CN114703565B - Graphene fiber, graphene fiber reinforced heat conduction gasket and preparation method - Google Patents

Graphene fiber, graphene fiber reinforced heat conduction gasket and preparation method Download PDF

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Publication number
CN114703565B
CN114703565B CN202210423277.XA CN202210423277A CN114703565B CN 114703565 B CN114703565 B CN 114703565B CN 202210423277 A CN202210423277 A CN 202210423277A CN 114703565 B CN114703565 B CN 114703565B
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graphene
fibers
fiber reinforced
heat
gasket
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CN114703565A (en
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葛翔
胡佳佳
杨淑洁
周曙
张鹏
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Changzhou Fuxi Technology Co Ltd
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Changzhou Fuxi Technology Co Ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a graphene fiber and a preparation method thereof, comprising the following steps: and slotting the graphene heat conducting film to form a plurality of graphene fibers. The invention also provides a graphene fiber reinforced heat conduction gasket and a preparation method thereof, comprising the following steps: preparing rows of graphene fibers; bonding the rows of graphene fibers into blocks by using a high polymer; solidifying and forming to obtain a heat conducting block; and cutting the heat conduction block to obtain the graphene fiber reinforced heat conduction gasket. The preparation method of the graphene fiber is simple, the prepared graphene fibers have high directionality, and in the obtained heat conduction gasket, the graphene fibers are good in combination, and can keep pace with a high-molecular polymer when being pressed and rebounded, and can bear high compression rate without cracking.

Description

Graphene fiber, graphene fiber reinforced heat conduction gasket and preparation method
Technical Field
The invention relates to the technical field of graphene materials, in particular to graphene fibers and a preparation method thereof, and a graphene fiber reinforced heat conduction gasket and a preparation method thereof.
Background
Graphene is used as a heat conduction reinforcing body and combined with an elastic high polymer, so that the graphene fiber reinforced heat conduction gasket with high heat conduction performance can be manufactured. In the prior art, graphene is generally made into heat-conducting micro-sheet powder, and the heat-conducting micro-sheet powder is vertically arranged to form a longitudinal high-heat-conductivity gasket, such as document CN113321933A, CN113334731A, CN113337253A, CN113560146A, CN113789590A; or directly stacking graphene heat-conducting films layer by layer so as to enable the graphene heat-conducting films to be arranged along the longitudinal direction, and obtaining the graphene fiber reinforced heat-conducting gasket with high longitudinal heat conduction, such as document CN113183544A, CN113290958A, CN113556925A.
For the first type of method, since graphene is made into powder, the graphene does not have a continuous structure, and the heat conduction resistance between the powder inside the heat conduction gasket is large, so that the heat conduction performance of the gasket is relatively low on a macroscopic scale. The thermal conductivity of the high-thermal-conductivity graphene powder is generally above 1000W/(m K), and if the requirements of the thermal conductivity, the thermal resistance, the compression property, the compression retraction elasticity and the like of the thermal-conductivity gasket are met at the same time, the filling amount of the high-thermal-conductivity graphene powder is difficult to exceed 50wt.%, and the obtained thermal-conductivity gasket is generally not more than 20W/(m K). If the filling amount is increased uniformly to improve the heat conduction performance, the gasket is easy to crack, and a large amount of powder falling phenomenon is generated on the surface of the gasket.
For the second method, although a graphene continuous structure is formed, the high-molecular polymer between the layers is difficult to form connection due to the blocking of the graphene heat-conducting film, and the obtained gasket is easy to crack due to the fact that the graphene heat-conducting film is easy to delaminate. Although through holes can be arranged on the graphene heat conducting film, only some connecting points can be added, a complete continuous structure cannot be formed between macromolecules, and the cracking problem of the obtained heat conducting gasket cannot be fundamentally solved. In addition, the whole graphene heat-conducting film is combined with the high-molecular polymer, so that the graphene heat-conducting film is difficult to keep pace with the high-molecular polymer when being pressed and rebounded, and internal cracking is easy to occur.
In fact, it is important to analyze the application requirements of thermally conductive gaskets to be able to obtain high thermal conductivity in the longitudinal direction and to ensure structural stability of the gasket when it is rebound under pressure.
Disclosure of Invention
Aiming at one or more of the problems in the prior art, the invention provides a preparation method of graphene fibers, which comprises the following steps:
and slotting the graphene heat conducting film to form a plurality of graphene fibers.
Optionally, the step of grooving the graphene heat-conducting film includes:
and (3) slotting the graphene film in an array manner to form a plurality of graphene fibers.
Optionally, the plurality of graphene fibers are arranged in parallel.
Optionally, at least one end of the plurality of graphene fibers is connected.
Optionally, the two ends of the graphene fibers are connected, and preferably, the two ends of the graphene fibers are connected in parallel.
Optionally, the slotting mode on the graphene heat-conducting film is punching slotting, laser slotting or chemical etching.
Optionally, the width of the graphene fiber and the spacing between adjacent graphene fibers are controlled by controlling the width of the grooves and the center-to-center distance of the grooves.
Alternatively, the width of the groove is 0.05-3mm, preferably 0.1-0.5.
Alternatively, adjacent grooves may have a center-to-center distance of 0.1-6mm, preferably 0.2-1mm.
Optionally, the preparation method of the graphene heat conduction film comprises the following steps:
the graphene oxide slurry is used for coating, drying, heat treatment and calendaring to obtain the graphene oxide composite material; or/and (or)
The polymer film is carbonized, graphitized and rolled to obtain the composite material; or/and (or)
And directly calendaring by using expanded graphite.
