CN110104632B - Method for preparing high-thermal-conductivity graphene film at normal temperature - Google Patents
Method for preparing high-thermal-conductivity graphene film at normal temperature Download PDFInfo
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- CN110104632B CN110104632B CN201910277061.5A CN201910277061A CN110104632B CN 110104632 B CN110104632 B CN 110104632B CN 201910277061 A CN201910277061 A CN 201910277061A CN 110104632 B CN110104632 B CN 110104632B
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Abstract
The invention discloses a method for preparing a high-thermal-conductivity graphene film at normal temperature. According to the invention, large-size graphene sheets and small-size graphene sheets are mixed to obtain a prepared graphene oxide solution, and then the reduced graphene oxide film is prepared by wet spinning and hydroiodic acid. The reduced graphene oxide obtained by the method has quite excellent thermal conductivity without high-temperature heat treatment, and the thermal conductivity of the product can be adjusted within a certain range according to needs. The method has the characteristics of relatively simple synthesis process and low cost, and simultaneously provides a brand-new research direction for applying the graphene to the field of heat dissipation materials: the internal defects of the graphene film product are improved by adjusting the size distribution to improve the thermal conductivity, rather than cost consumption for high-temperature heat treatment to eliminate the defects, and a wider prospect is provided for the application of the graphene in the thermal management direction of the integrated circuit.
Description
Technical Field
The invention relates to a method for preparing a graphene film at normal temperature, in particular to a method for preparing a high-thermal-conductivity graphene film by regulating and controlling the size distribution of graphene oxide lamella and then reducing.
Background
With the continuous development of the modern electronic and electrical industry, the problem of effective heat dissipation gradually becomes the elbow of the development of the modern electronic and electrical industry, and in the chip industry, the effective heat dissipation becomes the bottleneck restricting the continuous reduction of the chip size; in the development of the equipment industry such as electric and cable, the filler or coating capable of enhancing heat dissipation is more prominent and important in the fields of preventing equipment aging and the like; especially in the field of aerospace, heat dissipation is also a key factor in determining the performance of many devices. In order to solve the problem of effective heat dissipation, various high-performance heat dissipation materials are produced. The carbon material is an ideal material for high-performance heat dissipation fins due to the characteristics of good heat conductivity, high chemical thermal stability, light weight, human friendliness and the like. Wherein the graphene material is extremely highThermal conductivity (up to 5300 W.m)-1·K-1) And a natural two-dimensional structure, and has great potential in the field of preparing transverse heat dissipation materials.
There are various conventional methods for preparing a graphene film having high thermal conductivity, such as a liquid lift-off method, an electrospray deposition method, a chemical vapor deposition method, and the like. But they are not suitable for large-scale production of graphene films due to cost issues. In recent years, self-assembly re-reduction of graphene oxide has proven to be an effective way to mass-produce graphene thin films with excellent heat dissipation properties. However, in the current research, the method usually needs a high-temperature post-treatment at 1000 to 3000 ℃ to obtain high thermal conductivity, and the post-treatment greatly increases the energy consumption and time cost of film preparation, and is not beneficial to popularization of mass production.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art, and provide a method for directly preparing a high-thermal-conductivity graphene film at normal temperature, which does not need high-temperature post-treatment, simplifies the preparation, reduces the cost and realizes batch production.
