CN109650892B - High-thermal-conductivity graphene film and preparation method thereof - Google Patents
High-thermal-conductivity graphene film and preparation method thereof Download PDFInfo
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Abstract
The invention provides a high-thermal-conductivity graphene film and a preparation method thereof, wherein the preparation method comprises the following steps: A) sequentially coating polyamide acid resin and graphene oxide solution on the surface of a base material, and drying to obtain a graphene oxide composite film; B) stripping the graphene oxide composite film from a base material to obtain a continuous graphene oxide composite film coiled material; C) carrying out heat treatment on the graphene oxide composite film coiled material to obtain a carbonized graphene oxide composite film; D) and carrying out graphitization treatment on the carbonized graphene oxide composite membrane to obtain the high-thermal-conductivity graphene membrane. According to the invention, the polyamic acid resin and the graphene oxide solution are sequentially formed into a film to form a structure in which two films of the graphene oxide film and the polyamic acid film are overlapped, so that the high heat-conducting property of graphene can be more fully exerted, a thicker graphene film can be obtained by stripping, the special requirements in the aerospace field can be met, and the product yield of the stripped graphene is also improved.
Description
Technical Field
The invention belongs to the technical field of heat conduction materials, and particularly relates to a graphene film with high heat conduction and a preparation method thereof.
Background
Graphite is an allotrope formed by carbon elements, has unique thermal, electrical and chemical properties due to the perfect molecular structure, and can be widely applied to industries such as electronics, heat dissipation and the like. The high-thermal-conductivity graphite film with the plane thermal conductivity coefficient of 800-1500W/m.K, which is prepared at present, solves the problem of local overheating of small-power chips such as mobile phones. However, as the performance of the electronic device becomes better, the processing speed and frequency become higher. The volume weight is higher and higher, and power is bigger and larger, and electronic equipment generates heat more and more, and the requirement to the heat dissipation is also higher and more. Therefore, the common artificial graphite film cannot meet the requirement of high-end equipment for heat dissipation, and a material with higher heat conduction and heat dissipation is urgently needed to be found.
Two professors in manchester university in the united kingdom in 2010 have won the nobel prize on physics due to the first successful separation of the stably existing graphene, and have raised the hot trend of graphene research worldwide. Graphene is used as a basic unit for forming graphite, has excellent heat conduction performance, and the theoretical thermal conductivity of single-layer graphene can reach more than 5000W/m.K. The graphene has the advantages of high thermal conductivity, low density, easiness in processing and the like, so that the graphene has great market potential.
Chinese patent CN105510794A, the pretreated graphene oxide is coated on a PET film, and the graphene film is prepared by drying, stripping, carbonizing and graphitizing. In the chinese patent CN105502368A, graphene oxide is scraped on a substrate, and then graphitized, rolled, and the substrate is peeled to obtain a graphene thin film. Through comparative analysis and practical production experience, the following problems exist in the prior art: the difficulty is high when the graphene is coated on a substrate and then peeled off, the product yield is low, and the efficiency is low; the size and the process of the prepared film are difficult to produce and apply on a large scale; the rolled film cannot be continuously produced, and the production efficiency is low.
Disclosure of Invention
The invention aims to provide a high-thermal-conductivity graphene film and a preparation method thereof.
The invention provides a preparation method of a graphene film with high thermal conductivity, which comprises the following steps:
A) sequentially coating polyamide acid resin and graphene oxide solution on the surface of a base material, and drying to obtain a graphene oxide composite film;
B) stripping the graphene oxide composite film from a base material to obtain a continuous graphene oxide composite film coiled material;
C) carrying out heat treatment on the graphene oxide composite film coiled material to obtain a carbonized graphene oxide composite film;
D) and carrying out graphitization treatment on the carbonized graphene oxide composite membrane to obtain the high-thermal-conductivity graphene membrane.
Preferably, the polyamic acid resin is prepared by performing polycondensation reaction on dianhydride and diamine in a strong polar solvent;
the dianhydride is one or more of biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride and benzophenone tetracarboxylic dianhydride;
the diamine is one or more of diaminodiphenyl ether, p-phenylenediamine and diaminobenzophenone.
