CN113184842A - High-graphitization graphite thick film and preparation method thereof - Google Patents
High-graphitization graphite thick film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-graphitization graphite thick film and a preparation method thereof, and belongs to the technical field of graphite thick films. According to the invention, the nano-sheet material doped polyimide film is prepared, and then the nano-sheet material doped polyimide film is subjected to carbonization treatment and graphitization treatment in sequence to obtain the high-graphitization graphite thick film. The invention has simple process, no need of spraying in the preparation process, strong practicability, energy conservation, easy realization of industrial production and wide industrial prospect. The graphite thick film prepared by the method is light in weight and flexible, and the introduction of the nano-sheet layer material is beneficial to improving the graphitization degree inside the polyimide thick film, and solves the problems of brittleness, incomplete graphitization inside and the like of a finished product, so that the electric conductivity and the heat conductivity of the finished product are improved, and the application range of the finished product is widened.
Description
Technical Field
The invention relates to the technical field of graphite thick films, in particular to a high-graphitization graphite thick film and a preparation method thereof.
Background
At present, the 5G technology in China is developed rapidly, components are upgraded due to the rise of the technology, heat generated by matched components is increased, the temperature of the surface of a material is increased, and the service life of an electronic component and the stability of the whole system are affected if the heat cannot be discharged in time.
High heat conduction material is as the important component of heat dissipation solution, and the material that the quality is light, the flexibility is strong and have high thermal conductivity has very big demand, and traditional metal heat dissipation material is because the density is big, the thermal expansion coefficient is high, heat conductivity height such as not enough shortcomings, has hardly satisfied more and more rigorous heat dissipation demand. The graphite radiating fin has the characteristics of light weight, strong flexibility, small density, high heat conductivity coefficient and the like, is widely applied to the fields of intelligent components and the like, and can successfully solve various radiating problems.
Polyimide is used as a precursor with high carbon residue rate, and a graphite film material and a carbon/carbon (C/C) composite material prepared by carbonization and graphitization are materials with the highest usable temperature in all materials. The heat conduction material required in the specific fields of 5G and the like has extremely high heat conduction coefficient, the increase of the thickness of the graphite film is an effective method for improving the heat conduction performance of the graphite film, but the film forming rate of the thick film is low, and the graphitization temperature required by the thin film is higher while the thickness is increased, so that the generation of the ordered structure of the material is inhibited, and the energy consumption is increased.
At present, a single-walled carbon nanotube, a multi-walled carbon nanotube, carbon fiber and the like are mostly adopted as raw materials in a preparation process of a graphite film, but the carbon nanotube and the carbon fiber have a strip microstructure, the strip structure is easy to agglomerate and difficult to disperse, and the problems of uneven dispersion inside a filler matrix, incomplete graphitization of the graphite film and the like are easily caused in the preparation process of the graphite film.
The modes of improving the preparation process of raw materials, crosslinking film materials, adding a large amount of nano fillers and the like are general methods for enhancing the heat conductivity of the graphite film, but the operation steps are complex, the efficiency is low and the cost is high. In view of the above problems, it is necessary to provide a method for preparing a highly graphitized graphite thick film to solve the deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a highly graphitized graphite thick film and a preparation method thereof, which are used for solving a series of problems of nonuniform dispersion in the filler matrix, incomplete graphitization of the graphite film and the like in the prior art.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a preparation method of a high-graphitization graphite thick film, which comprises the following steps:
(1) preparing a nano-sheet material doped polyimide film:
the method comprises the following steps: respectively adding a nano-sheet material and diamine into an organic solvent, mixing the organic solvent and the diamine, continuously adding dianhydride to react, coating the obtained polyamic acid solution on a carrier, and performing drying and thermal imidization treatment to obtain a nano-sheet material doped polyimide film;
the method 2 comprises the following steps: respectively adding a nano-sheet material and a polyimide material into an organic solvent, mixing the nano-sheet material and the polyimide material, coating the obtained polyimide glue solution on a carrier, and drying to obtain a nano-sheet material doped polyimide film;
(2) carrying out carbonization treatment on the nano-sheet material doped polyimide film;
(3) and carrying out graphitization treatment on the carbonized sample to obtain the high-graphitization graphite thick film.
