CN109251733B - Graphene composite material heat-conducting film and preparation method thereof - Google Patents
Graphene composite material heat-conducting film and preparation method thereof Download PDFInfo
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Abstract
The invention provides a graphene composite material heat-conducting film and a preparation method thereof, wherein the raw material of the graphene composite material heat-conducting film comprises grapheneCerium zirconium solid solution, lanthanum oxide-modified cerium oxide, and V2O5The invention relates to a preparation method of a graphene oxide dispersion liquid, which comprises the steps of adding a cerium-zirconium solid solution, lanthanum oxide modified cerium dioxide and V into raw material graphene2O5The graphene composite material can effectively reduce the agglomeration among the graphene, improve the thermal conductivity and mechanical tensile strength of the graphene in the heat dissipation coating, and in addition, cerium-zirconium solid solution, lanthanum oxide modified cerium dioxide and V2O5The graphene composite material heat-conducting film can be added to form a net-shaped or chain-shaped structure inside the graphene composite material heat-conducting film, so that the graphene heat-conducting film forms a heat-conducting net chain, and the heat-conducting performance of the graphene heat-conducting film is greatly improved.
Description
Technical Field
The invention relates to the technical field of graphene, in particular to a graphene composite material heat-conducting film and a preparation method thereof.
Background
Graphene (Graphene) is a new material with a single-layer sheet structure composed of carbon atoms, which is sp from carbon atoms2The hexagonal honeycomb lattice planar film composed of the hybrid tracks is a two-dimensional material with the thickness of only one carbon atom.
Due to the special structure of graphene, researchers have been concerned about the development of graphene-related products, and various uses of graphene are increasingly shown. Among them, a graphene thermal conductive film with thermal conductivity, also called a thermal conductive graphene sheet, becomes a new thermal conductive and heat dissipating material emerging in recent years, and has been widely applied to many fields such as electronics, communications, lighting, aviation, national defense and military industry, and the like. The graphene heat-conducting film has the performances of higher heat conductivity coefficient, lower thermal resistance, lighter weight and the like, and the heat conductivity coefficient of the graphene heat-conducting film is higher than that of the carbon nano tube and the diamond; the thermal resistance is lower than that of aluminum and copper; the weight of the alloy is lower than that of aluminum and copper; in addition, the surface of the graphene heat-conducting film can be combined with other materials such as metal, plastic and adhesive sticker to meet more design functions and requirements, and the graphene heat-conducting film can be cut according to actual shape requirements, so that the graphene heat-conducting film has great market potential.
For example, chinese patent document CN104232027A discloses a method for preparing a graphene thermal conductive film, in which the raw materials of the graphene thermal conductive film include: the preparation method comprises the steps of firstly, uniformly dispersing graphene oxide or graphene modified by high-molecular-weight matrix materials such as polyvinyl alcohol, polystyrene and cellulose, namely functionalized graphene, the graphene oxide and the stabilizer in a solvent to obtain mixed slurry, then, rolling the mixed slurry, and separating a film from the matrix to finally obtain the graphene heat-conducting film. However, the thermal conductivity of the graphene thermal conductive film prepared by the above technology needs to be improved. Therefore, it is a technical problem to be solved urgently for those skilled in the art to develop a graphene thermal conductive film with a high thermal conductivity to meet the requirements of the thermal conductive film with a high thermal conductivity in the fields of electronics, communication, illumination, aviation, national defense, military industry and the like.
Disclosure of Invention
The invention provides a graphene composite material heat-conducting film which has a high heat-conducting coefficient. The invention further provides a preparation method of the compound.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a graphene composite material heat-conducting film, which comprises the following raw materials in parts by weight: 35-50 parts of graphene, 5-8 parts of cerium-zirconium solid solution, 2-6 parts of lanthanum oxide modified cerium dioxide and V2O53-8 parts by weight of a dispersing agent, 3-6 parts by weight of a coupling agent, 5-10 parts by weight of a heat stabilizer and 20-30 parts by weight of a solvent.