Preferably, the solid content of the polyamic acid resin is 10-25 wt%.
Preferably, the graphene oxide solution is an organic surfactant solution of graphene oxide powder;
the organic surfactant is one or more of polyvinylpyrrolidone, polyvinyl alcohol, sodium dodecyl sulfate and carboxymethyl cellulose.
Preferably, in the graphene oxide solution, the mass concentration of the graphene oxide is 3-10 wt%, and the concentration of the organic surfactant is 0.01-0.05 wt%;
the viscosity of the graphene oxide solution is 5000-30000 cPs.
Preferably, the coating thickness of the polyamic acid resin is 80-400 μm;
the coating thickness of the graphene oxide solution is 200-1000 mu m.
Preferably, the drying temperature in the step A) is 70-200 ℃;
the drying time in the step A) is 15-30 min.
Preferably, the temperature of the heat treatment in the step C) is 700-1500 ℃;
the time of heat treatment in the step C) is 4-10 hours.
Preferably, the temperature of the graphitization treatment in the step D) is 2700-3000 ℃;
the graphitization treatment time in the step D) is 3-8 hours.
The invention provides a high-thermal-conductivity graphene film prepared by the preparation method of any one of claims 1 to 9,
the thickness of the high-thermal-conductivity graphene film is 50-200 mu m.
The invention provides a preparation method of a graphene film with high thermal conductivity, which comprises the following steps: A) sequentially coating polyamide acid resin and graphene oxide solution on the surface of a base material, and drying to obtain a graphene oxide composite film; B) stripping the graphene oxide composite film from a base material to obtain a continuous graphene oxide composite film coiled material; C) carrying out heat treatment on the graphene oxide composite film coiled material to obtain a carbonized graphene oxide composite film; D) and carrying out graphitization treatment on the carbonized graphene oxide composite membrane to obtain the high-thermal-conductivity graphene membrane. According to the invention, the polyamic acid resin and the graphene oxide solution are sequentially formed into a film to form a structure in which two films of the graphene oxide film and the polyamic acid film are overlapped, so that the high heat-conducting property of graphene can be more fully exerted, a thicker graphene film can be obtained by stripping, the special requirements in the aerospace field can be met, and the product yield of the stripped graphene is also improved. Experimental results show that the graphene film obtained by the preparation method has the thermal conductivity of 1850wW/m.k, the tensile strength of 38MPa, the bending resistance times of more than 10 ten thousand and the density of 1.92g/m3。
Detailed Description
The invention provides a preparation method of a graphene film with high thermal conductivity, which comprises the following steps:
A) sequentially coating polyamide acid resin and graphene oxide solution on the surface of a base material, and drying to obtain a graphene oxide composite film;
B) stripping the graphene oxide composite film from a base material to obtain a continuous graphene oxide composite film coiled material;
C) carrying out heat treatment on the graphene oxide composite film coiled material to obtain a carbonized graphene oxide composite film;
D) and carrying out graphitization treatment on the carbonized graphene oxide composite membrane to obtain the high-thermal-conductivity graphene membrane.
The present invention preferably prepares the polyamic acid resin according to the following method:
carrying out polycondensation reaction on dianhydride and diamine in a strong polar solvent to obtain polyamide acid resin;
the dianhydride is preferably one or more of biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride and benzophenone tetracarboxylic dianhydride; the diamine is one or more of diaminodiphenyl ether, p-phenylenediamine and diaminobenzophenone; the molar ratio of dianhydride to diamine is preferably 1: (0.9 to 1.1), and more preferably 1: 1. The strongly polar solvent is preferably Dimethylacetamide (DMAC) and/or N-methylpyrrolidone (NMP).
The solid content of the polyamic acid resin obtained by the polycondensation reaction is preferably 10 to 25wt%, and more preferably 15 to 20 wt%.
The graphene oxide solution is preferably prepared according to the following steps:
and stirring and dispersing the graphene oxide powder in a solvent containing an organic surfactant by using a vacuum ultrasonic stirring dispersion machine to form uniform graphene oxide slurry, and performing vacuum defoaming.