Further, the nano-sheet layer material is one of a carbon nitride nano-sheet, a boron nitride nano-sheet, a graphene oxide nano-sheet, graphite oxide alkyne powder, a titanium carbide nano-sheet and acetylene black; in the step (1), the organic solvent is at least one of N, N-dimethylformamide, N-methylpyrrolidone, N-dimethylacetamide, tetrahydrofuran, gamma-butyrolactone, hexamethylphosphoramide, dimethyl sulfoxide, and m-cresol.
Further, in the method 1 of the step (1), the diamine is one or more of an aromatic diamine and an aliphatic diamine, and the dianhydride is an aromatic ring-containing dianhydride monomer; the molar ratio of the diamine to the dianhydride is 1: 1-1: 1.05; the mass of the polyamic acid in the polyamic acid solution is 10-25% of that of the organic solvent; the nanosheet layer material accounts for 0.1-10% of the mass of the polyamic acid.
Further, in the method 1 of the step (1), the dianhydride is added for reaction after protective gas is introduced; the reaction temperature is-10-60 ℃, and the reaction time is 4-72 hours.
Further, in the method 1 of the step (1), the drying treatment is carried out at a temperature of 80-150 ℃ for 1-2 hours, and the thermal imidization treatment is carried out by firstly heating to 200-250 ℃ and maintaining for 0.5-1 hour, then heating to 300-400 ℃ and maintaining for 0.5-1 hour; the thickness of the nano-sheet material doped polyimide film is 80-250 mu m.
Further, in the method 2 in the step (1), the polyimide material is polyimide soluble in the organic solvent, the polyimide in the polyimide glue solution accounts for 10-25% of the mass of the organic solvent, and the nanosheet layer material accounts for 0.1-10% of the mass of the polyimide.
Further, in the method 2 in the step (1), the drying temperature is 80-150 ℃ and the drying time is 1-2 h.
Further, in the step (2), the end point temperature of the carbonization treatment is 900-1200 ℃, the temperature rise rate is 1-5 ℃/min, and the carbonization treatment is kept for 1-5 h after the end temperature is reached.
Further, in the step (3), the end temperature of the graphitization treatment is 2800-3000 ℃, the temperature rise rate is 5-10 ℃/min, and the treatment is kept for 2-3 h after the end temperature is reached.
The invention also provides the high-graphitization graphite thick film prepared by the preparation method, and the thickness of the graphite thick film is 75-150 mu m.
The invention discloses the following technical effects:
the nano-sheet layer material used in the invention has a lamellar structure, and compared with a strip microstructure (easy agglomeration and difficult dispersion) of substances such as carbon nanotubes and carbon fibers, the graphene-like structure in the graphite film is easier to arrange and easier to disperse in a matrix due to the lamellar structure.
The nano-sheet material can also enable the microstructure of polyimide to be looser, so that heat can enter the material more easily in the carbonization and graphitization processes, and the carbonization and graphitization are more complete. Elemental substances decomposed from the nanosheet layer material by heating can supplement carbon sites of the graphite film, so that the microstructure of the graphite film is more regular, and the conductivity and heat conductivity of the material are improved.
The method has the advantages of simple process operation, strong practicability, energy conservation, easy realization of industrial production and wide industrial prospect. The graphite thick film prepared by the method not only maintains the advantages of light weight, high use temperature and the like of the graphite film, but also has the function of catalyzing graphitization by the nano sheet material, is beneficial to improving the graphitization degree of the polyimide thick film by introducing the nano sheet material, has high graphitization degree on the surface and the inside, solves the problems of low film-forming rate, incomplete graphitization inside and the like of a finished product, improves the electric conduction and heat conduction performance of the finished product, and widens the application range of the finished product.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a scanning electron micrograph of graphite-phase carbon nitride.