Optionally, the polymer film is selected from at least one of polyimide film, nylon film, polyamide, polybenzoxazole, polybenzobisoxazole, polyoxadiazole, polythiazole, polybenzobisoxizole, polybenzothiazole, polybenzimidazole or polybenzobiimidazole or polyparaphenylene vinylene.
According to another aspect of the present invention, there is provided a graphene fiber prepared by the above-described preparation method.
Optionally, the thickness of the graphene fiber is 1-200 micrometers, preferably, the thickness of the graphene fiber is 10-50 micrometers; or/and (or)
The graphene fiber density is 1.0-2.2g/cm 3 Preferably 1.5-2.2g/cm 3 。
According to a third aspect of the present invention, there is provided a method for preparing a graphene fiber reinforced thermal conductive gasket, comprising:
preparing rows of graphene fibers;
bonding the rows of graphene fibers into blocks by using a high polymer;
solidifying and forming to obtain a heat conducting block;
the heat conducting block is cut to obtain the graphene fiber reinforced heat conducting gasket, preferably, the heat conducting block is cut along the direction 45-135 degrees relative to the longitudinal direction, and further preferably, the heat conducting block is cut along the direction 90 degrees relative to the longitudinal direction.
Optionally, in the step of bonding the rows of graphene fibers into blocks by using the high polymer, multiple layers of rows of graphene fibers are stacked and bonded layer by using the high polymer, and preferably, the rows of graphene fibers of two adjacent layers are completely corresponding, not corresponding or not completely corresponding; or/and (or)
In the step of solidifying and forming to obtain the heat conducting block, the solidifying mode adopts normal pressure solidifying or pressurizing solidifying, preferably, the solidifying mode adopts pressurizing solidifying; preferably, the pressurization is controlled by the compression ratio during the curing, more preferably, the compression ratio is 5 to 50%, still more preferably, 15 to 20%; preferably, the curing temperature is 40-150 ℃ or normal temperature; or/and (or)
And in the step of cutting the heat conducting block to obtain the graphene fiber reinforced heat conducting gasket, cutting is performed along the stacking direction to obtain the graphene fiber reinforced heat conducting gasket.
Optionally, in the step of bonding the rows of graphene fibers into blocks by using the high molecular polymer, bonding and rolling the rows of graphene fibers into blocks by using the high molecular polymer; or/and (or)
In the step of solidifying and forming to obtain the heat conducting block, the solidifying mode adopts normal pressure solidifying or pressurizing solidifying, one direction or a plurality of directions are selected for pressurizing during pressurizing solidifying, and preferably, the solidifying mode adopts normal pressure solidifying; preferably, the pressurization is controlled by the compression ratio during the curing, more preferably, the compression ratio is 5 to 50%, still more preferably, 15 to 20%; preferably, the curing temperature is 40-150 ℃ or normal temperature.
Optionally, the step of cutting the heat conducting block to obtain the graphene fiber reinforced heat conducting gasket further comprises: the connected ends of the rows of graphene fibers are cut away.
Optionally, the method further comprises the step of carrying out surface treatment on the graphene fiber reinforced heat-conducting pad, wherein the surface treatment comprises grinding or/and polishing.
According to a fourth aspect of the present invention, there is provided a graphene fiber reinforced thermal conductive gasket comprising graphene fibers and a high molecular polymer, the graphene fibers being longitudinally arranged.
Optionally, the graphene fibers are present in an amount of 15-70wt.%, preferably 30-60wt.%.
Optionally, the high molecular polymer adopts epoxy resin, phenolic resin, furfural resin, polyurethane, acrylic resin, polybutene and organic silica gel.
Optionally, the high molecular polymer adopts organic silica gel.
Optionally, the high molecular polymer adopts at least one of polydimethylsiloxane, alpha, omega-dihydroxypolydimethylsiloxane, polydiphenylsiloxane, alpha, omega-dihydroxypolymethyls (3, 3, 3-trifluoropropyl) siloxane, cyano-siloxysilane and alpha, omega-diethylpolydimethylsiloxane.
Optionally, the high polymer contains other heat conducting fillers, and the other heat conducting fillers are at least one of graphene powder, graphite powder, boron nitride powder, aluminum oxide, aluminum nitride or silicon carbide.
Optionally, the other thermally conductive filler is present in the high molecular polymer in a ratio of 5wt.% to 50wt.%, preferably 10wt.% to 30wt.%.
The preparation method of the graphene fiber is simple, the prepared graphene fibers have high directionality, and in the obtained heat conduction gasket, the graphene fibers are good in combination, and can keep pace with a high-molecular polymer when being pressed and rebounded, and can bear high compression rate without cracking.
The graphene fibers are arranged in rows, and can be uniformly arranged in a certain mode in a layer-by-layer stacking mode or a roll forming mode, so that the graphene fibers in the obtained graphene fiber reinforced heat conduction gasket are uniformly distributed, and the heat conduction consistency is high;
according to the graphene fiber reinforced heat conduction gasket, heat conduction is carried out almost along the longitudinal direction, so that heat accumulation caused by heat conduction along the transverse direction is avoided.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIGS. 1a-1d are schematic views of rows of graphene fibers of the present invention at different connected locations;
FIG. 2 is a schematic diagram of one embodiment of a graphene fiber reinforced thermal conductive gasket according to the present invention;
FIG. 3 is a schematic view of another embodiment of a graphene fiber reinforced thermal conductive gasket according to the present invention;
FIG. 4 is a schematic diagram of an embodiment of a method for preparing a graphene fiber reinforced thermal conductive gasket according to the present invention;
FIGS. 5 a-5 d are schematic illustrations of a thermally conductive block formed in the embodiment of FIG. 4 from rows of graphene fibers in different connected locations according to the present invention;
FIG. 6 is a schematic diagram of another embodiment of a method for preparing a graphene fiber reinforced thermal conductive gasket according to the present invention;
fig. 7 a-7 d are schematic diagrams of a thermally conductive block formed in the embodiment of fig. 6 from rows of graphene fibers at different connected locations according to the present invention.