In the graphene composite material heat conduction membrane, the preparation method of the lanthanum oxide modified cerium dioxide comprises the following steps: preparing soluble lanthanum salt solution, dipping the solution on cerium dioxide, drying and roasting to obtain the cerium dioxide modified by lanthanum oxide.
Preferably, the dispersant is hexenyl bis stearamide or glyceryl tristearate; the coupling agent is 3-aminopropyl trimethoxy silane or gamma-mercaptopropyl triethoxy silane; the heat stabilizer is mono-tert-butyl malonate or butylene diacrylate; the solvent is ethanol.
Preferably, the soluble lanthanum salt is lanthanum nitrate; the drying temperature of the impregnated cerium dioxide is 70-90 ℃, preferably 80-85 ℃, the drying time is 2-4 hours, the roasting temperature is 260-400 ℃, preferably 300-350 ℃, and the drying time is 2-3 hours.
In a second aspect of the present invention, a preparation method of the graphene composite material thermal conductive film is provided, which includes the following steps:
(1) preparing graphene:
uniformly mixing the flake graphite powder and an intercalation agent sodium carbonate, and then adopting a mechanical grinding mode to obtain a mixed precursor; mixing the mixed precursor with an organic solvent, sequentially adding the poly-dopamine modified by the thiolated hydroxyethyl starch and a dispersing agent, uniformly stirring, and treating in an ultrasonic generator to obtain graphene;
(2) selecting the weight parts of the graphene prepared in the step (1) and the selected weight parts of cerium-zirconium solid solution, lanthanum oxide modified cerium dioxide and V2O5Mixing, grinding and shearing a dispersing agent, a coupling agent, a heat stabilizer and a solvent under the ultrasonic action, wherein the ultrasonic power is 1000-1200W, and the time is 40-60 min to obtain composite slurry;
(3) corona treatment of PET film: corona treatment is carried out on PET with the thickness of 30 mu m by adopting a corona machine;
(4) coating the uniformly mixed composite slurry on a PET film subjected to corona treatment in a hanging coating mode by adopting a table type coating machine, wherein the height of a scraper is 10-50 mm;
(5) drying the PET film coated in the step (4);
(6) carrying out hot rolling treatment on the dried PET film by using a pair roller press to obtain a PET-based graphene heat-conducting film;
(7) and carrying out edge cutting treatment on the PET-based graphene heat-conducting film subjected to the rolling treatment to obtain the graphene composite material heat-conducting film.
Preferably, in the step (1), the mass ratio of the flake graphite powder to the intercalation agent sodium carbonate is 1: 5; the dispersing agent is sodium dodecyl benzene sulfonate; the mass ratio of the flake graphite powder to the poly-dopamine modified by the sulfhydrylation hydroxyethyl starch to the dispersing agent is 1: 10: 80.
preferably, in the step (5), the drying temperature is 50-80 ℃ and the drying time is 12-18 h, preferably 15 h.
Preferably, in the step (6), the temperature of the upper die is stabilized to 80-110 ℃, preferably 90 ℃, the temperature of the lower die is stabilized to 80-110 ℃, preferably 90-100 ℃, and the rotating speed is 30-100 r/min.
In a third aspect of the invention, the graphene composite material heat-conducting film prepared by the preparation method is provided.
The technical scheme of the invention has the following advantages:
(1) the graphene composite material heat-conducting film comprises graphene, a cerium-zirconium solid solution, lanthanum oxide modified cerium dioxide and V2O5The invention relates to a preparation method of a graphene oxide dispersion liquid, which comprises the steps of adding a cerium-zirconium solid solution, lanthanum oxide modified cerium dioxide and V into raw material graphene2O5The graphene composite material can effectively reduce the agglomeration among the graphene, improve the thermal conductivity and mechanical tensile strength of the graphene in the heat dissipation coating, and in addition, cerium-zirconium solid solution, lanthanum oxide modified cerium dioxide and V2O5The graphene composite material heat-conducting film can be added to form a net-shaped or chain-shaped structure inside the graphene composite material heat-conducting film, so that the graphene heat-conducting film forms a heat-conducting net chain, and the heat-conducting performance of the graphene heat-conducting film is greatly improved. Through determination, the heat conductivity coefficient of the graphene composite material heat-conducting film prepared by the invention is 1800-2300W/m.K.