Fig. 2 is a SEM image of a highly graphitized graphite thick film.
Figure 3 is a TEM image of a highly graphitized graphite thick film.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
In the invention, the material of the nanosheet layer is preferably a graphite-phase carbon nitride nanosheet, the purity of the graphite-phase carbon nitride nanosheet is more than 99%, and the diameter of the nanosheet is 1-10 μm.
In the invention, the nano-sheet layer material can also be one of boron nitride nano-sheet, graphene oxide nano-sheet, graphite oxide alkyne powder, titanium carbide nano-sheet and acetylene black.
In the invention, the purity of the boron nitride nanosheet is more than 98%, and the diameter of the nanosheet is 0.1-0.4 μm; the purity of the graphene nanosheet is greater than 98%, the diameter of the graphene nanosheet is 1-3 mu m, and the number of layers is 1-6; the purity of the graphene oxide nanosheet is more than 98%, the sheet diameter is more than 5 microns, and the number of layers is 1-6; the purity of the graphite oxide alkyne powder is more than 98%, and the sheet diameter is 50-80 nm; the purity of the titanium carbide nanosheet is more than 99%, and the thickness of the titanium carbide nanosheet is 100-200 nm; the purity of the acetylene black is more than 95%, and the sheet diameter is 35-45 nm;
in the invention, the nano-sheet material is added into an organic solvent, and preferably pressurized ultrasonic dispersion is carried out, wherein the pressure is preferably 0-0.1 MPa, the ultrasonic frequency is preferably 18-22 KHz, and the time is preferably 1-3 h.
In the present invention, the diamine is preferably at least one of diaminobenzene or a derivative thereof, diaminonaphthalene or a derivative thereof, benzidine or a derivative thereof, a diamine monomer containing an ether bond, a diamine monomer containing an ester bond, a diamine monomer containing an amide bond, diaminobenzene or a derivative thereof, diaminodiphenylmethane or a derivative thereof, diaminobenzophenone or a derivative thereof, diaminodiphenylsulfone or a derivative thereof, a diamine monomer containing a thioether structure, a diamine monomer containing a fluorene or fluorenone structure or a derivative thereof, a diamine monomer containing a three-fused ring structure or a derivative thereof, a diamine monomer containing a pyridine ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrimidine ring or triazine ring heterocyclic structure, and a diamine monomer containing a silicon or phosphorus element.
In the present invention, the dianhydride is preferably at least one of a benzene dianhydride-based compound, a biphenyl dianhydride-based compound, a polybiphenyl structure-containing dianhydride, a diphenylmethane dianhydride-based compound, a ketocarbonyl dianhydride-containing compound, a diphenyl ether dianhydride or a derivative thereof, an ether bond structure-containing dianhydride compound, a thioether bond structure-containing dianhydride compound, a sulfone group structure-containing dianhydride compound, a dianhydride compound in which two phthalic anhydrides are separated by an aliphatic chain, a tricyclic ring structure-containing dianhydride compound, and a dianhydride compound containing an ester group or an amide unit derived from trimellitic acid.
In the invention, the blade coating thickness of the polyamic acid solution or the polyimide glue solution on the carrier is preferably 1000-2000 μm.
In the invention, the carbonization treatment is preferably carried out in a carbonization furnace under the atmosphere of protective gas, and the carbonization treatment is vacuum-pumping high-temperature carbonization; the graphitization treatment is preferably performed in a graphite furnace under a protective gas atmosphere.
In the present invention, the shielding gas is preferably one of nitrogen, helium and argon.
In the invention, the graphite-phase carbon nitride can be doped with phosphorus, so that the catalytic performance of the graphite-phase carbon nitride can be further improved, and further the graphitization degree and the electric and heat conduction performance of the graphite film are improved.