Detailed Description
Hereinafter, only certain exemplary embodiments are briefly described. As will be recognized by those of skill in the pertinent art, the described embodiments may be modified in various different ways without departing from the spirit or scope of the present invention. Accordingly, the drawings and description are to be regarded as illustrative in nature and not as restrictive.
The following disclosure provides many different embodiments, or examples, for implementing different features of the invention. They are, of course, merely examples and are not intended to limit the invention. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art will recognize the application of other processes and/or the use of other materials.
The preferred embodiments of the present invention will be described below with reference to the accompanying drawings, it being understood that the preferred embodiments described herein are for illustration and explanation of the present invention only, and are not intended to limit the present invention.
Fig. 1a to 1d are schematic diagrams of the graphene fibers in rows according to the present invention at different connection positions, as shown in fig. 1a to 1d, at least one end of each of the graphene fibers in rows is connected, either one end (as shown in fig. 1 b) or both ends are connected (as shown in fig. 1 a), or the other end is connected (as shown in fig. 1 d), or one end is connected to the middle, or both ends are connected to the middle (as shown in fig. 1 c), if the graphene fibers are not connected, they are easy to be scattered, and when a product is prepared, the orientation in the high polymer is greatly affected, the complexity of the preparation process is increased, and the heat conducting property of the obtained product is necessarily affected.
In one embodiment, a plurality of graphene fibers in the rows of graphene fibers are arranged in parallel.
In one embodiment, the graphene fibers have a thickness of 1-200 microns, a thickness of less than 1 micron, and are too thin to be broken; above 200 microns, the fibers are too stiff and tend to separate from the polymer when pressed, causing cracking.
Preferably, the graphene fibers have a thickness of 10-50 microns.
In one embodiment, the graphene fiber density is 1.0-2.2g/cm 3 Preferably 1.5-2.2g/cm 3 Theoretical density of graphite 2.26g/cm 3 Density 2.2g/cm 3 Has approached the theoretical value ifUpon further densification, the associated equipment may be destroyed; density of less than 1.0g/cm 3 The heat conduction performance of the rows of graphene fibers is poor.
The preparation method of the rows of graphene fibers comprises the following steps: and slotting the graphene heat conducting film to form a plurality of graphene fibers.
In one embodiment, a plurality of graphene fibers are formed by array grooving on a graphene film.
Preferably, the plurality of graphene fibers are arranged in parallel.
Preferably, at least one end of the plurality of graphene fibers is connected.
Preferably, two ends of the plurality of graphene fibers are connected, and further preferably, two ends of the plurality of graphene fibers are connected in parallel.
In one embodiment, the manner of slotting on the graphene heat-conducting film is punching slotting, laser slotting or chemical etching.
In one embodiment, the method for preparing graphene fibers further comprises: the width of the groove and the center distance of the groove are controlled, so that the width of the graphene fiber and the distance between adjacent graphene fibers are controlled.
Preferably, the width of the groove is 0.05-3mm, and the width of the groove is less than 0.05mm, so that the groove is not easy to realize, and is not beneficial to combining with a polymer; if the width is more than 3mm, the graphene fibers are too sparse, and the heat conduction channels per unit area/volume are too few, so that the heat conduction performance is seriously affected, and the more preferable range is 0.1-0.5.
Preferably, the center distance of adjacent grooves is 0.1-6mm, the center distance is matched with the groove width to control the width and the distance of the fibers, the center distance is smaller than 0.1mm, the width of the fibers is too small to be broken easily, the center distance is larger than 6mm, the width of the fibers is too large to be bonded with a polymer for molding, and the graphene is further preferably 0.2-1mm because of being easily layered.
In one embodiment, the preparation method of the graphene heat conducting film comprises the following steps:
the graphene oxide slurry is used for coating, drying, heat treatment and calendaring.
In one embodiment, the preparation method of the graphene heat conducting film comprises the following steps:
the polymer film is carbonized, graphitized and rolled to obtain the product.
Preferably, the polymer film is selected from at least one of polyimide film, nylon film, polyamide, polybenzoxazole, polybenzobisoxazole, polyoxadiazole, polythiazole, polybenzobisoxizole, polybenzothiazole, polybenzimidazole or polybenzobiimidazole or polyparaphenylene vinylene.
In one embodiment, the preparation method of the graphene heat conducting film comprises the following steps:
and directly calendaring by using expanded graphite.
Three examples of different preparation methods for obtaining the graphene heat-conducting film are given above, but the present invention is not limited to the graphene, and any combination of the above three preparation methods may be used.
Fig. 2 is a schematic view of one embodiment of a graphene fiber reinforced thermal conductive gasket according to the present invention, and fig. 3 is a schematic view of another embodiment of a graphene fiber reinforced thermal conductive gasket according to the present invention, wherein the thermal conductive gasket comprises graphene fibers and a high molecular polymer, and the graphene fibers are longitudinally arranged as shown in fig. 2 and 3.
As a heat conduction gasket product, the heat conduction performance of the heat conduction gasket product is mainly reflected in the longitudinal direction, and graphene fibers are used as one-dimensional materials, and the graphene fibers are required to be arranged in a high-degree orientation along the longitudinal direction so as to obtain the high heat conduction performance in the longitudinal direction.
In one embodiment, the graphene fiber is 15-70wt.%, less than 15wt.%, and has a low thermal conductivity; if the content is higher than 70wt.%, the gasket sample is easily cracked due to insufficient content of the high molecular polymer.