(2) The preparation method of the graphene composite material heat-conducting film comprises the steps of firstly uniformly mixing graphite powder and an intercalating agent, adopting a mechanical grinding mode to obtain a mixed precursor, then mixing the prepared mixed precursor with an organic solvent, sequentially adding the polydopamine modified by the sulfhydrylated hydroxyethyl starch and a dispersing agent, uniformly stirring, and carrying out ultrasonic treatment to obtain a graphene product. According to the preparation method of the graphene, the mild poly-dopamine modified by the sulfhydrylation hydroxyethyl starch and the dispersing agent are adopted for stripping, wherein the poly-dopamine modified by the sulfhydrylation hydroxyethyl starch has special surface activity and shows strong adsorption capacity, so that the poly-dopamine can be adsorbed with pi-pi electron cloud between benzene ring structures of graphite, the graphene on the outermost layer of natural graphite falls off from a graphite substrate into a solvent, and the chemical bond structure of the graphene is hardly damaged by continuously repeating the process.
(3) According to the preparation method of the graphene composite material heat-conducting film, the PET/graphene film after coating is dried at a proper temperature, and the solvent is controlled to volatilize at a slow speed, so that the phenomenon that a graphene film layer has a cavity is prevented; meanwhile, the temperature of the upper die, the temperature of the lower die and the rotating speed of the hot rolling are adjusted, so that the gaps among graphene sheet layers in the graphene film are reduced, the density of the graphene heat-conducting film is improved, and the heat transfer efficiency is improved.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The embodiment provides a preparation method of graphene, which comprises the following steps:
(1) preparation of polydopamine modified by thiolated hydroxyethyl starch
Dissolving 1g of hydroxyethyl starch with the molecular weight of 25000Da and the hydroxyethyl substitution degree of 0.5 in 10mL of deionized water, stirring until the hydroxyethyl starch is dissolved, then sequentially adding 1.2g of sodium hydroxide and 1.5g of chloroacetic acid to form a reaction system, reacting the reaction system at 100 ℃ for 5 hours, stopping the reaction, cooling to room temperature, pouring the reaction system into 20mL of methanol, stirring, and centrifuging to obtain white precipitate, namely carboxylated hydroxyethyl starch;
dissolving 0.8g of the carboxylated hydroxyethyl starch prepared in the previous step in 10mL of deionized water, adding 250mg of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 75mg of N-hydroxysuccinimide and 150mg of 2- (pyridyldithio) -ethylamine hydrochloride to form a reaction system, stirring the reaction system at 30 ℃ for reaction for 30 hours, centrifuging, dialyzing the supernatant by using dialysis bag deionized water with molecular weight cutoff of 3500Da for 3 days, and freeze-drying to obtain hydroxyethyl starch-2- (pyridyldithio);
dissolving 0.5g of hydroxyethyl starch-2- (pyridine disulfide) prepared in the above step in 10mL of dimethyl sulfoxide, adding 420mg of dithiothreitol, stirring and reacting at room temperature for 24h under the protection of nitrogen, dialyzing with dialysis bag deionized water with molecular weight cutoff of 3500Da for 3 days, and freeze-drying to obtain thiolated hydroxyethyl starch;
dispersing 40mg of polydopamine in 10mL of deionized water, carrying out stirring and ultrasonic treatment for 30min, adding sodium hydroxide to adjust the pH value to 10, then slowly adding 200mg of the thiolated hydroxyethyl starch prepared in the previous step while stirring, after the addition is finished, carrying out stirring reaction for 30h at room temperature, carrying out ultrafiltration to remove unreacted thiolated hydroxyethyl starch, wherein the molecular weight cut-off of the ultrafiltration tube is 100kDa, and the ultrafiltration speed is 4000 rpm, so as to obtain the polydopamine modified by the thiolated hydroxyethyl starch;
(2) preparation of graphene
Uniformly mixing 1g of flake graphite powder and 5g of sodium carbonate serving as an intercalation agent, and mechanically and horizontally grinding for 50 hours to obtain a mixed precursor;
and (2) mixing the mixed precursor with 250mL of methanol, sequentially adding 10g of the dopamine modified by the thiolated hydroxyethyl starch prepared in the step (1) and 80g of sodium dodecyl benzene sulfonate, uniformly stirring, performing ultrasonic treatment by using an ultrasonic generator for 1h at the ultrasonic power of 300W, washing with water, centrifuging, and drying at 50 ℃ to obtain the graphene.