The specific preparation steps of the phosphorus-doped graphite-phase carbon nitride are as follows:
(1) dissolving urea in water, wherein the mass volume ratio of the urea to the water is 10-20 g: 40-50 mL; drying the obtained solution at the temperature of 100-110 ℃; then, calcining, wherein the end point temperature is 450-550 ℃, the heating rate is 3-4 ℃/min, and the final temperature is kept for 2-4 h; grinding the obtained product to obtain g-C3N4。
(2) Mixing urea with g-C3N4Mixing with diammonium hydrogen phosphate, wherein the mass volume ratio of urea to diammonium hydrogen phosphate is 10-20 g: 30-40 mL, and the phosphorus element in diammonium hydrogen phosphate accounts for g-C3N4The mass ratio of (A) to (B) is 1-5%; then, drying and calcining are sequentially carried out, wherein the temperature of the drying treatment is 90-100 ℃, the end point temperature of the calcining treatment is 450-480 ℃, the heating rate is 2-3 ℃/min, and the temperature is kept for 3-4 h after the end point temperature is reached; and grinding the obtained product to obtain the phosphorus-doped graphite-phase carbon nitride.
Example 1
(1) Preparing a graphite-phase carbon nitride-doped polyimide film:
placing 0.04g of graphite-phase carbon nitride in 10mL of N-methyl pyrrolidone, and pressurizing and ultrasonically dispersing for 3h to obtain graphite-phase carbon nitride dispersion liquid; 2.4g of m-phenylenediamine was placed in 100mL of N-methylpyrrolidone, and magnetically stirred for 1 hour to obtain a diamine solution.
Mixing the graphite phase carbon nitride dispersion liquid and the diamine solution, magnetically stirring for 1h, adding 11.6g of bisphenol A dianhydride into the solution in batches under the protection of nitrogen, and reacting for 7h by mechanical stirring at the rotating speed of 300r/min to obtain a polyamic acid solution, wherein the polyamic acid accounts for 14% of the mass of the organic solvent, and the graphite phase carbon nitride accounts for 0.29% of the mass of the polyamic acid. The solution is coated on a glass plate in a blade coating thickness of 1000 mu m, the glass plate is placed in a high-temperature oven, the temperature is 100 ℃, the glass plate is kept for 2h, the temperature is continuously raised to 250 ℃ and kept for 1h, then the temperature is raised to 350 ℃ and kept for 0.5h, and the graphite-phase carbon nitride-doped polyimide film is obtained, and the film thickness is 110 mu m.
(2) And (3) placing the graphite-phase carbon nitride-doped polyimide film into a carbonization furnace for high-temperature carbonization in an argon atmosphere, wherein the carbonization end point temperature is 1000 ℃, the heating rate is 5 ℃/min, and keeping for 5h after the final temperature is reached.
(3) And transferring the carbonized sample into a graphite furnace for high-temperature graphitization in an argon atmosphere, wherein the graphitization end temperature is 3000 ℃, the temperature rise rate is 10 ℃/min, and the temperature is kept for 2.5h after the final temperature is reached, so that a high graphitization graphite thick film with the thickness of 108 micrometers is obtained.
Example 2
(1) Preparing a boron nitride-doped polyimide film:
placing 0.04g of boron nitride in 10mL of N-methyl pyrrolidone, and carrying out pressurized ultrasonic dispersion for 3h to obtain a boron nitride dispersion liquid; and (3) placing 5g of the polyimide film in 25.7mL of N, N-dimethylformamide, adding the boron nitride dispersion liquid, and uniformly stirring to obtain a polyimide glue solution containing boron nitride. Wherein the polyimide accounts for 14% of the mass of the organic solvent, and the boron nitride accounts for 0.29% of the mass of the polyimide. And (3) blade-coating the glue solution on a glass plate with the blade-coating thickness of 2000 mu m, and placing the glass plate in a high-temperature oven at the temperature of 100 ℃ for 1.5h to obtain the boron nitride doped polyimide film with the film thickness of 108 mu m.