In the invention, the sheet size of the graphene oxide powder is preferably 50-100 μm, more preferably 60-90 μm, and most preferably 70-80 μm; the organic surfactant is preferably one or more of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), Sodium Dodecyl Sulfate (SDS) and carboxymethyl cellulose (CMC).
In the graphene oxide solution, the mass concentration of the graphene oxide is preferably 3-10 wt%, and more preferably 5-6 wt%; the concentration of the organic surfactant is preferably 0.01-0.05 wt%, and more preferably 0.02-0.04 wt%; the viscosity of the graphene oxide solution is preferably 5000-30000 cPs, more preferably 10000-25000 cPs, and most preferably 10000-20000 cPs.
After preparing polyamic acid resin and graphene oxide solution, the invention sequentially coats polyimide acid and graphene oxide solution on a substrate through two coating heads connected in series or two coating heads with double feeding and double coating ports to form a graphene oxide composite film with a certain thickness, then carries out drying to remove solvent and form a film, carries out continuous rolling and is made into a coiled material.
In the invention, the substrate is preferably a steel belt or a PET substrate, and the wet film coating thickness of the polyamic acid resin is preferably 80-400 μm, more preferably 100-300 μm, and most preferably 200-250 μm; the wet film coating thickness of the graphene oxide solution is preferably 200-1000 μm, more preferably 300-800 μm, and most preferably 500-600 μm. The drying temperature is preferably 70-200 ℃, more preferably 80-160 ℃, and most preferably 140-160 ℃; the drying time is preferably 15-30 min, and most preferably 25-30 min.
After drying, the obtained coiled material is a composite material, and the graphene oxide composite film on the substrate is provided with a graphene oxide layer and a polyamic acid layer, wherein the polyamic acid layer is in contact with the substrate.
Stripping the graphene oxide composite film from the base material by adopting stripping equipment to form a continuous graphene oxide composite film coiled material; in the present invention, the peeling apparatus comprises one or two automatic winding mechanisms. If the base material is a steel belt, the composite film is manually peeled off and then stuck on a winding roll for automatic winding; if the base material is a PET base material, the composite film needs to be manually peeled off and stuck to two different automatic winding rollers for automatic winding.
Most of graphene oxide films in the prior art are coated with a layer of graphene oxide alone, and the graphene oxide films are modified by mixing the graphene oxide with other modified materials, however, the existing method has a problem that the graphene oxide layer cannot be coated too thick, and if the graphene oxide layer is too thin or too thick, the film is easily torn in a stripping step, so that the yield is affected, and the mass production is not easy to realize. However, in the aerospace field, a graphene oxide film with a certain thickness is required, and the existing graphene oxide film cannot meet the requirement of the aerospace field on the film thickness. However, the graphene oxide film in the invention not only can meet the requirements for the film thickness in the aerospace field, but also can ensure excellent performance.
Carrying out heat treatment on a stripped graphene oxide composite film coiled material in a protective atmosphere to obtain a carbonized coiled material;
in the heat treatment process in the step, three processes of high-temperature thermal reduction, imidization and carbonization are simultaneously carried out, wherein the high-temperature thermal reduction reduces graphene oxide into a graphene material, the imidization prepares a polyimide layer from a polyamide acid layer, and the carbonization can reduce organic matters and functional groups, release gas and carbonize the organic matters.
In the invention, the temperature of the heat treatment is preferably 700-1500 ℃, and more preferably 1200-1500 ℃; specifically, in an embodiment of the present invention, 1250 ℃; the time of the heat treatment is preferably 4 to 10 hours, and more preferably 6 to 8 hours.
In the present invention, the protective atmosphere is preferably an inert gas atmosphere or a reducing atmosphere, such as nitrogen, argon, helium or hydrogen.
After the carbonized coiled material is obtained, the carbonized coiled material is graphitized to obtain the graphene film with high thermal conductivity.
In the invention, the graphitization temperature is preferably 2700-3000 ℃, more preferably 2800-2900 ℃, and most preferably 2850 ℃; the graphitization time is preferably 3-8 hours, more preferably 4-7 hours, and most preferably 5-6 hours.