Example 2
The embodiment provides a graphene composite material heat-conducting film, which comprises the following raw materials in parts by weight:
35g of graphene, 8g of cerium-zirconium solid solution, 2g of lanthanum oxide-modified cerium oxide, and V2O58g of hexenyl bis stearamide, 3g of gamma-mercaptopropyl triethoxysilane, 4g of mono-tert-butyl malonate and 30g of ethanol;
the preparation method of the lanthana-modified ceria in this example is as follows:
preparing a lanthanum nitrate aqueous solution with the mass concentration of 10 t%, dipping the lanthanum nitrate aqueous solution on cerium dioxide, drying the dipped cerium dioxide at 90 ℃ for 2h, and roasting at 260 ℃ for 3h to obtain lanthanum oxide modified cerium dioxide; wherein the mass ratio of the lanthanum nitrate aqueous solution with the mass concentration of 10 t% to the cerium dioxide is 1: 5;
the embodiment also provides a preparation method of the graphene composite material heat-conducting film, which comprises the following steps:
(1) 35g of the graphene obtained in example 1, 8g of a cerium-zirconium solid solution, 2g of lanthanum oxide-modified cerium oxide, and 8gV2O53g of hexenyl bis stearamide, 10g of gamma-mercaptopropyltriethoxysilane, 4g of mono-tert-butyl malonate and 30g of ethanol are mixed, ground and sheared under the ultrasonic action, the ultrasonic power is 1000W, and the ultrasonic action lasts 60min to obtain composite slurry;
(2) corona treatment of PET film: corona treatment is carried out on PET with the thickness of 30 mu m by adopting a corona machine;
(3) coating the uniformly mixed composite slurry on a PET film subjected to corona treatment in a hanging coating mode by adopting a table type coating machine, wherein the height of a scraper is 10 mm;
(4) drying the PET film coated in the step (3) at 50 ℃ for 18 h;
(5) carrying out hot rolling treatment on the dried PET film by using a pair roller press to obtain a PET-based graphene heat-conducting film, wherein the temperature of an upper die of the hot rolling treatment is stabilized at 80 ℃, the temperature of a lower die of the hot rolling treatment is stabilized at 110 ℃, and the rotating speed is 30 r/min;
(6) and carrying out edge cutting treatment on the PET-based graphene heat-conducting film subjected to the rolling treatment to obtain the graphene composite material heat-conducting film.