(2) And (3) placing the boron nitride-doped polyimide film into a carbonization furnace for high-temperature carbonization in an argon atmosphere, wherein the carbonization end point temperature is 1000 ℃, the heating rate is 5 ℃/min, and keeping for 5h after the final temperature is reached.
(3) And transferring the carbonized sample into a graphite furnace for high-temperature graphitization in an argon atmosphere, wherein the graphitization end temperature is 3000 ℃, the temperature rise rate is 10 ℃/min, and the temperature is kept for 2.5h after the final temperature is reached, so that a high graphitization graphite thick film with the thickness of 106 mu m is obtained.
Example 3
(1) Preparing a titanium carbide doped polyimide film:
placing 0.015g of titanium carbide in 10mL of N, N-dimethylformamide, and carrying out pressurized ultrasonic dispersion for 2 hours to obtain a titanium carbide dispersion liquid; 0.66g of p-phenylenediamine and 1.22g of 4,4' -diaminodiphenyl ether were placed in 25.7mL of N, N-dimethylformamide and magnetically stirred for 1 hour to obtain a diamine solution.
Mixing the titanium carbide dispersion liquid and a diamine solution, magnetically stirring for 2 hours, adding 1.33g of pyromellitic dianhydride and 1.79g of biphenyl tetracarboxylic dianhydride into the solution in batches under the protection of nitrogen, and reacting for 8 hours by mechanical stirring at the rotating speed of 500r/min to obtain a polyamic acid solution, wherein the polyamic acid accounts for 14% of the mass of the organic solvent, and the titanium carbide accounts for 0.3% of the mass of the polyamic acid. The solution is coated on a glass plate in a blade coating thickness of 1900 μm, the glass plate is placed in a high-temperature oven at a temperature of 100 ℃ for 1.5h, the temperature is continuously raised to 250 ℃ for 1h, then the temperature is raised to 350 ℃ for 0.5h, and the titanium carbide doped polyimide film is obtained, and the film thickness is 105 μm.
(2) And (3) putting the titanium carbide doped polyimide film into a carbonization furnace for high-temperature carbonization in an argon atmosphere, wherein the carbonization end point temperature is 1000 ℃, the heating rate is 1.5 ℃/min, and the titanium carbide doped polyimide film is kept for 1h after the final temperature is reached.
(3) And transferring the carbonized sample into a graphite furnace for high-temperature graphitization in an argon atmosphere, wherein the graphitization end temperature is 3000 ℃, the temperature rise rate is 5 ℃/min, and the temperature is kept for 2h after the final temperature is reached, so that a high graphitization graphite thick film with the film thickness of 100 mu m is obtained.
Example 4
(1) Preparing the acetylene black doped polyimide film:
placing 0.01g of acetylene black into 10mL of N, N-dimethylformamide, and carrying out pressurized ultrasonic dispersion for 2 hours to obtain an acetylene black dispersion liquid; 1.26g of p-phenylenediamine was placed in 25.7mL of N, N-dimethylformamide and magnetically stirred for 0.5h to give a diamine solution.
Mixing the acetylene carbon black dispersion liquid with a diamine solution, magnetically stirring for 1h, adding 3.74g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride into the solution in batches under the protection of nitrogen, and reacting for 8h by mechanical stirring at the rotating speed of 700r/min to obtain a polyamic acid solution, wherein the polyamic acid accounts for 14% of the mass of the organic solvent, and the acetylene carbon black accounts for 0.2% of the mass of the polyamic acid. The solution is coated on a glass plate in a blade coating thickness of 1900 μm, the glass plate is placed in a high-temperature oven at a temperature of 130 ℃ for 1.5h, the temperature is continuously raised to 250 ℃ for 1h, then the temperature is raised to 350 ℃ for 0.5h, and the acetylene black doped polyimide film with the film thickness of 107 μm is obtained.