Therefore, the invention adopts the following technical scheme: the method for preparing the high-thermal-conductivity graphene film at normal temperature comprises the following steps:
1) preparing a graphene oxide solution: carrying out cell ultrasonic crushing treatment on a part of uniformly dispersed large-size graphene oxide solution with the concentration of 8-18mg/ml to obtain a small-size graphene oxide solution with the same concentration, and then uniformly mixing the other part of large-size graphene oxide solution and the small-size graphene oxide solution to obtain a mixed graphene oxide solution;
2) injecting the mixed graphene oxide solution obtained in the step 1) into a coagulation bath consisting of calcium chloride, ethanol and water for flocculation, and conveying the solution through a polyethylene glycol terephthalate film to obtain a graphene oxide film treated by the coagulation bath;
3) collecting the graphene oxide film subjected to coagulation bath treatment obtained in the step 2), soaking the graphene oxide film in an ethanol water solution for cleaning, then placing the graphene oxide film on a hot bench at the temperature of 30-60 ℃, drying for 1-3 hours, then placing the graphene oxide film in a vacuum oven, keeping the temperature at 50-80 ℃, and further drying for 3-8 hours;
4) soaking the product obtained in the step 3) and a polyethylene glycol terephthalate film in deionized water for 1-5 hours, then stripping in the deionized water to obtain an unsupported graphene oxide film, placing the unsupported graphene oxide film in a vacuum oven again, and drying for 6-12 hours at the temperature of 50-80 ℃;
5) soaking the unsupported graphene oxide film dried in the step 4) in a reducing agent for reaction, and meanwhile, placing the reaction system in a water bath at the temperature of 60-90 ℃ for heating for 8-14 hours;
6) washing the film reacted in the step 5) with a saturated sodium bicarbonate solution, deionized water and absolute ethyl alcohol in sequence, then placing the film in a vacuum oven, and drying at the temperature of 80-120 ℃ for 10-16 hours to obtain the graphene film with high thermal conductivity.
Compared with other methods for preparing a reduced graphene oxide film, the method for preparing the high-thermal-conductivity graphene film at normal temperature provided by the invention has the following advantages: the thickness of the reduced graphene oxide film can be effectively controlled by controlling the concentration of the graphene oxide solution, and the thermal conductivity of the reduced graphene oxide film can be further controlled by controlling the size distribution of graphene oxide lamella; in addition, the method does not need high-temperature post-treatment, and has the advantages of simple and convenient operation, low cost, large-scale production, high efficiency and the like.
Further, in the step 1), the particle size of the large-size graphene oxide is 10-15 μm; the particle size of the small-size graphene oxide is 2-4 mu m.
Further, in the step 2), the mass fraction of the small-sized graphene oxide in the mixed graphene oxide solution is 10 to 90%, preferably 30 to 70%, and most preferably 50%.
Further, in the step 2), the coagulating bath component is a mixed solution of ethanol and water in a volume ratio of 1:2-1:5, and calcium chloride with a mass fraction of 3-8%.
Further, in the step 5), the reducing agent is a hydroiodic acid solution, and the mass fraction of the hydroiodic acid solution is 30-50%.
Further, in the step 3), the mass fraction of the ethanol in the ethanol aqueous solution is 90-95%.
Compared with the existing method for preparing the high-thermal-conductivity graphene film, the method has the following advantages:
(1) in the invention, a plurality of reducing agents can be selected, and the graphene oxide film can be reduced to obtain the required high-thermal-conductivity graphene film by using common graphene oxide reducing agents such as hydroiodic acid, ascorbic acid and the like;
(2) the method can adjust the concentration of the graphene oxide solution, thereby being beneficial to controlling the thickness of the graphene film obtained by reduction;
(3) the method of the invention does not need large-scale equipment, has simple operation and low cost, can carry out the reduction reaction at room temperature without the traditional high-temperature heating of 1000-3000 ℃, and is safer and high in efficiency;
(4) the method of the invention is not only suitable for wet spinning technology, but also can be widely used for other redox methods, such as a roll coating method, a vacuum filtration method, a metal in-situ reduction method and the like, thereby being beneficial to the large-scale industrial production and popularization.
Drawings
Fig. 1 is a graph of the relationship between the electrical conductivity and the thermal conductivity of the graphene thin films prepared in examples 1 and 2 of the present invention and the content of small-sized graphene.
