CN108503383B - Preparation method of graphene composite film with high thermal conductivity - Google Patents

Preparation method of graphene composite film with high thermal conductivity Download PDF

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CN108503383B
CN108503383B CN201810352536.8A CN201810352536A CN108503383B CN 108503383 B CN108503383 B CN 108503383B CN 201810352536 A CN201810352536 A CN 201810352536A CN 108503383 B CN108503383 B CN 108503383B
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thermal conductivity
high thermal
composite film
graphene composite
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CN108503383A (en
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韩金玲
吕振瑞
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Xiamen Chengyu Industrial Co ltd
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Abstract

Graphene has wide application prospects in various fields due to excellent physicochemical characteristics, and has wide application prospects in the field of heat conduction due to the fact that graphene has a heat conductivity coefficient as high as 3500W/mK, and the graphene is also widely applied to the field of heat conduction.

Description

Preparation method of graphene composite film with high thermal conductivity
Technical Field
The invention belongs to the field of preparation of high-thermal-conductivity composite materials, and particularly relates to the technical field of preparation of a high-thermal-conductivity thin film material of a graphene composite high-molecular polymer.
Background
Along with the continuous development of the electronic industry, the integration level of electronic products is higher and higher, meanwhile, the heat generated by chips is also increased sharply, and the unit heat density of the products is increased inevitably and rapidly due to the miniaturization development of the products, and the traditional physical heat dissipation modes using copper pipes, aluminum sheets and the like are more and more difficult to meet the actual requirements, for example, the heat conductivity coefficients of the current commercial copper pipes or aluminum sheets are only 380W/mK and 200W/mK respectively, and the densities thereof are 8.96g/cm respectively3And 2.7g/cm3Therefore, the development of a material with low density and high thermal conductivity to replace the traditional copper pipe and aluminum sheet has important significance for the sustainable development of the whole electronic industry at present.
The graphite film attracts the attention of a large number of researchers due to good thermal conductivity and low density, and due to the layered structure of graphite, the graphite film has obvious anisotropy in heat conduction, which is greatly different from the current traditional materials, for example, the thermal conductivity in the horizontal direction is as high as 1500-3000W/mK, the thermal conductivity in the vertical direction is only one percent of the thermal conductivity in the horizontal direction, and the density can be as low as 1-2g/cm3These excellent properties make graphite films have great potential for use.
In contrast, chinese patent CN105235307A discloses a heat-conducting film graphite composite material, and discloses a heat-conducting film graphite composite material used in various electronic device heat dissipation occasions; the structure of the composite material comprises a PET (polyethylene terephthalate) back adhesive film, a metal foil layer, heat-conducting silicone grease, a graphite film, an acrylic adhesive and a release film from top to bottom, wherein the metal foil layer and the graphite film are respectively provided with an aperture and a through hole which are corresponding to each other, the metal foil layer is attached to the PET back adhesive film and provided with a metal foil layer bulge, the PI film is carbonized and graphitized to prepare the graphite film and then is perforated during preparation, the graphite film through hole is formed, the metal foil layer is perforated to form the metal foil layer through hole, then one side of the metal foil layer is coated with the heat-conducting silicone grease and then is compounded with the graphite film coated with the acrylic adhesive, then the metal foil layer is attached to the release film, finally the other side of the metal. Chinese patent CN103011141A discloses a method for manufacturing a graphite film with high thermal conductivity, which uses a polyimide film as a raw material, and the method comprises two processes of carbonization and graphitization, and the process comprises the following steps: a. selecting polyimide films as raw materials, and sandwiching graphite paper between every two layers of polyimide films; b. putting the polyimide film alternately laminated with the graphite paper into a carbonization furnace to be carbonized in a nitrogen or argon environment, wherein the carbonization temperature is 1000-1400 ℃, and the time is controlled to be 1-6 hours; c. after carbonization, graphitization is carried out, and graphitization is also carried out in a nitrogen or argon environment, and the temperature is controlled to be about 2500 ℃ to 3000 ℃ within 12 hours. Although the heat-conducting films are graphite films and have high heat conductivity coefficient, the polyimide is used as the film base material, so that the process of converting the polyimide into the graphite film is complex, carbonization is needed first and then graphitization is needed, time and energy are consumed continuously, and the controllability of the prepared product is worse, and the large-scale production is not facilitated.
Disclosure of Invention
Based on the above problems, the applicant has made extensive studies in the field of functional nanomaterials for a long time, and now proposes a technical scheme for solving the technical problem, and proposes a technical scheme for preparing a thin film, which has a simple process and high repeatability, and the prepared heat-conducting film has a higher heat conductivity than the existing heat-conducting film.
