CN115010119B - Graphene thick film and preparation method thereof - Google Patents
Graphene thick film and preparation method thereof Download PDFInfo
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- CN115010119B CN115010119B CN202210651995.2A CN202210651995A CN115010119B CN 115010119 B CN115010119 B CN 115010119B CN 202210651995 A CN202210651995 A CN 202210651995A CN 115010119 B CN115010119 B CN 115010119B
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Abstract
The invention relates to a graphene thick film and a preparation method thereof. The graphene thick film mainly comprises graphene nano sheets and polymer resin carbide, and has the volume density of 1.7g/cm 3 ～2.5g/cm 3 The thickness is 50-200 μm, and has high thermal diffusivity. The preparation process of the graphene thick film mainly comprises the preparation of the graphene oxide film and the preparation of the graphene thick film. The invention particularly obtains the functional graphene thick film mainly composed of graphene nano sheets and polymer resin carbide by regulating and controlling the components of the graphene oxide film, and solves the problems that the existing heat conducting film product is small in thickness and thermal diffusion coefficient, and the heat radiation performance requirement of a high-power electronic product is not met.
Description
Technical Field
The present invention relates to the field of materials science; mainly relates to a graphene thick film and a preparation method thereof.
Background
The 5G era comes, the integrated function of the electronic product is greatly increased, but the volume of the electronic product is smaller, and the heat dissipation requirement of core parts is obviously improved, so the electronic product has higher requirements on the heat management technology, such as higher heat diffusion coefficient and better heat diffusion stability for long-time working, can be processed into a 3D three-dimensional structure product, and can be combined with other materials to form a multifunctional composite material with heat conduction, heat storage and electromagnetic shielding.
The strong pi-pi accumulation and van der Waals force action in the graphene atomic layer can lead the graphene atomic layer to have small phonon scattering and large thermal diffusion coefficient. The film material prepared from graphene is the best choice of high thermal conductivity film material. Currently, chemical or thermal reduction of graphene oxide films is the most important method for preparing graphene films, wherein the quality of graphene oxide films is critical to the performance of graphene films. The graphene oxide film is limited by the size, density, components, reduction equipment and the like of the graphene oxide film, and the performances of the graphene film product such as specification, volume density, thickness, thermal diffusion coefficient and the like still have defects, so that the large-scale production and the application cannot be realized. The patent provides a graphene thick film and a preparation method thereof, and particularly, the graphene thick film consisting of graphene nano sheets and high polymer resin carbide is obtained by optimizing components of a graphene oxide film and combining mechanical cold pressing and dipping process technology, so that the graphene thick film has a large thermal diffusion coefficient.
Disclosure of Invention
The invention aims at: solves the problems of low volume density, small thickness and small thermal diffusion coefficient of the existing heat conducting film product, and provides a preparation method of a graphene thick film. The invention particularly obtains the graphene oxide film composed of special components through optimizing the components of the graphene oxide film and combining mechanical cold pressing and dipping process technology, and finally obtains the graphene thick film composed of graphene nano sheets and high polymer resin carbide, wherein the graphene thick film has large thermal diffusion coefficient and customizable thickness.
The technical scheme of the invention is as follows:
provides a graphene thick film which mainly comprises graphene nano sheets and polymer resin carbide, wherein the volume density of the graphene thick film is 1.7g/cm 3 ～2.5g/cm 3 The thickness is 50-200 mu m, the thermal diffusivity is 700mm 2 /s～1000mm 2 /s。
The preparation method of the graphene thick film comprises the following steps:
step 1, stirring, ultrasonic and vacuumizing a nano sheet composition of graphene oxide nano sheets and reduced graphene oxide nano sheets, a polyhydroxy compound and deionized water to obtain graphene oxide dispersion liquid; the dispersion liquid is placed in a mould made of polypropylene or aluminum foil, freeze-dried or supercritical dried to form solid, and then mechanically cold-pressed and vacuum heat-treated at 100-200 ℃ to obtain the reduced graphene oxide film.