Preferably, the graphene fibers are present in an amount of 30-60wt.%.
In one embodiment, the high molecular polymer is epoxy resin, phenolic resin, furfural resin, polyurethane, acrylic resin, polybutene or organic silica gel.
In one embodiment, the high molecular polymer is a silicone gel.
In one embodiment, the high molecular polymer is at least one of polydimethylsiloxane, alpha, omega-dihydroxypolydimethylsiloxane, polydiphenylsiloxane, alpha, omega-dihydroxypolymethyl3, 3, 3-trifluoropropyl siloxane, cyanosiloxysilane, and alpha, omega-diethylpolydimethylsiloxane.
The high polymer adopts organic silica gel, which has excellent high temperature resistance and low temperature resistance, can generally bear-50-150 ℃ and can bear lower temperature or higher temperature, and has good compression performance and compression rebound resilience, so that the high polymer is suitable for preparing the heat-conducting gasket. Other types of high molecular polymers have better bonding strength and hardness than organic silica gel, and are suitable for preparing occasions with higher mechanical strength requirements and harder materials.
In an embodiment, the high polymer contains other heat conductive fillers, so that the heat conductive performance is further improved, the other heat conductive fillers are at least one of graphene powder, graphite powder, boron nitride powder, aluminum oxide, aluminum nitride or silicon carbide, for example, the adhesion between silica gel and graphene can be effectively improved by the other fillers in organic silica gel, and the bonding effect is better.
Preferably, the other heat conductive filler is present in the high molecular polymer in an amount of 5wt.% to 50wt.%, preferably 10wt.% to 30wt.%, and if the ratio is less than 5wt.%, the effect is comparable to that without the other heat conductive filler; if the ratio is more than 50wt.%, the binding force of the high molecular polymer and the graphene fiber is affected.
In one embodiment, the thermally conductive pad does not include thermally conductive pads formed by rows of connected ends of graphene fibers.
The heat-conducting gasket adopts rows of graphene fibers as reinforcements of the heat-conducting gasket; the graphene fibers in the rows are connected at least at one end, the graphene fibers can be orderly arranged without disorder, and the graphene fibers can be oriented to a high degree by direct stacking; one end of the graphene fibers are connected into a row, and the uniform distribution of the graphene fibers in a final sample is fully ensured by utilizing the array characteristic of the space of the graphene fibers; the high heat transfer performance of the graphene heat conducting film in a two-dimensional plane is converted into the high heat transfer performance along a one-dimensional direction.
The preparation method of the graphene fiber reinforced heat conduction gasket comprises the following steps:
preparing rows of graphene fibers;
bonding the rows of graphene fibers into blocks by using a high polymer;
solidifying and forming to obtain a heat conducting block;
and cutting the heat conduction block to obtain the graphene fiber reinforced heat conduction gasket.
Preferably, the cutting is performed in a direction of 45 ° -135 ° to the longitudinal direction, preferably 60 ° o -120 o That is, the included angle between the graphene fiber and the transverse direction is 45 o -135 o Preferably 60 o -120 o During cutting, the cutting angle can be controlled, so that the angle formed between the graphene fiber and the transverse direction is realized; when the angle is less than 45 o Or higher than 135 o When the graphene fiber reinforced thermal conductive gaskets are arranged not in the longitudinal direction but in the transverse direction, the thermal conductivity coefficient of the obtained graphene fiber reinforced thermal conductive gaskets in the longitudinal direction is remarkably reduced, and more preferably, the graphene fiber reinforced thermal conductive gaskets are cut in the direction which is 90 degrees from the longitudinal direction.
The graphene fibers are arranged in the longitudinal direction in the obtained heat conduction gasket, and almost 100% of 90% of the graphene fibers can be obtained o The vertical arrangement degree can realize the included angle between the graphene fiber and the plane from 45 through the adjustment of the cutting angle o -135 o Is controlled by the control program.
Fig. 4 is a schematic diagram of an embodiment of a preparation method of a graphene fiber reinforced thermal conductive gasket according to the present invention, as shown in fig. 4, the preparation method includes:
step S11, preparing graphene fibers in rows;
step S12, bonding and stacking multiple layers of rows of graphene fibers layer by layer into blocks by utilizing a high polymer, and curing and forming to obtain a heat conduction block, wherein FIG. 5a is a heat conduction block formed by multiple layers of rows of graphene fibers with one end connected, FIG. 5b is a heat conduction block formed by multiple layers of rows of graphene fibers with two ends connected, FIG. 5c is a heat conduction block formed by multiple layers of rows of graphene fibers with two ends connected with the middle, and FIG. 5d is a heat conduction block formed by multiple layers of rows of graphene fibers with the middle connected;
and S13, cutting the heat conduction block to obtain the graphene fiber reinforced heat conduction gasket.
In the preparation method, if the graphene fibers in rows with a fibrous structure are not adopted, but the integral graphene heat conducting film is adopted, the upper and lower layers of high polymer can not be connected into a whole when being bonded and stacked, and the inside of the graphene heat conducting film is easy to delaminate, so that the obtained graphene fiber reinforced heat conducting gasket is cracked; meanwhile, when the graphene heat conduction film is pressed, the difference between the graphene heat conduction film and the high polymer in compression, rebound and other aspects is large, so that the cracking of the obtained graphene fiber reinforced heat conduction gasket is further aggravated.
In one embodiment, step S13 is preceded by: and cutting off the connected ends of the rows of graphene fibers.
In the manufactured graphene fiber reinforced heat conduction gasket, the joints of the rows of graphene fibers are cut off, and finally, graphene is uniformly dispersed in the gasket; this is because the connection not only can make the gasket when using the pressurized, inside atress is uneven, leads to deformation and resilience unstable, can arouse the conduction of heat in horizontal direction moreover to influence the effect of the vertical heat conduction of gasket, cause the accumulation of heat, be unfavorable for the radiating effect of heat conduction gasket.