(2) And (2) putting the acetylene black doped polyimide film into a carbonization furnace for high-temperature carbonization in an argon atmosphere, wherein the carbonization end temperature is 1000 ℃, the heating rate is 4 ℃/min, and the final temperature is kept for 1.5 h.
(3) And transferring the carbonized sample into a graphite furnace for high-temperature graphitization in an argon atmosphere, wherein the graphitization end temperature is 3000 ℃, the temperature rise rate is 10 ℃/min, and the temperature is kept for 2.5h after the final temperature is reached, so that a high graphitization graphite thick film with the thickness of 106 mu m is obtained.
Example 5
(1) Preparing a graphene-doped polyimide film:
placing 0.04g of graphene nanosheet in 10mL of N-methyl pyrrolidone, and performing pressurized ultrasonic dispersion for 1h to obtain a graphene dispersion liquid; 2.4g of 4,4' -diaminodiphenyl ether was placed in 25.7mL of N-methylpyrrolidone, and magnetically stirred for 0.5h to obtain a diamine solution.
Mixing the graphene dispersion liquid and a diamine solution, stirring for 1h by magnetic force, adding 2.6g of pyromellitic dianhydride into the solution in batches under the protection of nitrogen, and reacting for 7h by mechanical stirring at the rotating speed of 600r/min to obtain a polyamic acid solution, wherein the polyamic acid accounts for 14% of the mass of the organic solvent, and the graphene accounts for 0.8% of the mass of the polyamic acid. The solution is coated on a glass plate in a blade coating thickness of 1900 μm, the glass plate is placed in a high-temperature oven at a temperature of 115 ℃ for 1.5h, the temperature is continuously raised to 250 ℃ for 1h, then the temperature is raised to 355 ℃ for 0.5h, and the graphene-doped polyimide film is obtained, and the film thickness is 103 μm.
(2) And (3) placing the graphene-doped polyimide film in a carbonization furnace for high-temperature carbonization in an argon atmosphere, wherein the carbonization end point temperature is 1000 ℃, the heating rate is 3 ℃/min, and keeping for 1h after the final temperature is reached.
(3) And transferring the carbonized sample into a graphite furnace for high-temperature graphitization in an argon atmosphere, wherein the graphitization end temperature is 3000 ℃, the temperature rise rate is 10 ℃/min, and the temperature is kept for 2h after the final temperature is reached, so that a high graphitization graphite thick film with the film thickness of 100 mu m is obtained.
Example 6
(1) Preparing a phosphorus-doped graphite-phase carbon nitride-doped polyimide film:
placing 0.04g of phosphorus-doped graphite-phase carbon nitride in 10mL of N-methyl pyrrolidone, and performing pressurized ultrasonic dispersion for 1h to obtain phosphorus-doped graphite-phase carbon nitride dispersion liquid; 2.4g of m-phenylenediamine was placed in 25.7mL of N-methylpyrrolidone, and magnetically stirred for 0.5h to obtain a diamine solution.
Mixing the phosphorus-doped graphite-phase carbon nitride dispersion liquid and a diamine solution, magnetically stirring for 1h, adding 2.6g of pyromellitic dianhydride into the solution in batches under the protection of nitrogen, and reacting for 7h by mechanical stirring at the rotating speed of 300r/min to obtain a polyamic acid solution, wherein the polyamic acid accounts for 14% of the mass of the organic solvent, and the phosphorus-doped graphite-phase carbon nitride accounts for 0.8% of the mass of the polyamic acid. The solution is coated on a glass plate in a blade coating thickness of 1900 μm, the glass plate is placed in a high-temperature oven at a temperature of 115 ℃ for 1.5h, the temperature is continuously raised to 250 ℃ for 1h, then the temperature is raised to 350 ℃ for 0.5h, and the polyimide film doped with the phosphorus-doped graphite-phase carbon nitride is obtained, and the film thickness is 105 μm.