After graphitization, the graphene film obtained is preferably subjected to calendering treatment to increase the density, and finally, is subjected to cutting processing according to the required size. The pressure of the rolling treatment is preferably 0.5 to 20MPa, more preferably 5 to 15MPa, and most preferably 10 to 13 MPa.
The invention also provides a high-thermal-conductivity graphene film, which is prepared according to the preparation method, wherein the thickness of the high-thermal-conductivity graphene film is preferably 50-200 micrometers, and more preferably 100-150 micrometers; the density of the graphene heat-conducting film is 0.5-2.1 g/m3(ii) a The heat conductivity coefficient of the graphene heat-conducting film is 1800-2200W/m.K; the tensile strength of the graphene heat-conducting film is 15-50 MPa; bending-resistant times of graphene heat-conducting filmThe number is more than 10 ten thousand times.
The invention provides a preparation method of a graphene film with high thermal conductivity, which comprises the following steps: A) sequentially coating polyamide acid resin and graphene oxide solution on the surface of a base material, and drying to obtain a graphene oxide composite film; B) stripping the graphene oxide composite film from a base material to obtain a continuous graphene oxide composite film coiled material; C) carrying out heat treatment on the graphene oxide composite film coiled material to obtain a carbonized graphene oxide composite film; D) and carrying out graphitization treatment on the carbonized graphene oxide composite membrane to obtain the high-thermal-conductivity graphene membrane. According to the invention, the polyamic acid resin and the graphene oxide solution are sequentially formed into a film to form a structure in which two films of the graphene oxide film and the polyamic acid film are overlapped, so that the high heat-conducting property of graphene can be more fully exerted, the mechanical property is improved, a thicker graphene film can be obtained by stripping, the special requirements in the aerospace field can be met, and the product yield of the stripped graphene is also improved. Experimental results show that the graphene film obtained by the preparation method has the thermal conductivity of 1850wW/m.k, the tensile strength of 38MPa, the bending resistance times of more than 10 ten thousand and the density of 1.92g/m3。
In order to further illustrate the present invention, the following describes in detail a high thermal conductivity graphene film and a method for preparing the same with reference to examples, which should not be construed as limiting the scope of the present invention.
Example 1
Biphenyl tetracarboxylic dianhydride (BPDA), Benzophenone Tetracarboxylic Dianhydride (BTDA), diaminodiphenyl ether (ODA) and p-phenylenediamine (PPDA) are subjected to polycondensation reaction in a strong polar solvent DMAC to prepare polyimide acid (PAA) matrix resin with the solid content of 20%;
dispersing graphene oxide powder in NMP containing PVA by using a vacuum ultrasonic stirring disperser to form uniform graphene oxide slurry and carrying out vacuum defoaming; wherein the concentration of the graphene oxide in the prepared graphene oxide slurry is 5wt%, the viscosity is 10000cPs, and the content of the organic surfactant is 0.02wt%
Sequentially coating the polyimide acid and the graphene oxide solution on a base material through a coating head with double feeding and double coating ports to form a graphene oxide composite film with a certain thickness, drying the graphene oxide composite film in a coating machine oven to remove a solvent and form a film, and continuously rolling to obtain a coiled material; the base material is PET; the wet film coating thickness of the PAA resin is 200 μm; the coating thickness of the wet film of the graphene oxide solution is 500 mu m; drying temperature of a coating machine oven is 150 ℃, and drying time of a wet film is 30 min;
stripping the graphene oxide composite film from PET (polyethylene terephthalate) by using stripping equipment and rolling to form a continuous graphene oxide composite film coiled material;
placing the obtained graphene oxide composite membrane coiled material into a high-temperature furnace at 1250 ℃ under the protection of nitrogen atmosphere for thermal reduction, imidization and carbonization for 6 hours;
putting the obtained carbonized material into a graphitization furnace at 2850 ℃ for graphitization treatment for 6 h;
carrying out calendaring treatment on the obtained graphene film, improving the density, and carrying out edge cutting and the like to process the graphene film into the graphene film with the required size; wherein the rolling pressure is controlled to be 10 MPa.
