out first calendering to obtain a first graphene film;
(4) Graphitizing the first graphene film under the protection of inert gas to obtain a second graphene film; controlling the carbon residue formed by the bonding resin after graphitization treatment to account for 2-5% of the weight of the second graphene film;
(5) Placing the second graphene film in the calender for secondary calendering until the density of the obtained film is more than or equal to 2g/cm 3 The thickness is more than or equal to 100 mu m, and the high-performance graphene heat conduction film is obtained, the heat conductivity of the obtained graphene heat conduction film reaches more than 1700W/m.K, and the heat diffusion reaches 950mm 2 And/s.
2. The method for preparing the high-performance graphene heat conducting film according to claim 1, wherein the specific process of the step (1) is as follows: under the protection of normal pressure and nitrogen, introducing mixed gas of gaseous carbon source and nitrogen below the liquid level of the molten metal, generating bubbles below the liquid level of the molten metal, growing graphene on the surfaces of the bubbles by the gaseous carbon source under the catalysis of the molten metal, and separating and collecting graphene powder from the molten metal after the bubbles rise above the liquid level of the molten metal due to the difference of surface tension.
3. The method for preparing a high-performance graphene heat conducting film according to claim 2, wherein the temperature of the molten metal is 1050-1600 ℃;
the gaseous carbon source is one of methane, ethane, propane, propylene, propyne, ethylene, acetylene, natural gas, liquefied petroleum gas, butane and butene;
the flow rate of the gaseous carbon source is 1-15L/min, and the flow rate of the nitrogen is 50-300L/min.
4. The method for preparing a high-performance graphene heat-conducting film according to claim 1, wherein,
the solvent used for dilution in the step (2) is water and/or an organic solvent, and a corresponding dilution solvent is selected according to the type of the resin;
spraying and mixing in the step (2) are carried out in a spraying mixer, the spraying pressure is 0.5-2.5MPa, the spraying solution flow is 3-15mL/min, the mixing speed is 800-2200rpm, and the mixing time is 1-3h.
5. The method for preparing a high-performance graphene heat-conducting film according to claim 1, wherein the pressure of the first rolling in the step (3) is 10-20MPa; the pressure of the second rolling in the step (5) is 8-25MPa.
6. The method for preparing a high-performance graphene heat-conducting film according to claim 1, wherein the graphitization treatment in the step (4) is performed by heating to 500 ℃ at a speed of 2-5 ℃/min, heating from 500 ℃ to 2800-3200 ℃ at a speed of 5-10 ℃/min, and then performing heat preservation treatment at 2800-3200 ℃ for 1-3 hours.
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