The thickness of the graphene oxide nano sheet is 10 nm-20 nm, and the reduced graphene oxide nano sheet is obtained by treating the graphene oxide nano sheet for 30 min-90 min at 900-1200 ℃ under inert atmosphere or vacuum condition. Wherein, the hydroxyl and other reactive functional groups on the polyhydroxy compound can form chemical bonds between the nano sheets, perfect phonon transmission channels and improve the thermal diffusion coefficient of the material; in addition, the block material obtained by drying the graphene oxide dispersion liquid has a honeycomb microstructure, and the honeycomb walls connect the upper layer and the lower layer, so that the bonding force between the reduced graphene oxide film layers is improved, a new heat diffusion channel can be formed, the heat diffusion coefficient of the material is increased, and the heat conduction performance is improved. Particularly, polypropylene or aluminum foil is required to be selected as the mold, and because the polypropylene or aluminum foil has plasticity, the internal stress caused by volume expansion of the graphene oxide dispersion liquid from liquid to solid in the freezing process can be reduced and dissipated, so that the cracking of the material is effectively restrained and improved, and the product yield is improved.
Step 2, under the vacuum condition, immersing the reduced graphene oxide film in the mixture of the graphene oxide nano-sheets, deionized water and high polymer resin for 30-60 min, and further drying to obtain a graphene oxide macroscopic body; the graphene oxide macroscopic body is subjected to mechanical cold pressing to obtain the graphene oxide film. The surface density of the graphene oxide film is not less than 250g/m 2 The graphene oxide nano-sheet is mainly composed of graphene oxide nano-sheets, reduced graphene oxide nano-sheets, polyhydroxy compounds such as nanocellulose and the like, high polymer resins such as high carbon residue phenolic resin and the like, and the thickness of the graphene oxide nano-sheets is 10nm. The graphene oxide is subjected to heat treatment at 200 ℃ to release a large amount of volatile matters, so that a large amount of pores exist in the film, the thermal diffusivity of the material is reduced, so that the pores in the film are filled by impregnation, and further high polymer resins such as graphene oxide nano sheets, high carbon phenolic resin and the like are converted into carbide under the high temperature condition, so that the pores of the graphene film formed by the graphene nano sheets are reduced, and the compactness, the film thickness and the thermal diffusivity of the graphene film are improved. The areal density of the graphene oxide film prepared by impregnation based on the above assumption is greater than 250g/m 2 The thermal diffusivity of the prepared graphene thick film is not less than 700mm 2 And/s, exhibits excellent heat conduction properties when the areal density of the graphene oxide film is less than 250g/m 2 The thermal diffusivity of the prepared graphene film is not more than 300mm 2 /s。
And thirdly, pretreating the graphene oxide film in the second step under the inert atmosphere or vacuum condition at 150-600 ℃, then performing heat treatment at 2300-3000 ℃, and finally cooling the film material to room temperature and applying the pressure of 20-200 MPa to obtain the target graphene thick film.
Further, the mass of the reduced graphene oxide nanoplatelets in the nanoplatelet composition in the step one is not more than 50wt% of the mass of the graphene oxide nanoplatelets.
Further, in the first step, the polyhydroxy compound is at least one of dopamine, sodium alginate, tannic acid, nanocellulose and the like.
Further, in the first step, the mass ratio of the nano-sheet composition to the deionized water is 25-50 wt%;
further, the mass of the polyhydroxy compound in the step one is not more than 1 weight percent of the mass of deionized water.
Further, in the second step, the polymer resin is at least one of an alkynyl functional group-containing polymer, a benzoxazine resin, a phenolphthalein type polyether ether ketone, polyamide acid, soluble polyimide, high carbon residue phenolic resin and soluble asphalt.
Further, the pretreatment time in the step three is 200-600 min; the inert atmosphere is one or two of argon and nitrogen.
Further, in the third step, the heat treatment time is 480 min-1440 min, and the heat treatment atmosphere is one or two of argon and nitrogen.