The density of the graphene heat-conducting film prepared by the embodiment is 1.92g/m3The thickness is 50 μm, the thermal conductivity is 1850W/m.K, the tensile strength is 38MPa, and the bending resistance times is more than 10 ten thousand.
Example 2
Biphenyl tetracarboxylic dianhydride (BPDA), Benzophenone Tetracarboxylic Dianhydride (BTDA), diaminodiphenyl ether (ODA) and p-phenylenediamine (PPDA) are subjected to polycondensation reaction in a strong polar solvent DMAC to prepare polyimide acid (PAA) matrix resin with the solid content of 15%;
dispersing graphene oxide powder in NMP containing PVA by using a vacuum ultrasonic stirring disperser to form uniform graphene oxide slurry and carrying out vacuum defoaming; wherein the concentration of the graphene oxide in the prepared graphene oxide slurry is 7wt%, the viscosity is 20000cPs, and the content of the organic surfactant is 0.03wt%
Sequentially coating the polyimide acid and the graphene oxide solution on a base material through a coating head with double feeding and double coating ports to form a graphene oxide composite film with a certain thickness, drying the graphene oxide composite film in a coating machine oven to remove a solvent and form a film, and continuously rolling to obtain a coiled material; the base material is PET; the PAA resin has a wet film coating thickness of 240 μm; the coating thickness of the wet film of the graphene oxide solution is 600 mu m; the drying temperature of the oven of the coating machine is 140 ℃, and the drying time of the wet film is 25 min;
stripping the graphene oxide composite film from PET (polyethylene terephthalate) by using stripping equipment and rolling to form a continuous graphene oxide composite film coiled material;
placing the obtained graphene oxide composite film coiled material into a high-temperature furnace at 1200 ℃ under the protection of helium atmosphere for thermal reduction, imidization and carbonization for 4 hours;
placing the obtained carbonized material into a graphitization furnace at 2750 ℃ for graphitization treatment for 5 h;
carrying out calendaring treatment on the obtained graphene film, improving the density, and carrying out edge cutting and the like to process the graphene film into the graphene film with the required size; wherein the rolling pressure is controlled to be 7 MPa.
The density of the graphene heat-conducting film prepared by the embodiment is 1.72g/m3The thickness is 60 μm, the thermal conductivity is 1350W/m.K, the tensile strength is 21MPa, and the bending resistance times is less than 5 ten thousand.
Example 3
Biphenyl tetracarboxylic dianhydride (BPDA), Benzophenone Tetracarboxylic Dianhydride (BTDA), diaminodiphenyl ether (ODA) and p-phenylenediamine (PPDA) are subjected to polycondensation reaction in a strong polar solvent DMAC to prepare polyimide acid (PAA) matrix resin with the solid content of 12%;
dispersing graphene oxide powder in NMP containing PVA by using a vacuum ultrasonic stirring disperser to form uniform graphene oxide slurry and carrying out vacuum defoaming; wherein the concentration of the graphene oxide in the prepared graphene oxide slurry is 10wt%, the viscosity is 28000cPs, and the content of the organic surfactant is 0.04wt%
Sequentially coating the polyimide acid and the graphene oxide solution on a base material through a coating head with double feeding and double coating ports to form a graphene oxide composite film with a certain thickness, drying the graphene oxide composite film in a coating machine oven to remove a solvent and form a film, and continuously rolling to obtain a coiled material; the base material is PET; the coating thickness of the PAA resin is 250 μm; the coating thickness of the graphene oxide solution is 300 mu m; the drying temperature of the oven of the coating machine is 140 ℃, and the drying time of the wet film is 20 min;
stripping the graphene oxide composite film from PET (polyethylene terephthalate) by using stripping equipment and rolling to form a continuous graphene oxide composite film coiled material;
placing the obtained graphene oxide composite film coiled material into a high-temperature furnace at 1100 ℃ under the protection of helium atmosphere for thermal reduction, imidization and carbonization for 4 hours;
placing the obtained carbonized material into a graphitization furnace at 2700 ℃ for graphitization treatment for 5 h;
carrying out calendaring treatment on the obtained graphene film, improving the density, and carrying out edge cutting and the like to process the graphene film into the graphene film with the required size; wherein the rolling pressure is controlled to be 5 MPa.