(2) And (3) putting the polyimide film doped with the phosphorus-doped graphite-phase carbon nitride into a carbonization furnace for high-temperature carbonization in the argon atmosphere, wherein the carbonization end point temperature is 1000 ℃, the heating rate is 5 ℃/min, and the polyimide film is kept for 2h after the final temperature is reached.
(3) And transferring the carbonized sample into a graphite furnace for high-temperature graphitization in an argon atmosphere, wherein the graphitization end temperature is 3000 ℃, the temperature rise rate is 10 ℃/min, and the temperature is kept for 2h after the final temperature is reached, so that a high graphitization graphite thick film with the film thickness of 103 mu m is obtained.
Comparative example 1
(1) Preparing a polyimide film:
2.4g of 4,4' -diaminodiphenyl ether was placed in 35.7mL of N-methylpyrrolidone, and magnetically stirred for 0.5h to obtain a diamine solution.
Under the protection of nitrogen, 2.6g of pyromellitic dianhydride is added into the solution in batches, and the solution is mechanically stirred and reacted for 8 hours at the rotating speed of 500r/min to obtain a polyamic acid solution, wherein the polyamic acid accounts for 14% of the mass of the organic solvent. The solution was drawn down to a thickness of 1900 μm, and the glass plate was placed in a high-temperature oven at 100 ℃ for 1.5 hours, then heated to 250 ℃ for 1 hour, and then heated to 350 ℃ for 0.5 hour to give a polyimide film having a thickness of 105 μm.
(2) And (3) putting the polyimide film into a carbonization furnace for high-temperature carbonization in an argon atmosphere, wherein the carbonization end point temperature is 1000 ℃, the heating rate is 1.5 ℃/min, and the polyimide film is kept for 1h after the final temperature is reached.
(3) And transferring the carbonized sample into a graphite furnace for high-temperature graphitization in an argon atmosphere, wherein the graphitization end temperature is 3000 ℃, the temperature rise rate is 5 ℃/min, and the temperature is kept for 2h after the final temperature is reached, so that a high graphitization graphite thick film with the film thickness of 100 mu m is obtained.
Comparative example 2
(1) Preparing a polyimide film:
2.4g of m-phenylenediamine was placed in 100mL of N-methylpyrrolidone, and magnetically stirred for 1 hour to obtain a diamine solution.
Under the protection of nitrogen, 11.6g of bisphenol A dianhydride is added into the solution in batches and is reacted for 7 hours by mechanical stirring at the rotating speed of 300r/min to obtain polyamic acid solution, wherein the polyamic acid accounts for 14% of the mass of the organic solvent. The solution was drawn down to a thickness of 1000. mu.m, and the glass plate was placed in a high-temperature oven at 100 ℃ for 2 hours, then heated to 250 ℃ for 1 hour, and then heated to 350 ℃ for 0.5 hour to give a polyimide film having a thickness of 108. mu.m.
(2) And (3) putting the polyimide film into a carbonization furnace for high-temperature carbonization in an argon atmosphere, wherein the carbonization end point temperature is 1000 ℃, the heating rate is 5 ℃/min, and the polyimide film is kept for 4h after the final temperature is reached.
(3) And transferring the carbonized sample into a graphite furnace for high-temperature graphitization in an argon atmosphere, wherein the graphitization end temperature is 3000 ℃, the temperature rise rate is 8 ℃/min, and the temperature is kept for 2h after the final temperature is reached, so that a high graphitization graphite thick film with the thickness of 105 mu m is obtained.