In recent years, graphene has a wide application prospect in various fields due to excellent physicochemical characteristics, and in the field of heat conduction, the graphene has a heat conductivity coefficient as high as 3500W/mK, so that the application of the graphene in the field of heat conduction is also widely researched, and the applicant introduces the graphene into a high molecular polymer according to the related research of the graphene in the field of self and rapidly prepares a graphene composite film with high heat conductivity by a simple method.
In order to enable a person skilled in the art to further understand the technical solution of the applicant, the applicant describes the technical solution in detail as follows:
a preparation method of a graphene composite film with high thermal conductivity comprises the following steps:
step 1, adding a plurality of amine substances and anhydride substances into an organic solvent, and uniformly stirring until the amine substances and the anhydride substances are completely dissolved to obtain a solution A;
step 2, taking a plurality of single-layer graphene oxides, dispersing the single-layer graphene oxides in the solution, and performing ultrasonic treatment for 5-10min at the temperature of 30-60 ℃ to obtain an orange-yellow graphene oxide colloid dispersion liquid B;
step 3, continuously stirring in a water bath kettle at the temperature of 50-80 ℃, and uniformly mixing the solution A in the step 1 and the dispersion liquid B in the step 2 to form a stable block system C;
step 4, placing the pretreated polytetrafluoroethylene mold in an oven, adding a plurality of block systems C in the step 3 into the polytetrafluoroethylene mold, and curing and drying at 50-300 ℃; obtaining a dry product D;
and 5, ablating the dried product D in the step 4 by using a plasma ablation machine, and obtaining the graphene composite membrane with high thermal conductivity after 30-70 seconds.
Further, the organic solvent in step 1 includes one or more of acetone, nitrogen-nitrogen dimethylformamide and dimethylsulfoxide.
Further, the amine substance in the step 1 comprises one or more of p-phenylenediamine, m-phenylenediamine and dichloro-p-diaminobiphenyl.
Further, the anhydride substances in the step 1 comprise one or more of pyromellitic dianhydride, diphenyl ether tetracarboxylic dianhydride and biphenyl tetracarboxylic dianhydride.
Further, the molar ratio of the amine substance to the anhydride substance in the step 1 is 1: 1-2.
Further, the single-layer graphene oxide in the step 2 is purchased from a pioneer nano material, and has a sheet diameter of 0.5-5 microns and a thickness of 0.8-1.2 nm.
Further, the concentration of the monolayer graphene oxide in the step 2 is 0.05-0.1 mg/ml.
Further, the polytetrafluoroethylene mold in the step 4 can be in any shape, the temperature of the oven is 80-100 ℃, and the drying time is 0.5-1 h.
Further, the pretreatment in step 4 is to spray a polytetrafluoroethylene mold with a mold release agent.
Further, in step 4, the volume of the liquid in the polytetrafluoroethylene can be determined according to the thickness of the required heat-conducting film.
Further, the plasma ablation machine in step 5 carries out ablation at 2100-3000 ℃, and the object to be ablated is horizontally or vertically moved at the speed of 1-5mm/s in the ablation process.
Further, step 5 includes naturally cooling the ablated film to room temperature, and then rolling the ablated film by using a hot press to improve the flexibility of the product.
The plasma ablation apparatus in the present invention is an apparatus capable of generating a plasma flame.
Compared with the prior art, the invention has the following beneficial technical effects:
1. according to the invention, a plasma ablation machine is introduced to carry out ablation treatment on the prepared polyimide composite membrane in the process of preparing the high-thermal-conductivity graphite membrane for the first time, so that the carbonization and graphitization time is greatly shortened.
2. Due to the use of the plasma ablation machine, the carbonized graphene in the original process is simplified into one step, so that the preparation process is simplified, the energy consumption is reduced, and the production efficiency of the product is improved.
3. Due to the fact that the prepared polyimide film is introduced with the graphene, the single-layer graphene oxide with high quality is adopted, under the condition of good dispersity, carbonization and graphitization treatment of the polyimide film and reduction of the graphene oxide are achieved by one step through high-temperature ablation, and the final product shows excellent heat conducting performance.
Detailed Description
The present invention is further described in detail with reference to the following specific examples, which are not to be construed as limiting the invention, and any simple modifications made without departing from the spirit of the invention are within the scope of the invention as claimed.
Example 1
Adding m-phenylenediamine and pyromellitic dianhydride into N, N-dimethylformamide, and uniformly stirring until the m-phenylenediamine and the pyromellitic dianhydride are completely dissolved to obtain a solution A; taking 1g of single-layer graphene oxide, dispersing in 10ml of solution, and performing ultrasonic treatment for 10min at 40 ℃ to obtain an orange-yellow graphene oxide colloid dispersion liquid B; continuously stirring in a water bath kettle at 50 ℃, and uniformly mixing the solution A in the step 1 and the dispersion liquid B in the step 2 to form a stable block system C; placing a polytetrafluoroethylene mold subjected to mold release agent spraying treatment in an oven, adding a plurality of block systems C obtained in the step (3) into the polytetrafluoroethylene mold, and curing and drying at 100 ℃ for 0.5 h; obtaining a dry product D; and (4) ablating the dried product D in the step (4) by using a plasma ablation machine, obtaining the graphene composite film with high thermal conductivity after 70S ablation at 2500 ℃, and rolling by using a hot press after the heat-conducting film is naturally cooled to room temperature to obtain a final product.