The density of the graphene heat-conducting film prepared by the embodiment is 1.52g/m3The thickness is 45 μm, the heat conductivity coefficient is 1200W/m.K, the tensile strength is 20MPa, and the bending resistance times is less than 3 ten thousand.
Comparative example 1
A graphene film was prepared according to the method of example 1, except that the graphene oxide solution was directly coated on the substrate without coating the polyamic acid resin, and the coating thickness of the graphene oxide solution was 300 μm.
The density of the graphene heat-conducting film prepared in the comparative example is 1.81g/m3The thickness is 10 μm, the heat conductivity coefficient is 1450W/m.K, the tensile strength is 15MPa, the bending resistant times are less than 2 ten thousand, and a large amount of tearing and breakage phenomena occur in the stripping and rolling processes.
Comparative example 2
A graphene film was prepared according to the method of example 1, except that the present comparative example mixed a graphene solution with a polyamic acid resin and then applied to a substrate.
The density of the graphene heat-conducting film prepared in the comparative example is 1.76g/m3The thickness is 54 μm, the heat conductivity coefficient is 950W/m.K, the tensile strength is 23MPa, and the bending resistance times is less than 5 ten thousand.
Comparative example 3
A graphene film was prepared according to the method of example 1, except that the temperature for thermal reduction, imidization, and carbonization in the high temperature furnace in this application was 600 ℃.
The density of the graphene heat-conducting film prepared in the comparative example is 1.56g/m3The thickness is 40 μm, the thermal conductivity is 690W/m.K, the tensile strength is 8MPa, and the bending resistance times is less than 1 ten thousand.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of a graphene film with high thermal conductivity comprises the following steps:
A) sequentially coating polyamide acid resin and graphene oxide solution on the surface of a base material, and drying to obtain a graphene oxide composite film;
the coating thickness of the polyamic acid resin is 80-400 mu m; the coating thickness of the graphene oxide solution is 200-1000 mu m;
B) stripping the graphene oxide composite film from a base material to obtain a continuous graphene oxide composite film coiled material;
C) carrying out heat treatment on the graphene oxide composite film coiled material to obtain a carbonized graphene oxide composite film;
D) and carrying out graphitization treatment on the carbonized graphene oxide composite membrane to obtain the high-thermal-conductivity graphene membrane.
2. The method according to claim 1, wherein the polyamic acid resin is prepared by polycondensation reaction of dianhydride and diamine in a strongly polar solvent;
the dianhydride is one or more of biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride and benzophenone tetracarboxylic dianhydride;
the diamine is one or more of diaminodiphenyl ether, p-phenylenediamine and diaminobenzophenone.
3. The method according to claim 1, wherein the polyamic acid resin has a solid content of 10 to 25 wt%.
4. The preparation method according to claim 1, wherein the graphene oxide solution is an organic surfactant solution of graphene oxide powder;
the organic surfactant is one or more of polyvinylpyrrolidone, polyvinyl alcohol, sodium dodecyl sulfate and carboxymethyl cellulose.
5. The preparation method according to claim 4, wherein the graphene oxide solution contains 3 to 10wt% of graphene oxide and 0.01 to 0.05wt% of organic surfactant;
the viscosity of the graphene oxide solution is 5000-30000 cPs.
6. The method for preparing the compound of claim 1, wherein the temperature for drying in the step A) is 70-200 ℃;
the drying time in the step A) is 15-30 min.
7. The preparation method according to claim 1, wherein the temperature of the heat treatment in the step C) is 700 to 1500 ℃;
the time of heat treatment in the step C) is 4-10 hours.
8. The preparation method according to claim 1, wherein the temperature of the graphitization treatment in the step D) is 2700-3000 ℃;
the graphitization treatment time in the step D) is 3-8 hours.
9. A graphene film with high thermal conductivity, which is prepared by the preparation method of any one of claims 1 to 8,
the thickness of the high-thermal-conductivity graphene film is 50-200 mu m.
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