Example 3
The embodiment provides a graphene composite material heat-conducting film, which comprises the following raw materials in parts by weight:
50g of graphene, 5g of cerium-zirconium solid solution, 6g of lanthanum oxide modified cerium oxide and V2O53g of glyceryl tristearate, 6g of 3-aminopropyltrimethoxysilane, 5g of 3-aminopropyltrimethoxysilane, 9g of butylene diacrylate and 20g of ethanol;
the preparation method of the lanthana-modified ceria in this example is as follows:
preparing a lanthanum nitrate aqueous solution with the mass concentration of 10 t%, dipping the lanthanum nitrate aqueous solution on cerium dioxide, drying the dipped cerium dioxide at 70 ℃ for 4h, and roasting at 400 ℃ for 2h to obtain lanthanum oxide modified cerium dioxide; wherein the mass ratio of the lanthanum nitrate aqueous solution with the mass concentration of 10 t% to the cerium dioxide is 1: 5;
the embodiment also provides a preparation method of the graphene composite material heat-conducting film, which comprises the following steps:
(1) 50g of the graphene obtained in example 1, 5g of a cerium-zirconium solid solution, 6g of lanthanum oxide-modified cerium oxide, and 3gV2O56g of glyceryl tristearate, 5g of 3-aminopropyltrimethoxysilane, 9g of butylene diacrylate and 20g of ethanol are mixed, ground and sheared under the ultrasonic action, the ultrasonic power is 1200W, and the ultrasonic time is 40min, so that composite slurry is obtained;
(2) corona treatment of PET film: corona treatment is carried out on PET with the thickness of 30 mu m by adopting a corona machine;
(3) coating the uniformly mixed composite slurry on a PET film subjected to corona treatment in a hanging coating mode by adopting a table type coating machine, wherein the height of a scraper is 50 mm;
(4) drying the PET film coated in the step (3) at 80 ℃ for 12 h;
(5) carrying out hot rolling treatment on the dried PET film by using a pair roller press to obtain a PET-based graphene heat-conducting film, wherein the temperature of an upper die of the hot rolling treatment is stabilized to be 110 ℃, the temperature of a lower die of the hot rolling treatment is stabilized to be 80 ℃, and the rotating speed is 100 r/min;
(6) and carrying out edge cutting treatment on the PET-based graphene heat-conducting film subjected to the rolling treatment to obtain the graphene composite material heat-conducting film.
Example 4
The embodiment provides a graphene composite material heat-conducting film, which comprises the following raw materials in parts by weight:
40g of graphene, 7g of cerium-zirconium solid solution, 4g of lanthanum oxide-modified cerium oxide, and V2O55g of hexenyl bis stearamide, 4g of 3-aminopropyl trimethoxy silane, 6g of butylene diacrylate and 25g of ethanol;
the preparation method of the lanthana-modified ceria in this example is as follows:
preparing a lanthanum nitrate aqueous solution with the mass concentration of 10 t%, dipping the lanthanum nitrate aqueous solution on cerium dioxide, drying the dipped cerium dioxide at 80 ℃ for 3h, and roasting at 350 ℃ for 2.5h to obtain lanthanum oxide modified cerium dioxide; wherein the mass ratio of the lanthanum nitrate aqueous solution with the mass concentration of 10 t% to the cerium dioxide is 1: 5;
the embodiment also provides a preparation method of the graphene composite material heat-conducting film, which comprises the following steps:
(1) 40g of the graphene obtained in example 1, 7g of a cerium-zirconium solid solution, 4g of lanthanum oxide-modified cerium oxide, and 5gV2O54g of hexenyl bis stearamide, 8g of 3-aminopropyltrimethoxysilane, 6g of butylene diacrylate and 25g of ethanol are mixed, ground and sheared under the ultrasonic action, the ultrasonic power is 1200W, and the ultrasonic time is 40min, so that composite slurry is obtained;
(2) corona treatment of PET film: corona treatment is carried out on PET with the thickness of 30 mu m by adopting a corona machine;
(3) coating the uniformly mixed composite slurry on a PET film subjected to corona treatment in a hanging coating mode by adopting a table type coating machine, wherein the height of a scraper is 50 mm;
(4) drying the PET film coated in the step (3) at 80 ℃ for 15 h;
(5) carrying out hot rolling treatment on the dried PET film by using a pair roller press to obtain a PET-based graphene heat-conducting film, wherein the temperature of an upper die of the hot rolling treatment is stabilized at 90 ℃, the temperature of a lower die of the hot rolling treatment is stabilized at 100 ℃, and the rotating speed of the hot rolling treatment is 50 r/min;
(6) and carrying out edge cutting treatment on the PET-based graphene heat-conducting film subjected to the rolling treatment to obtain the graphene composite material heat-conducting film.