Preferably, the connected ends of the rows of graphene fibers are cut off before curing and forming.
In one embodiment, in step S11, a row of graphene fibers with the middle unconnected is adopted, if the row of graphene fibers is connected at a plurality of positions in the middle, although the preparation of the graphene fiber reinforced heat conduction gasket can be facilitated, the connection is required to be removed, which inevitably leads to the increased loss of the gasket.
In one embodiment, in step S12, the curing mode is normal pressure curing or pressure curing.
Preferably, the curing mode adopts pressurization curing, pressurization is carried out in the stacking direction, and tight combination between the graphene layers in rows is realized.
Preferably, the compression is controlled by the compression ratio during curing, more preferably, the compression ratio is 5 to 50%, the degree of bonding is insufficient when the compression ratio is less than 5%, the sample is easily cracked, and when the compression ratio is more than 50%, the compression ratio is too large, the sample is easily cracked, and even more preferably, 15 to 20%.
Preferably, the curing temperature is 40-150 ℃ or normal temperature, and if the curing temperature is too high, the curing is too fast, causing internal cracking.
In one embodiment, in step S13, cutting is performed along the stacking direction to obtain the graphene fiber reinforced thermal conductive gasket.
In one embodiment, in step S12, the rows of graphene fibers of two adjacent layers are fully corresponding, not corresponding, or not fully corresponding.
In one embodiment, the above preparation method further comprises a step of performing surface treatment on the graphene fiber reinforced heat-conducting pad, wherein the surface treatment comprises grinding or/and polishing.
Fig. 6 is a schematic diagram of an embodiment of a method for preparing a graphene fiber reinforced thermal conductive gasket according to the present invention, as shown in fig. 6, where the preparation method includes:
step S21, preparing graphene fibers in longitudinal rows;
step S22, bonding and rolling the rows of graphene fibers into a block body by using a high polymer, and curing and forming to obtain a heat conduction block, wherein FIG. 7a is a heat conduction block formed by rows of graphene fibers with one end connected, FIG. 7b is a heat conduction block formed by rows of graphene fibers with two ends connected, FIG. 7c is a heat conduction block formed by rows of graphene fibers with two ends and the middle connected, and FIG. 7d is a heat conduction block formed by rows of graphene fibers with the middle connected;
and S23, cutting the heat conduction block to obtain the graphene fiber reinforced heat conduction gasket.
In one embodiment, step S23 is preceded by: the graphene fibers in the row are cut off to be connected with the ends, and the connection points not only enable the gasket to be unevenly stressed when the gasket is rolled, so that deformation and rebound are unstable, but also heat conduction in the transverse direction can be caused, the effect of longitudinal heat conduction of the gasket is affected, heat accumulation is caused, and the heat dissipation effect of the heat conduction gasket is not facilitated.
Preferably, the connected ends of the rows of graphene fibers are cut off before curing and forming.
In one embodiment, in step S21, a row of graphene fibers with the middle unconnected is adopted, if the row of graphene fibers is connected at a plurality of positions in the middle, although the preparation of the graphene fiber reinforced heat conduction gasket can be facilitated, the connection is required to be removed, which inevitably leads to the increased loss of the gasket.
In one embodiment, in step S22, the curing mode is normal pressure curing or pressure curing.
The pressurizing and curing are performed in one direction or a plurality of directions (except the direction of the orientation of the graphene fibers), but the section of the rolled block will correspondingly change along with the pressurizing mode, and preferably, the curing mode adopts normal pressure curing.
In one embodiment, the compression is controlled during curing by a compression ratio, preferably 5-50%, which is comparable to the effect of normal pressure when the compression ratio is below 5%, and is too high for a compression ratio above 50%, which can easily lead to sample fracturing, preferably 15-20%.
The graphene fiber reinforced heat conduction gasket at least comprises graphene fibers and a high polymer, wherein the graphene fibers are arranged in the heat conduction gasket along the longitudinal direction to a high degree. The preparation method of the graphene fiber reinforced heat conduction gasket comprises the following steps: bonding and stacking the graphene fibers in a row layer by layer into blocks or bonding and rolling the graphene fibers into blocks by utilizing a high polymer; and cutting into graphene fiber reinforced heat conduction gaskets after solidification and molding, wherein the graphene fibers in the gaskets are arranged in a longitudinal high-degree orientation mode. Other thermally conductive fillers may be included in the high molecular weight polymer. The graphene fiber reinforced heat conduction gasket has the performance advantages of high orientation, high heat conduction, low thermal resistance and the like.
In one embodiment, the method further comprises the step of surface treating the graphene fiber reinforced thermally conductive pad, the surface treatment comprising grinding or/and polishing.
The graphene fiber reinforced thermal conductive gaskets of the following examples were tested for their related properties using the following methods, respectively:
the thermal conductivity of the samples at 40psi was tested by ASTM D5470;
the applied thermal resistance (the sum of the intrinsic thermal resistance of the sample and the thermal resistance of the upper and lower contact surfaces) of a sample having a thickness of 0.5mm at 40psi was tested by ASTM D5470;
samples having a thickness of 0.5mm were tested for compression resilience under 50% strain by ASTM D575.
In the following embodiments 1 to 5, the preparation method of the rows of graphene fibers and the graphene fiber reinforced heat conduction gasket includes:
grooves which are vertically communicated are formed in the graphene heat conducting film, so that rows of graphene fibers are formed;
bonding and stacking the rows of graphene fibers layer by layer into blocks by utilizing a high polymer;
solidifying and forming;
cutting into pieces along the stacking direction to obtain the graphene fiber reinforced heat conduction gasket, wherein the graphene fibers are arranged along the longitudinal direction of the heat conduction gasket.