In fig. 2, (a-c) are scanning electron microscope plan views of graphene thin films of pure large size, containing 50% mass fraction of small-sized graphene, and pure small size, respectively; (d-f) are scanning electron microscopic cross-sectional views of graphene thin films of pure large size, containing 50% mass fraction of small-sized graphene, and pure small size, respectively.
Fig. 3 is a raman spectrum of the graphene thin films obtained in examples 1 and 2 of the present invention.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes and are not intended to limit the scope of the present invention. The conditions used in the examples may be further adjusted according to the conditions of the particular manufacturer, and the conditions not specified are generally the conditions in routine experiments.
The present invention will be described in detail with reference to examples, but it should be understood that the examples described herein are only illustrative and not restrictive.
Example 1
(1) Preparing a sample solution, namely performing cell ultrasonic crushing treatment on a large-size graphene oxide sample solution with the uniform dispersion concentration of 8mg/ml to obtain a small-size graphene oxide solution with the same concentration, and then uniformly mixing the two solutions according to a one-to-one mass ratio.
(2) Injecting the uniformly mixed graphene oxide sample solution obtained in the step (1) into a coagulating bath mixed with calcium chloride, ethanol and water through an injector pump for flocculation, and conveying the solution through a polyethylene terephthalate film.
(3) And (3) collecting the graphene oxide film obtained in the step (2), soaking the graphene oxide film in an ethanol water solution for cleaning, then placing the graphene oxide film on a hot bench at 40 ℃ for drying for 1 hour, and then placing the graphene oxide film in a vacuum oven for further drying for 4 hours at 60 ℃.
(4) And (4) soaking the film dried in the step (3) and the polyethylene glycol terephthalate film in deionized water for 3 hours, then stripping in water to obtain a graphene oxide film, and placing the graphene oxide film in a vacuum oven again to keep the temperature of 60 ℃ for drying for 8 hours.
(5) And (4) soaking the graphene oxide film dried in the step (4) in a hydriodic acid solution for reaction, and meanwhile, placing the reaction system in a water bath at the temperature of 80 ℃ for heating for 12 hours.
(6) And (3) washing the graphene film reacted in the step (5) with a saturated sodium bicarbonate solution, deionized water and absolute ethyl alcohol respectively, and then placing the film in a vacuum oven to keep the temperature of 100 ℃ for drying for 12 hours to obtain the high-performance graphene film.
Example 2 is the same as example 1, except that the mass ratio of 50% of small-size graphene oxide to 50% of large-size graphene oxide is changed to 0 to 100%, 10 to 90%, 30 to 70%, 70 to 30%, 90 to 10%, 100 to 0%.
Example 3, same as example 1, but the graphene oxide solution concentration was changed to 12mg/ml or 18 mg/ml.
FIG. 1 is a graph showing the relationship between the electrical conductivity and the thermal conductivity of the graphene thin film prepared by the present invention and the content of the small-sized graphene, from which it can be found that the electrical conductivity and the thermal conductivity are improved to some extent when the small-sized graphene and the large-sized graphene are mixed compared with the case where the small-sized graphene and the large-sized graphene are not mixed, and particularly, the graphene thin film prepared in example 1 has a value as high as 1102.62 W.m-1·K-1Has a thermal conductivity of 8982.18 S.m-1The conductivity of the graphene film is respectively improved by 188.87% and 81.41% compared with the heat conduction and electric conductivity of a pure large-size graphene film. FIG. 2 is a scanning electron microscope plan view and a cross-sectional view of a graphene film with a pure large size, a graphene film with a small size of 50% by mass, and a pure small size, as shown in the figure, the graphene film with the pure large size is well arranged, but a plurality of pores still exist; the pure small-size graphene film is arranged worst, and the warping structure and the pores of the cross section on the surface are the most; the graphene thin film containing 50% of small-sized graphene in mass fraction obtained in example 1 was arranged most smoothly and tightly, and had the least number of pores. FIG. 3 is a Raman spectrum of a graphene film containing different mass fractions of small-sized graphene, as shown by the D peak to G peak intensity ratio (I)D/IG) And the mean distance between defects (L) calculated therefromD) It is known that by doping small-sized graphene, the average distance between the film defects is improved compared with the case of no doping, which means that the number of defects is reduced, especially the number of defects of the graphene film containing 50% mass fraction of small-sized graphene obtained in example 1 is the least, thereby illustrating the reason why the thermal conductivity and the electrical conductivity are the best.