The performance tests of examples 1-5 and comparative examples 1-2 are shown in Table 1 below:
TABLE 1 Properties of graphite Thick films
The graphitization degree is obtained by Raman spectrum test, any point of a cross section of the sample is taken as a test point, the number of the test point is the ratio of a disordered peak D peak to an ordered peak G peak, and the lower the numerical value is, the higher the graphitization degree is. As can be seen from table 1, the addition of the nanosheet material effectively improves the graphitization degree and the thermal conductivity of the sample. Therefore, the graphite thick film prepared by the method has high graphitization degree and good heat conduction performance, and is an ideal material for heat dissipation.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. The preparation method of the highly graphitized graphite thick film is characterized by comprising the following steps:
(1) preparing a nano-sheet material doped polyimide film:
the method comprises the following steps: respectively adding a nano-sheet material and diamine into an organic solvent, mixing the organic solvent and the diamine, continuously adding dianhydride to react, coating the obtained polyamic acid solution on a carrier, and performing drying and thermal imidization treatment to obtain a nano-sheet material doped polyimide film;
the method 2 comprises the following steps: respectively adding a nano-sheet material and a polyimide material into an organic solvent, mixing the nano-sheet material and the polyimide material, coating the obtained polyimide glue solution on a carrier, and drying to obtain a nano-sheet material doped polyimide film;
(2) carrying out carbonization treatment on the nano-sheet material doped polyimide film;
(3) and carrying out graphitization treatment on the carbonized sample to obtain the high-graphitization graphite thick film.
2. The method for preparing a highly graphitized graphite thick film according to claim 1, wherein the nanosheet material is one of carbon nitride nanosheets, boron nitride nanosheets, graphene oxide nanosheets, graphite oxide acetylene powder, titanium carbide nanosheets, and acetylene black; in the step (1), the organic solvent is at least one of N, N-dimethylformamide, N-methylpyrrolidone, N-dimethylacetamide, tetrahydrofuran, gamma-butyrolactone, hexamethylphosphoramide, dimethyl sulfoxide, and m-cresol.
3. The method for preparing a highly graphitized graphite thick film according to claim 1, wherein in the method 1 of the step (1), the diamine is one or more of aromatic diamine and aliphatic diamine, and the dianhydride is an aromatic ring-containing dianhydride monomer; the molar ratio of the diamine to the dianhydride is 1: 1-1: 1.05; the mass of the polyamic acid in the polyamic acid solution is 10-25% of that of the organic solvent; the nanosheet layer material accounts for 0.1-10% of the mass of the polyamic acid.
4. The method for preparing a highly graphitized graphite thick film according to claim 1, wherein in the method 1 of the step (1), the dianhydride is added for reaction after a protective gas is introduced; the reaction temperature is-10-60 ℃, and the reaction time is 4-72 hours.
5. The method for preparing a highly graphitized graphite thick film according to claim 1, wherein in the step (1), the drying treatment is performed at a temperature of 80 to 150 ℃ for 1 to 2 hours, and the thermal imidization treatment is performed by heating to 200 to 250 ℃ for 0.5 to 1 hour, then heating to 300 to 400 ℃ for 0.5 to 1 hour; the thickness of the nano-sheet material doped polyimide film is 80-250 mu m.
6. The method for preparing a highly graphitized graphite thick film according to claim 1, wherein in the method 2 in the step (1), the polyimide material is polyimide soluble in the organic solvent, the polyimide in the polyimide glue solution accounts for 10-25% by mass of the organic solvent, and the nanosheet material accounts for 0.1-10% by mass of the polyimide.
7. The method for preparing a highly graphitized graphite thick film according to claim 1, wherein in the method 2 of the step (1), the temperature of the drying treatment is 80 to 150 ℃ for 1 to 2 hours.
8. The method for preparing a highly graphitized graphite thick film according to claim 1, wherein in the step (2), the final temperature of the carbonization treatment is 900 to 1200 ℃, the temperature rise rate is 1 to 5 ℃/min, and the temperature is maintained for 1 to 5 hours after the final temperature is reached.
9. The method for preparing a highly graphitized graphite thick film according to claim 1, wherein in the step (3), the end temperature of the graphitization treatment is 2800-3000 ℃, the temperature increase rate is 5-10 ℃/min, and the temperature is maintained for 2-3 h after the end temperature is reached.
10. A highly graphitized graphite thick film obtained by the production process according to any one of claims 1 to 9, wherein the thickness of the graphite thick film is 75 to 150 μm.
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