Example 1
In the embodiment, the rows of graphene fibers are obtained by grooving the surface of a graphene heat-conducting film, and the graphene heat-conducting film is obtained by coating, drying, heat-treating and calendaring graphene oxide slurry;
the thickness of the rows of graphene fibers is 10 μm; density 1.5g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The width of the groove is 0.1mm; the center distance of the grooves is 0.2mm;
the high molecular polymer is polydiphenylsiloxane, which contains 30wt.% of aluminum nitride powder;
solidifying and shaping the block body stacked layer by layer at 40 DEG CThe compression ratio is 15% during press curing; cutting angle is 60 o The graphene fiber reinforced heat conduction gasket is obtained after surface grinding and polishing;
the content of graphene fibers in the graphene fiber reinforced heat conduction gasket is 55wt.%;
through testing, the performance of the obtained graphene fiber reinforced heat conduction gasket is as follows:
thermal conductivity coefficient: 92.46W/(mK);
applying thermal resistance: 0.21K cm 2 /W；
Compression spring rate: 96.56%.
Example 2
In the embodiment, the rows of graphene fibers are obtained by grooving the surface of a graphene heat-conducting film, and the graphene heat-conducting film is obtained by coating, drying, heat-treating and calendaring graphene oxide slurry;
the thickness of the rows of graphene fibers is 50 μm; density 1.8g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The width of the groove is 0.5mm; the center distance of the grooves is 1mm;
the high molecular polymer is polydimethyl cyclosiloxane, which contains 10wt.% of alumina powder;
solidifying and forming the block body stacked layer by layer under the normal temperature condition, wherein the compression rate is 20% when the block body is pressed and solidified; cutting angle is 120 o The graphene fiber reinforced heat conduction gasket is obtained after surface grinding and polishing;
the content of graphene fibers in the graphene fiber reinforced heat conduction gasket is 45wt.%;
through testing, the performance of the obtained graphene fiber reinforced heat conduction gasket is as follows:
thermal conductivity coefficient: 74.71W/(mK);
applying thermal resistance: 0.24K cm 2 /W；
Compression spring rate: 94.63%.
Example 3
In the embodiment, the rows of graphene fibers are obtained by grooving the surface of a graphene heat-conducting film, and the graphene heat-conducting film is obtained by coating, drying, heat-treating and calendaring graphene oxide slurry;
the thickness of the rows of graphene fibers is 25 μm; density 2.0g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The width of the groove is 0.2mm; the center distance of the grooves is 0.5mm;
the high molecular polymer is polydimethylsiloxane, which contains 15wt.% of graphene powder;
solidifying and forming the blocks stacked layer by layer at the temperature of 100 ℃, wherein the compression rate is 18% when the blocks are pressed and solidified; cutting angle is 90 o And (3) polishing the surface to obtain the graphene fiber reinforced heat conduction gasket.
The content of graphene fibers in the graphene fiber reinforced heat conduction gasket is 60wt.%;
through testing, the performance of the obtained graphene fiber reinforced heat conduction gasket is as follows:
thermal conductivity coefficient: 112.95W/(mK);
applying thermal resistance: 0.18K cm 2 /W；
Compression spring rate: 99.01%.
Example 4
In the embodiment, the rows of graphene fibers are obtained by grooving the surface of a graphene heat-conducting film, and the graphene heat-conducting film is obtained by carbonizing, graphitizing and calendaring a high polymer film;
the thickness of the rows of graphene fibers is 1 μm; density 1.2g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The width of the groove is 0.05mm; the center distance of the grooves is 0.1mm;
the high molecular polymer is alpha, omega-dihydroxy polydimethylsiloxane, which comprises 5wt.% of powdered graphite powder;
solidifying and forming the blocks stacked layer by layer at 150 ℃, wherein the compression rate is 5% when the blocks are pressed and solidified; cutting angle of 45 o And (3) polishing the surface to obtain the graphene fiber reinforced heat conduction gasket.
The content of graphene fibers in the graphene fiber reinforced heat conduction gasket is 40wt.%;
through testing, the performance of the obtained graphene fiber reinforced heat conduction gasket is as follows:
thermal conductivity coefficient: 62.47W/(mK);
using thermal resistance：0.28K·cm 2 /W；
Compression spring rate: 90.35%.
Example 5
In the embodiment, the rows of graphene fibers are obtained by grooving the surface of a graphene heat-conducting film, and the graphene heat-conducting film is obtained by rolling expanded graphite;
the thickness of the rows of graphene fibers is 200 μm; density 1.0g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The width of the groove is 3mm; the center distance of the grooves is 6mm;
the high molecular polymer is polyurethane, which contains 50wt.% of alumina powder;
solidifying and forming the blocks stacked layer by layer at 60 ℃, wherein the compression rate is 50% when the blocks are pressed and solidified; cutting angle 135 o And (3) polishing the surface to obtain the graphene fiber reinforced heat conduction gasket.
The content of graphene fibers in the graphene fiber reinforced heat conduction gasket is 30wt.%;
through testing, the performance of the obtained graphene fiber reinforced heat conduction gasket is as follows:
thermal conductivity coefficient: 59.05W/(mK);
applying thermal resistance: 0.30K cm 2 /W；
Compression spring rate: 91.18%.
In the following examples 6 and 7, the preparation method of the graphene fiber in rows and the graphene fiber reinforced heat conduction gasket includes:
grooves which are vertically communicated are formed in the graphene heat conducting film, so that rows of graphene fibers are formed;
bonding and rolling the rows of graphene fibers into blocks by using a high polymer;
solidifying and forming;
and cutting the graphene fiber-reinforced heat conduction gasket into a gasket to obtain the graphene fiber-reinforced heat conduction gasket, wherein the graphene fibers are arranged along the longitudinal direction of the gasket.