Example 5
The embodiment provides a graphene composite material heat-conducting film, which comprises the following raw materials in parts by weight:
45g of graphene, 6g of cerium-zirconium solid solution, 3g of lanthanum oxide-modified cerium oxide, and V2O57g of hexenyl bis stearamide, 4g of gamma-mercaptopropyl triethoxysilane, 5g of mono-tert-butyl malonate and 23g of ethanol;
the preparation method of the lanthana-modified ceria in this example is as follows:
preparing a lanthanum nitrate aqueous solution with the mass concentration of 10 t%, dipping the lanthanum nitrate aqueous solution on cerium dioxide, drying the dipped cerium dioxide at 90 ℃ for 2h, and roasting at 260 ℃ for 3h to obtain lanthanum oxide modified cerium dioxide; wherein the mass ratio of the lanthanum nitrate aqueous solution with the mass concentration of 10 t% to the cerium dioxide is 1: 5;
the embodiment also provides a preparation method of the graphene composite material heat-conducting film, which comprises the following steps:
(1) 45g of the graphene obtained in example 1, 6g of a ceria-zirconia solid solution, 3g of lanthanum oxide-modified ceria, and 7g of V2O54g of hexenyl bis stearamide, 9g of gamma-mercaptopropyltriethoxysilane, 5g of mono-tert-butyl malonate and 23g of ethanol are mixed, ground and sheared under the ultrasonic action, the ultrasonic power is 1100W, and the ultrasonic action lasts for 50min to obtain composite slurry;
(2) corona treatment of PET film: corona treatment is carried out on PET with the thickness of 30 mu m by adopting a corona machine;
(3) coating the uniformly mixed composite slurry on a PET film subjected to corona treatment in a hanging coating mode by adopting a table type coating machine, wherein the height of a scraper is 30 mm;
(4) drying the PET film coated in the step (3) at 70 ℃ for 16 h;
(5) carrying out hot rolling treatment on the dried PET film by using a pair roller press to obtain a PET-based graphene heat-conducting film, wherein the temperature of an upper die of the hot rolling treatment is stabilized at 100 ℃, the temperature of a lower die of the hot rolling treatment is stabilized at 90 ℃, and the rotating speed of the hot rolling treatment is 70 r/min;
(6) and carrying out edge cutting treatment on the PET-based graphene heat-conducting film subjected to the rolling treatment to obtain the graphene composite material heat-conducting film.
Experimental example 1
Calculating the heat conductivity coefficient of the graphene composite material heat-conducting film prepared in the embodiment 2-5:
the thermal conductivity of the graphene thermal conductive film prepared in each example was calculated according to the following formula (1),
K＝αi·Cp·ρ0(1)，
wherein K is a thermal conductivity coefficient, α i is a thermal diffusion coefficient of the sample, Cp is a constant pressure specific heat capacity of the test sample, and rho 0 is a density of the test sample, and the measured thermal conductivity coefficients of the graphene thermal conductive films of the embodiments are shown in Table 1.
Table 1 heat conductivity coefficients of graphene heat conductive films prepared in examples 2 to 5
| Thermal conductivity coefficient (W/m.K) of graphene thermal conductive film | |
| Example 2 | 2000 |
| Example 3 | 2300 |
| Example 4 | 1900 |
| Example 5 | 1800 |
As can be seen from table 1, the graphene thermal conductive film prepared by the present invention has good thermal conductivity.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. The graphene composite material heat-conducting film is characterized by comprising the following raw materials in parts by weight: 35-50 parts of graphene, 5-8 parts of cerium-zirconium solid solution, 2-6 parts of lanthanum oxide modified cerium dioxide and V2O53-8 parts by weight of a dispersant, 3-6 parts by weight of a coupling agent, 5-10 parts by weight of a heat stabilizer and 20-30 parts by weight of a solvent;
the preparation method comprises the following steps of uniformly mixing flake graphite powder and an intercalation agent sodium carbonate, obtaining a mixed precursor by adopting a mechanical grinding mode, mixing the mixed precursor with an organic solvent, sequentially adding polydopamine modified by sulfhydrylation hydroxyethyl starch and a dispersing agent, uniformly stirring, and processing in an ultrasonic generator to obtain the graphene.