Through the test of a universal tensile tester, when the bending radius is 2mm, 2 ten thousand uninterrupted continuous tests show that the heat-conducting film prepared by the invention does not break, has very good flexibility, and has heat conductivity up to 2300W/mK in the horizontal direction when tested by the heat conductivity.
Example 2
Adding a plurality of p-phenylenediamine and pyromellitic dianhydride into N, N-dimethylformamide, wherein the molar ratio of the p-phenylenediamine to the pyromellitic dianhydride is 10:11, and uniformly stirring until the p-phenylenediamine and the pyromellitic dianhydride are completely dissolved to obtain a solution A; taking 0.1g of single-layer graphene oxide, dispersing in 10ml of solution, and performing ultrasonic treatment for 10min at 40 ℃ to obtain an orange-yellow graphene oxide colloid dispersion liquid B; continuously stirring in a water bath kettle at 50 ℃, and uniformly mixing the solution A in the step 1 and the dispersion liquid B in the step 2 to form a stable block system C; placing a polytetrafluoroethylene mold subjected to mold release agent spraying treatment in an oven, adding a plurality of block systems C obtained in the step (3) into the polytetrafluoroethylene mold, and curing and drying for 1h at 100 ℃; obtaining a dry product D; and (4) ablating the dried product D in the step (4) by using a plasma ablation machine, obtaining the graphene composite film with high thermal conductivity after 70S ablation at 2800 ℃, and rolling by using a hot press after the thermal conductive film is naturally cooled to room temperature to obtain a final product.
Through the test of a universal tensile tester, when the bending radius is 2mm, 2 ten thousand uninterrupted continuous tests show that the heat-conducting film prepared by the invention does not break and has very good flexibility, and the heat conductivity of the heat-conducting film in the horizontal direction is up to 2150W/mK when the heat conductivity of the heat-conducting film is tested.
Example 3
Adding a plurality of p-phenylenediamine and pyromellitic dianhydride into N, N-dimethylformamide, wherein the molar ratio of m-phenylenediamine to pyromellitic dianhydride is 1:1, and uniformly stirring until the m-phenylenediamine and the pyromellitic dianhydride are completely dissolved to obtain a solution A; taking 0.5g of single-layer graphene oxide, dispersing in 10ml of solution, and performing ultrasonic treatment for 10min at 40 ℃ to obtain an orange-yellow graphene oxide colloid dispersion liquid B; continuously stirring in a water bath kettle at 50 ℃, and uniformly mixing the solution A in the step 1 and the dispersion liquid B in the step 2 to form a stable block system C; placing a polytetrafluoroethylene mold subjected to mold release agent spraying treatment in an oven, adding a plurality of block systems C obtained in the step (3) into the polytetrafluoroethylene mold, and curing and drying for 1h at 100 ℃; obtaining a dry product D; and (4) ablating the dried product D in the step (4) by using a plasma ablation machine, obtaining the graphene composite film with high thermal conductivity after 70S ablation at 2800 ℃, and rolling by using a hot press after the thermal conductive film is naturally cooled to room temperature to obtain a final product.
Through the test of a universal tensile tester, when the bending radius is 2mm, 2 ten thousand uninterrupted continuous tests show that the heat-conducting film prepared by the invention does not break, has very good flexibility, and has heat conductivity up to 2300W/mK in the horizontal direction when tested by the heat conductivity.
Example 4
Adding a plurality of p-phenylenediamine and pyromellitic dianhydride into dimethyl sulfoxide, wherein the molar ratio of m-phenylenediamine to pyromellitic dianhydride is 10:12, and uniformly stirring until the m-phenylenediamine and the pyromellitic dianhydride are completely dissolved to obtain a solution A; taking 0.1g of single-layer graphene oxide, dispersing in 10ml of solution, and performing ultrasonic treatment for 10min at 40 ℃ to obtain an orange-yellow graphene oxide colloid dispersion liquid B; continuously stirring in a water bath kettle at 50 ℃, and uniformly mixing the solution A in the step 1 and the dispersion liquid B in the step 2 to form a stable block system C; placing a polytetrafluoroethylene mold subjected to mold release agent spraying treatment in an oven, adding a plurality of block systems C obtained in the step (3) into the polytetrafluoroethylene mold, and curing and drying for 1h at 100 ℃; obtaining a dry product D; and (4) ablating the dried product D in the step (4) by using a plasma ablation machine, obtaining the graphene composite film with high thermal conductivity after 70S ablation at 2800 ℃, and rolling by using a hot press after the thermal conductive film is naturally cooled to room temperature to obtain a final product.
Through the test of a universal tensile tester, when the bending radius is 2mm, 2 ten thousand uninterrupted continuous tests show that the heat-conducting film prepared by the invention does not break and has very good flexibility, and the heat conductivity of the heat-conducting film in the horizontal direction is up to 2200W/mK when the heat-conducting film is subjected to heat conductivity test.
Comparative example 1
The other steps are the same as those of the example 1, except that the plasma ablation machine is not used for ablation, but a conventional carbonization-prior-graphitization treatment mode is adopted, and the thermal conductivity of the prepared graphene composite film is also more than 2000W/mK, which proves that the plasma ablation machine does not cause serious reduction influence on the performance of the product.
Comparative example 2
The other steps are the same as those in example 1, except that the graphene oxide prepared by using the conventional Hummers method has obviously lower performance than that of the graphene oxide using a single layer in terms of the thermal conductivity of the final product, which also indicates that the performance of the composite thermal conductive film has a great relationship with the quality of graphene.