Example 6
The thickness of the rows of graphene fibers is 20 μm; density 2.1g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The width of the groove is 0.3mm; the center distance of the grooves is 0.5mm;
the high molecular polymer is cyano-siloxysilane, which contains 20wt.% silicon carbide powder;
curing and forming the blocks stacked layer by layer at 90 ℃ and curing at normal pressure; cutting angle of 80 o And (3) polishing the surface to obtain the graphene fiber reinforced heat conduction gasket.
The content of graphene fibers in the graphene fiber reinforced heat conduction gasket is 70wt.%;
through testing, the performance of the obtained graphene fiber reinforced heat conduction gasket is as follows:
thermal conductivity coefficient: 93.25W/(mK);
applying thermal resistance: 0.22K cm 2 /W；
Compression spring rate: 98.78%.
Example 7
In this embodiment, the thickness of the rows of graphene fibers is 100 μm; density 1.4g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The groove width is 0.06mm; the center distance of the grooves is 0.15mm;
the high molecular polymer is alpha, omega-dihydroxy polymethyl (3, 3, 3-trifluoropropyl) siloxane, which contains 8wt.% silicon carbide powder;
solidifying and forming the block body stacked layer by layer at 130 ℃, wherein the compression rate is 10% during solidification; cutting angle is 50 o And (3) polishing the surface to obtain the graphene fiber reinforced heat conduction gasket.
Through testing, the performance of the obtained graphene fiber reinforced heat conduction gasket is as follows:
the content of graphene fibers in the graphene fiber reinforced heat conduction gasket is 25wt.%;
thermal conductivity coefficient: 52.08W/(mK);
applying thermal resistance: 0.33K cm 2 /W；
Compression spring rate: 90.35%.
Comparative example 1
In this comparative example, the same preparation process as in example 1 was used, except that the angle used in cutting was 15 o Through test, the heat conductivity coefficient is 7.46W/(m K), and the application thermal resistance is 1.28K cm 2 /W。
Comparative example 2
In this comparative example, the same preparation process as in example 2 was used, except that the angle used in cutting was 150 o Through test, the heat conductivity coefficient is 10.53W/(m K), and the application thermal resistance is 0.97K cm 2 /W。
Comparative example 3
In this comparative example, a groove width of 0.025mm was cut in the graphene heat-conducting film, and the other conditions were the same as in example 3. Because the groove width is too narrow, the high molecular polymer is blocked as the graphene heat conducting film which is not grooved is directly adopted, and can not be effectively bonded and molded, and the obtained sample is easy to crack.
Comparative example 4
In this comparative example, a groove width of 5mm was cut in the graphene heat-conducting film, and the other conditions were the same as in example 4. The too large slot width results in the thermal conductivity of the sample being 11.23W/(mK) and the thermal resistance being 0.92K cm 2 /W。
Comparative example 5
In this comparative example, the graphene heat conductive film was provided with a groove center distance of 0.08mm and a groove width of 0.05 as a parameter, and the other conditions were the same as in example 5. Because the center distance of the grooves is too small, the obtained rows of graphene fibers are easy to damage, and the heat-conducting gasket cannot be prepared.
Comparative example 6
In this comparative example, the graphene heat conductive film was provided with a groove center-to-center distance of 10mm, and the other conditions were the same as in example 5. Because the center distance of the grooves is too large, the high molecular polymer is similar to a graphene heat conducting film which is directly used without grooves, and the high molecular polymer cannot be effectively bonded and molded, and the obtained sample is easy to crack.
Comparative example 7
In this comparative example, the thickness of the graphene fibers in a row was 400 μm, and the other conditions were the same as in example 6. Because the rows of graphene fibers are too thick, the gasket has no good flexibility, and is easy to damage when the gasket sample is prepared.
Comparative example 8
In this comparative example, the thickness of the graphene fibers in a row was 0.5 μm, and the other conditions were the same as in example 6. Because the rows of graphene fibers are too thin, the graphene fibers are not enough to be made into the self-stability and are easy to break, and are not suitable for preparing gasket samples.
Comparative example 9
In this comparative example, the density of the graphene fibers in the rows was 0.5g/cm 3 Other conditions were the same as in example 7. Because the density of the rows of graphene fibers is too small, a large amount of air exists in the gasket, so that the gasket is not compact enough and has no flexibility, and the gasket is easy to damage when being prepared.
Comparative example 10
In this comparative example, the content of graphene fibers in the prepared gasket sample was 8wt.%, and the other conditions were the same as in example 6. Through tests, the heat conductivity coefficient of the obtained gasket is only 5.23W/(m.K), the application thermal resistance is high, and the heat conductivity is 1.98 K.cm 2 /W。
According to the invention, one-dimensional graphene fibers with ultrahigh heat conduction performance are adopted and are arranged in a high-degree orientation in the longitudinal direction, so that the high heat conduction performance in the longitudinal direction is obtained; simultaneously, graphene fiber combines with the polymer, and when compressing and kick-backing, both can keep the pace well to avoid the risk of inside fracture.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (34)

1. The preparation method of the graphene fiber reinforced heat conduction gasket is characterized by comprising the following steps of:
the graphene fibers are grooved into rows in the graphene heat conducting film, and the width of the grooves and the center distance of the grooves are controlled to control the width of the graphene fibers and the adjacent width of the graphene fibersThe distance between graphene fibers is 0.05-3mm, the width of each groove is 0.1-6mm, the center distance between adjacent grooves is 1-200 micrometers, the thickness of each graphene fiber is 1.0-2.2g/cm, and the density of each graphene fiber is 1.0-200 micrometers 3 ；
Bonding the rows of graphene fibers into blocks by using a high polymer;
solidifying and forming to obtain a heat conducting block;
cutting the heat conduction block to obtain a graphene fiber reinforced heat conduction gasket, cutting along the direction of 45-135 degrees with the longitudinal direction, and longitudinally arranging graphene fibers, wherein the content of the graphene fibers is 15-70 wt%;
before solidification forming, cutting off connected ends of the rows of graphene fibers.