2. The graphene composite material heat conduction membrane according to claim 1, wherein the preparation method of the lanthanum oxide modified cerium dioxide comprises the following steps:
preparing soluble lanthanum salt solution, dipping the solution on cerium dioxide, drying and roasting to obtain the cerium dioxide modified by lanthanum oxide.
3. The graphene composite material heat-conductive film according to claim 1 or 2,
the dispersing agent is hexenyl bis stearamide or glyceryl tristearate;
the coupling agent is 3-aminopropyl trimethoxy silane or gamma-mercaptopropyl triethoxy silane;
the heat stabilizer is mono-tert-butyl malonate or butylene diacrylate;
the solvent is ethanol.
4. The graphene composite material thermal conductive film according to claim 2, wherein the soluble lanthanum salt is lanthanum nitrate; the drying temperature of the impregnated cerium dioxide is 70-90 ℃, the drying time is 2-4 hours, the roasting temperature is 260-400 ℃, and the roasting time is 2-3 hours.
5. The preparation method of the graphene composite material heat conduction film according to any one of claims 1 to 4, characterized by comprising the following steps:
(1) preparing graphene:
uniformly mixing the flake graphite powder and an intercalation agent sodium carbonate, and then adopting a mechanical grinding mode to obtain a mixed precursor; mixing the mixed precursor with an organic solvent, sequentially adding the poly-dopamine modified by the thiolated hydroxyethyl starch and a dispersing agent, uniformly stirring, and treating in an ultrasonic generator to obtain graphene;
(2) selecting the weight parts of the graphene prepared in the step (1) and the selected weight parts of cerium-zirconium solid solution, lanthanum oxide modified cerium dioxide and V2O5Mixing, grinding and shearing a dispersing agent, a coupling agent, a heat stabilizer and a solvent under the ultrasonic action, wherein the ultrasonic power is 1000-1200W, and the time is 40-60 min to obtain composite slurry;
(3) corona treatment of PET film: corona treatment is carried out on PET with the thickness of 30 mu m by adopting a corona machine;
(4) coating the uniformly mixed composite slurry on a PET film subjected to corona treatment in a hanging coating mode by adopting a table type coating machine, wherein the height of a scraper is 10-50 mm;
(5) drying the PET film coated in the step (4);
(6) carrying out hot rolling treatment on the dried PET film by using a pair roller press to obtain a PET-based graphene heat-conducting film;
(7) and carrying out edge cutting treatment on the PET-based graphene heat-conducting film subjected to the rolling treatment to obtain the graphene composite material heat-conducting film.
6. The method for preparing the graphene composite material heat-conducting film according to claim 5, wherein in the step (1),
the mass ratio of the flake graphite powder to the intercalation agent sodium carbonate is 1: 5;
the dispersing agent is sodium dodecyl benzene sulfonate;
the mass ratio of the flake graphite powder to the poly-dopamine modified by the sulfhydrylation hydroxyethyl starch to the dispersing agent is 1: 10: 80.
7. the preparation method of the graphene composite material heat-conducting film according to claim 5 or 6, wherein in the step (5), the drying temperature is 50-80 ℃ and the drying time is 12-18 h.
8. The preparation method of the graphene composite material heat-conducting film according to claim 7, wherein in the step (6), the temperature of the upper die of the hot rolling treatment is stabilized to 80-110 ℃, the temperature of the lower die is stabilized to 80-110 ℃, and the rotating speed is 30-100 r/min.
9. The graphene composite material heat-conducting film prepared by the preparation method of any one of claims 5 to 8.
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| CN111628172A (en) * | 2020-05-12 | 2020-09-04 | 山东领军科技集团有限公司 | Production process of graphene-based battery conductive agent |
| CN115637118B (en) * | 2022-09-08 | 2023-11-21 | 湖南万祺科技有限公司 | Lithium battery double-sided hot melt adhesive based on high adhesion under thermal stability |
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