Claims (8)

1. A preparation method of a graphene composite film with high thermal conductivity is characterized by comprising the following steps:
step 1, adding a plurality of amine substances and anhydride substances into an organic solvent, and uniformly stirring until the amine substances and the anhydride substances are completely dissolved to obtain a solution A;
step 2, taking a plurality of single-layer graphene oxides, dispersing the single-layer graphene oxides in the solution, and performing ultrasonic treatment for 5-10min at the temperature of 30-60 ℃ to obtain an orange-yellow graphene oxide colloid dispersion liquid B;
step 3, continuously stirring in a water bath kettle at the temperature of 50-80 ℃, and uniformly mixing the solution A in the step 1 and the dispersion liquid B in the step 2 to form a stable block system C;
step 4, placing the pretreated polytetrafluoroethylene mold in an oven, adding a plurality of block systems C in the step 3 into the polytetrafluoroethylene mold, and curing and drying at 50-300 ℃; obtaining a dry product D;
and 5, ablating the dried product D in the step 4 at 2100-3000 ℃ by using a plasma ablation machine, horizontally or vertically moving the ablated object at the speed of 1-5mm/S in the ablation process, and ablating by 30-70S to obtain the graphene composite membrane with high thermal conductivity.
2. The method for preparing a graphene composite film with high thermal conductivity according to claim 1, wherein the method comprises the following steps: and naturally cooling the ablated film to room temperature, and then rolling by using a hot press.
3. The method for preparing a graphene composite film with high thermal conductivity according to claim 1, wherein the method comprises the following steps: the organic solvent in the step 1 comprises one or more of acetone, nitrogen-nitrogen dimethyl formamide and dimethyl sulfoxide.
4. The method for preparing a graphene composite film with high thermal conductivity according to claim 1, wherein the method comprises the following steps: the amine substance in the step 1 comprises one or more of p-phenylenediamine, m-phenylenediamine and dichloro-p-diaminobiphenyl.
5. The method for preparing a graphene composite film with high thermal conductivity according to claim 1, wherein the method comprises the following steps: the anhydride substances in the step 1 comprise one or more of pyromellitic dianhydride, diphenyl ether tetracarboxylic dianhydride and biphenyl tetracarboxylic dianhydride.
6. The method for preparing a graphene composite film with high thermal conductivity according to claim 1, wherein the method comprises the following steps: the molar ratio of the amine substance to the anhydride substance in the step 1 is 1: 1-2.
7. The method for preparing a graphene composite film with high thermal conductivity according to claim 1, wherein the method comprises the following steps: the sheet diameter of the single-layer graphene oxide in the step 2 is 0.5-5 microns, and the thickness of the single-layer graphene oxide is 0.8-1.2 nm; the concentration of the single-layer graphene oxide is 0.05-0.1 mg/ml.
8. The method for preparing a graphene composite film with high thermal conductivity according to claim 1, wherein the method comprises the following steps: the polytetrafluoroethylene mold in the step 4 can be in any shape, the temperature of the oven is 80-100 ℃, and the drying time is 0.5-1 h; the pretreatment is to spray a polytetrafluoroethylene mold by using a release agent.
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