2. The method of manufacturing according to claim 1, wherein in the step of cutting the heat conductive block, cutting is performed in a direction 90 ° to the longitudinal direction.
3. The method according to claim 1, wherein in the step of bonding the rows of graphene fibers into pieces using a polymer, a plurality of layers of the rows of graphene fibers are stacked in layers by bonding using the polymer into pieces.
4. A method of preparing as claimed in claim 3 wherein rows of graphene fibers of adjacent two layers are fully or not fully aligned.
5. The method according to claim 3, wherein in the step of solidifying and forming the heat conducting block, the solidifying is performed by normal pressure solidifying or pressure solidifying.
6. The method according to claim 5, wherein the curing is performed by press curing.
7. The method of claim 6, wherein the pressurization is controlled by the compression ratio during the curing process.
8. The process according to claim 7, wherein the compression ratio is 5 to 50%.
9. The method according to claim 8, wherein the compression ratio is 15 to 20%.
10. A method of preparation according to claim 3 wherein the curing temperature is 40-150 ℃ or ambient.
11. The method according to claim 3, wherein in the step of cutting the heat conductive block to obtain the graphene fiber reinforced heat conductive gasket, cutting is performed along the stacking direction to obtain the graphene fiber reinforced heat conductive gasket.
12. The method according to claim 1, wherein in the step of bonding the rows of graphene fibers into a block by using a polymer, the rows of graphene fibers are bonded and rolled into a block by using the polymer.
13. The method according to claim 12, wherein in the step of solidifying and forming the heat conducting block, the solidification mode adopts normal pressure solidification or pressure solidification, and one direction or a plurality of directions are selected for pressurization during the pressure solidification.
14. The method of claim 13, wherein the curing is performed at atmospheric pressure.
15. The method of claim 14, wherein the pressurization is controlled by the compression rate during the curing process.
16. The method of claim 15, wherein the compression ratio is 5-50%.
17. The method of claim 16, wherein the compression ratio is 15-20%.
18. The method of claim 13, wherein the curing temperature is 40-150 ℃ or ambient.
19. The method of manufacturing according to claim 1, further comprising the step of surface treating the graphene fiber reinforced thermally conductive gasket, the surface treatment comprising grinding or/and polishing.
20. The method of claim 1, wherein the groove has a width of 0.1 to 0.5. 0.5 mm.
21. The method of claim 1, wherein the adjacent grooves have a center-to-center distance of 0.2-1mm.
22. The preparation method of the graphene heat-conducting film according to claim 1, wherein the preparation method comprises:
the graphene oxide slurry is used for coating, drying, heat treatment and calendaring.
23. The preparation method of the graphene heat-conducting film according to claim 1, wherein the preparation method comprises:
the high polymer film is obtained by carbonization, graphitization and calendaring, and is selected from at least one of polyimide film, nylon film, polyamide, polybenzoxazole, polybenzobisoxazole, polyoxadiazole, polythiazole, polybenzobisoxizole, polybenzothiazole, polybenzimidazole, polybenzobisoximidazole or poly-p-phenylene vinylene.
24. The preparation method of the graphene heat-conducting film according to claim 1, wherein the preparation method comprises:
and directly calendaring by using expanded graphite.
25. The method of claim 1, wherein the graphene fibers have a thickness of 10-50 microns.
26. The method of claim 1, wherein the graphene fiber density is 1.5-2.2g/cm 3 。
27. The method of claim 1, wherein the graphene fibers are present in an amount of 30-60wt.%.
28. A graphene fiber reinforced thermal conductive gasket prepared by the preparation method of any one of claims 1 to 27, wherein the thermal conductive gasket comprises graphene fibers and a high molecular polymer, and the graphene fibers are longitudinally arranged.
29. The graphene fiber reinforced thermally conductive gasket of claim 28, wherein the high molecular polymer is an epoxy resin, a phenolic resin, a furfural resin, polyurethane, an acrylic resin, polybutene, or a silicone gel.
30. The graphene fiber reinforced thermally conductive gasket of claim 29, wherein the high molecular polymer is an organic silica gel.
31. The graphene fiber reinforced thermally conductive gasket of claim 30, wherein the high molecular polymer is at least one of polydimethylsiloxane, α, ω -dihydroxypolydimethylsiloxane, polydiphenylsiloxane, α, ω -dihydroxypolymethyl3, 3, 3-trifluoropropyl siloxane, cyanosiloxysilane, and α, ω -diethylpolydimethylsiloxane.
32. The graphene fiber reinforced thermal conductive gasket of claim 28, wherein the high molecular polymer comprises other thermal conductive fillers, and the other thermal conductive fillers are at least one of graphene powder, graphite powder, boron nitride powder, aluminum oxide, aluminum nitride or silicon carbide.
33. The graphene fiber reinforced thermally conductive gasket of claim 32, wherein the other thermally conductive filler is present in the high molecular polymer in a ratio of 5wt.% to 50wt.%.
34. The graphene fiber reinforced thermally conductive gasket of claim 33, wherein the other thermally conductive filler is present in the high molecular polymer in a ratio of 10wt.% to 30wt.%.
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