The above examples are only for illustrating the technical idea and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. A method for preparing a high-thermal-conductivity graphene film at normal temperature is characterized by comprising the following steps:
1) preparing a graphene oxide solution: carrying out cell ultrasonic crushing treatment on a part of uniformly dispersed large-size graphene oxide solution with the concentration of 8-18mg/ml to obtain a small-size graphene oxide solution with the same concentration, and then uniformly mixing the other part of large-size graphene oxide solution and the small-size graphene oxide solution to obtain a mixed graphene oxide solution;
2) injecting the mixed graphene oxide solution obtained in the step 1) into a coagulation bath consisting of calcium chloride, ethanol and water for flocculation, and conveying the solution through a polyethylene glycol terephthalate film to obtain a graphene oxide film treated by the coagulation bath;
3) collecting the graphene oxide film subjected to coagulation bath treatment obtained in the step 2), soaking the graphene oxide film in an ethanol water solution for cleaning, then placing the graphene oxide film on a hot bench at the temperature of 30-60 ℃, drying for 1-3 hours, then placing the graphene oxide film in a vacuum oven, keeping the temperature at 50-80 ℃, and further drying for 3-8 hours;
4) soaking the product obtained in the step 3) and a polyethylene glycol terephthalate film in deionized water for 1-5 hours, then stripping in the deionized water to obtain an unsupported graphene oxide film, placing the unsupported graphene oxide film in a vacuum oven again, and drying for 6-12 hours at the temperature of 50-80 ℃;
5) soaking the unsupported graphene oxide film dried in the step 4) in a reducing agent for reaction, and meanwhile, placing the reaction system in a water bath at the temperature of 60-90 ℃ for heating for 8-14 hours;
6) washing the film reacted in the step 5) with a saturated sodium bicarbonate solution, deionized water and absolute ethyl alcohol in sequence, then placing the film in a vacuum oven, and drying at the temperature of 80-120 ℃ for 10-16 hours to obtain the graphene film with high thermal conductivity.
2. The method for preparing the graphene film with high thermal conductivity at normal temperature according to claim 1, wherein in the step 1), the particle size of the large-size graphene oxide is 10-15 μm; the particle size of the small-size graphene oxide is 2-4 mu m.
3. The method for preparing the graphene film with high thermal conductivity at normal temperature according to claim 1, wherein in the step 2), the mass fraction of the small-sized graphene oxide in the mixed graphene oxide solution is 10-90%.
4. The method for preparing the graphene film with high thermal conductivity at normal temperature according to claim 3, wherein in the step 2), the mass fraction of the small-sized graphene oxide in the mixed graphene oxide solution is 30-70%.
5. The method for preparing a graphene film with high thermal conductivity at normal temperature according to claim 4, wherein in the step 2), the mass fraction of the small-sized graphene oxide in the mixed graphene oxide solution is 50%.
6. The method for preparing the graphene film with high thermal conductivity at normal temperature according to claim 1, wherein in the step 2), the coagulating bath component is a mixed solution of ethanol and water in a volume ratio of 1:2-1:5 and calcium chloride with a mass fraction of 3-8%.
7. The method for preparing the graphene film with high thermal conductivity at normal temperature according to claim 1, wherein in the step 5), the reducing agent is a hydroiodic acid solution, and the mass fraction of the hydroiodic acid solution is 30-50%.
8. The method for preparing the graphene film with high thermal conductivity at normal temperature according to claim 1, wherein in the step 3), the mass fraction of ethanol in the ethanol aqueous solution is 90-95%.
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