The invention has the following advantages: the invention particularly obtains the graphene oxide film composed of special components through optimizing the components of the graphene oxide film and combining a cold drying technology, an impregnation technology and a mechanical cold pressing technology, and finally obtains the graphene thick film composed of graphene nano sheets and carbides of high polymer resin. The application of the mechanical cold pressing technology overcomes the size limitation of the graphene film, the specification and the size of the graphene thick film are not limited, continuous production can be realized, and the requirements of different use scenes can be met; the specificity of the graphene thick film component also enables the graphene thick film component to have a large thermal diffusion coefficient, and meets the requirement of rapid heat dissipation of electronic products.
The specific embodiment is as follows:
the invention is further illustrated by the following preferred embodiments.
Case 1:
step one, graphene oxide nano-sheets with the sheet diameter of 100 mu m and the thickness of 10nm are treated for 30min at 1200 ℃ under the argon condition, and reduced graphene oxide nano-sheets are obtained for later use.
2100g of graphene oxide nano-sheet, 900g of reduced graphene oxide nano-sheet, 5g of dopamine compound and 10000g of deionized water, and stirring, ultrasonic treatment and vacuumizing treatment are carried out to obtain graphene oxide dispersion liquid for later use. And (3) placing part of the dispersion liquid in a mould made of 320mm aluminum foil material, performing freeze drying, mechanical cold pressing and vacuum heat treatment at 200 ℃ for 90min to obtain the reduced graphene oxide film.
Step two, under the vacuum condition, immersing the reduced graphene oxide film in the step one in a mixture of graphene oxide nano sheets, deionized water and high-carbon phenolic resin for 30min, further drying to remove volatile matters such as deionized water and the like to obtain a graphene oxide macroscopic body, and mechanically cold-pressing to obtain the graphene oxide film with the surface density of 600g/m 2 。
And thirdly, pretreating the graphene oxide film in the second step for 240min in an argon atmosphere at 560 ℃, then performing heat treatment for 600min in an argon atmosphere at 2850 ℃, and finally cooling the film material to room temperature and applying a pressure of 200MPa to obtain a target graphene thick film, wherein the performances are shown in the table below.
Case 2:
firstly, stirring, performing ultrasonic and vacuumizing treatment on 4000g of sodium alginate 10g and 10000g of deionized water of graphene oxide nano-sheets with the sheet diameter of 100 mu m and the thickness of 10nm to obtain graphene oxide dispersion liquid for later use. And (3) placing part of the dispersion liquid in a mould made of 320mm x 170mm aluminum foil, performing freeze drying, mechanical cold pressing and vacuum heat treatment at 200 ℃ for 120min to obtain the reduced graphene oxide film.
Step two, under the vacuum condition, the reduced graphene oxide film in the step one is immersed in a mixture of graphene oxide nano sheets, deionized water and soluble asphalt for 60min, and is further dried to removeVolatile matter to obtain graphene oxide macroscopic body, and mechanically cold pressing to obtain graphene oxide film with surface density of 400g/m 2 。
Step three, the graphene oxide film in the step two is pretreated for 400min in an argon atmosphere at 590 ℃, then is subjected to heat treatment for 1000min in an argon atmosphere at 2900 ℃, and finally the film material is cooled to room temperature and a pressure of 200MPa is applied to obtain a target graphene thick film, and the performance of the target graphene thick film is as follows: the length is 300mm, the width is 150mm, the film thickness is about 70 mu m, and the thermal diffusivity is about 815mm 2 /s。
Claims (9)
1. The preparation method of the graphene thick film comprises the following steps of:
step 1, stirring, ultrasonic and vacuumizing a nano sheet composition of graphene oxide nano sheets and reduced graphene oxide nano sheets, a polyhydroxy compound and deionized water to obtain graphene oxide dispersion liquid; placing the dispersion liquid into a mould made of polypropylene or aluminum foil, performing freeze drying or supercritical drying to form a solid state, performing mechanical cold pressing, and performing vacuum heat treatment at 100-200 ℃ to obtain a reduced graphene oxide film;
the thickness of the graphene oxide nano sheet is 10 nm-20 nm, and the reduced graphene oxide nano sheet is obtained by heating the graphene oxide nano sheet for 30-90 min at 900-1200 ℃ under inert atmosphere or vacuum condition;
step 2, under the vacuum condition, immersing the reduced graphene oxide film in a mixture of graphene oxide nano sheets, deionized water and high polymer resin for 30-60 min, and drying to obtain a graphene oxide macroscopic body; the graphene oxide macroscopic body is subjected to mechanical cold pressing to obtain a graphene oxide film;
the surface density of the graphene oxide film is not less than 250g/m 2 The graphene oxide/graphene composite material consists of graphene oxide nano sheets, reduced graphene oxide nano sheets, polyhydroxy compounds and high-carbon-residue polymer resin;
and step 3, pretreating the graphene oxide film under the inert atmosphere or vacuum condition at 150-600 ℃, then performing heat treatment at 2300-3000 ℃, finally cooling to room temperature and applying the pressure of 20-200 MPa to obtain a graphene thick film.
2. The method for preparing a graphene thick film according to claim 1, wherein: in the step 1, the mass of the reduced graphene oxide nanoplatelets in the nanoplatelet composition is not more than 50wt% of the mass of the graphene oxide nanoplatelets.
3. The method for preparing a graphene thick film according to claim 1 or 2, characterized in that: in the step 1, the polyhydroxy compound is at least one of dopamine, sodium alginate, tannic acid and nanocellulose.
4. The method for preparing a graphene thick film according to claim 1 or 2, characterized in that: in the step 1, the mass ratio of the nano-sheet composition to the deionized water is 25-50 wt%.
5. The method for preparing a graphene thick film according to claim 1 or 2, characterized in that: in step 1, the mass of the polyhydroxy compound is not more than 1wt% of the mass of deionized water.
6. The method for preparing a graphene thick film according to claim 1 or 2, characterized in that: in the step 2, the high carbon residue high polymer resin is at least one of polymer containing alkynyl functional groups, benzoxazine resin, phenolphthalein type polyether ether ketone, polyamic acid, soluble polyimide, high carbon residue phenolic resin and soluble asphalt.
7. The method for preparing a graphene thick film according to claim 1 or 2, characterized in that: in the step 3, the pretreatment time is 200-600 min; the inert atmosphere is composed of one or two of argon and nitrogen.
8. The method for preparing a graphene thick film according to claim 1 or 2, characterized in that: in the step 3, the heat treatment time is 480-1440 min, and the heat treatment atmosphere is one or two of argon and nitrogen.
9. A thick graphene film prepared by the method of any one of claims 1 to 8, consisting of graphene nanoplatelets, polymeric resin carbides, the bulk density of the thick graphene film being 1.7g/cm 3 ～2.5g/cm 3 The thickness is 50-200 mu m, the thermal diffusivity is 700mm 2 /s～1000mm 2 /s。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111232962A (en) * | 2020-01-17 | 2020-06-05 | 深圳垒石热管理技术有限公司 | Method for preparing ultra-thick graphene heat dissipation film |
| CN113321208A (en) * | 2021-07-06 | 2021-08-31 | 中国科学院山西煤炭化学研究所 | Preparation method of high-compactness graphene membrane |
| CN113354415A (en) * | 2021-07-06 | 2021-09-07 | 中国科学院山西煤炭化学研究所 | Preparation method of ultrahigh-thermal-conductivity graphene film |
| CN114394585A (en) * | 2021-12-31 | 2022-04-26 | 深圳市深瑞墨烯科技有限公司 | Composite film, preparation method thereof and electronic equipment |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111232962A (en) * | 2020-01-17 | 2020-06-05 | 深圳垒石热管理技术有限公司 | Method for preparing ultra-thick graphene heat dissipation film |
| CN113321208A (en) * | 2021-07-06 | 2021-08-31 | 中国科学院山西煤炭化学研究所 | Preparation method of high-compactness graphene membrane |
| CN113354415A (en) * | 2021-07-06 | 2021-09-07 | 中国科学院山西煤炭化学研究所 | Preparation method of ultrahigh-thermal-conductivity graphene film |
| CN114394585A (en) * | 2021-12-31 | 2022-04-26 | 深圳市深瑞墨烯科技有限公司 | Composite film, preparation method thereof and electronic equipment |
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