CN115057432B - Graphene foam block, heat conducting sheet, gasket, arrangement device and preparation method - Google Patents

Graphene foam block, heat conducting sheet, gasket, arrangement device and preparation method Download PDF

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CN115057432B
CN115057432B CN202210690310.5A CN202210690310A CN115057432B CN 115057432 B CN115057432 B CN 115057432B CN 202210690310 A CN202210690310 A CN 202210690310A CN 115057432 B CN115057432 B CN 115057432B
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graphene
heat
fiber
fibers
foam block
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CN115057432A (en
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张鹏
葛翔
史云凯
李壮
周曙
胡佳佳
杨淑洁
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Changzhou Fuxi Technology Co Ltd
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Changzhou Fuxi Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C11/00—Component parts, details or accessories not specifically provided for in groups B05C1/00 - B05C9/00
    • B05C11/02—Apparatus for spreading or distributing liquids or other fluent materials already applied to a surface ; Controlling means therefor; Control of the thickness of a coating by spreading or distributing liquids or other fluent materials already applied to the coated surface
    • B05C11/04—Apparatus for spreading or distributing liquids or other fluent materials already applied to a surface ; Controlling means therefor; Control of the thickness of a coating by spreading or distributing liquids or other fluent materials already applied to the coated surface with blades
    • B05C11/041—Apparatus for spreading or distributing liquids or other fluent materials already applied to a surface ; Controlling means therefor; Control of the thickness of a coating by spreading or distributing liquids or other fluent materials already applied to the coated surface with blades characterised by means for positioning, loading, or deforming the blades
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/38—Fibrous materials; Whiskers
    • C04B14/386—Carbon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B30/00—Compositions for artificial stone, not containing binders
    • C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
    • 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
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
    • C04B2201/32—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values for the thermal conductivity, e.g. K-factors
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
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    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • 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
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Abstract

The invention provides a graphene foam block, a heat conducting sheet, a heat conducting gasket, an arrangement device and a preparation method, wherein the preparation method comprises the following steps: arranging a fiber array on a substrate; leveling the array of fibers on the substrate along the coating direction; coating graphene oxide slurry along the laying direction; after coating, the fiber array is pulled up along the direction perpendicular to the coating direction, and drying treatment is carried out; repeating the steps of coating, pulling up and drying to obtain graphene oxide blocks; and carrying out heat treatment on the graphene oxide block to obtain a graphene foam block. The fiber is seamlessly inserted into the heat-conducting gasket and combined with the stacked graphene layer by layer, the whole structure is complete, the fiber insertion process does not have opening operation, the damage to structural stability is avoided, the mechanical reinforcing effect on the graphene heat-conducting gasket can be realized, the structure can not be damaged, and meanwhile, the requirement for preparing gaskets with various thickness can be met.

Description

Graphene foam block, heat conducting sheet, gasket, arrangement device and preparation method
Technical Field
The invention relates to the technical field of graphene heat-conducting interface materials, in particular to a graphene foam block, a heat-conducting sheet, a heat-conducting gasket, an arrangement device and a preparation method.
Background
The graphene has excellent heat conduction performance and has wide application prospects in the fields of heat conduction, heat dissipation, heat management and the like. The graphene film with high heat conductivity is stacked layer by layer and adhered, and cut into pieces along the stacking direction, so that the obtained graphene heat conduction gasket can obtain high heat conduction performance in the longitudinal direction, the heat dissipation requirement of a high-power chip in 5G communication equipment is met, and in the practical use process, graphene is not easy to prepare independently, and in order to give full play to the high heat conduction advantage of the graphene film, the graphene film can be combined with a high polymer in a mode of directional arrangement of the whole structure of the heat conduction film, such as document CN113183544A, CN113290958A, CN113556925A.
However, the graphene heat-conducting gasket in the above document has a structure in which graphene layers are bonded together, which often causes a risk of cracking the gasket. In view of this, patent document CN113829684a discloses a method for reinforcing a graphene thermal conductive pad by carbon fibers, which is to provide a through hole in the lateral direction of the graphene thermal conductive pad, and insert the carbon fibers into the through hole, thereby playing a reinforcing role and preventing the pad from cracking.
However, the whole structure of the graphene can be damaged by directly punching holes in the transverse direction of the gasket; meanwhile, the carbon fiber inserted into the through hole can produce a certain gap, so that the reinforcing effect is limited; in addition, the heat conducting pad is required to have a certain thickness (such as more than 1 mm) by arranging the through holes, and the heat conducting pad cannot be applied to an ultrathin heat conducting pad.
Disclosure of Invention
Aiming at one or more of the problems in the prior art, the invention provides a preparation method of a graphene foam block, which comprises the following steps:
arranging a fiber array on a substrate;
leveling the array of fibers on the substrate along the coating direction;
coating graphene oxide slurry along the laying direction;
after coating, the fiber array is pulled up along the direction perpendicular to the coating direction, and drying treatment is carried out;
repeating the steps of coating, pulling up and drying to obtain graphene oxide blocks;
and carrying out heat treatment on the graphene oxide block to obtain a graphene foam block.
According to one aspect of the invention, the graphene oxide slurry has a solids content of 1.5wt.% to 9wt.%, below 1.5wt.% the slurry is too dilute to facilitate multilayer coating; above 9wt.%, the slurry is too thick and there is some resistance to the fibers inside the graphene foam block, making blade coating difficult.
Preferably, the graphene oxide slurry has a solids content of 3wt.% to 6wt.%.
According to one aspect of the invention, in the step of coating graphene oxide slurry along the leveling direction, the thickness of each coating is 0.5-10mm, and the efficiency is too low when the thickness is lower than 0.5mm; above 10mm, cracking may occur easily due to excessive difference in drying rate between the upper layer and the inside.
Preferably, the thickness of each coating is 2-6mm.
According to one aspect of the present invention, the drying treatment is normal temperature drying or heat drying, preferably, heat drying; further preferably, the heating temperature is 40-150 ℃ and the temperature is lower than 40 ℃, so that the drying speed is slow; the temperature is higher than 150 ℃, and bubbles easily enter the graphene slurry layer to cause wrinkles.
According to one aspect of the present invention, in the step of heat-treating the graphene oxide block, the temperature of the heat treatment is equal to or higher than 2400 ℃, preferably equal to or higher than 2800 ℃; the heat treatment time is more than or equal to 2 hours, preferably more than or equal to 5 hours. The temperature is lower than 2400 ℃ or the time is lower than 2 hours, so that the heat treatment is incomplete, and the heat conduction performance of the sample is poor.
According to one aspect of the present invention, further comprising: pressing the graphene foam block, wherein the density of the graphene foam block is preferably 0.8-2.2g/cm after pressing 3 Further preferably 1.0 to 1.8g/cm 3 。
According to a second aspect of the present invention there is provided a graphene foam block comprising a plurality of graphene layers and an array of fibres, the plurality of graphene layers being oriented in a direction perpendicular to the array of fibres.
According to the second aspect of the invention, the thickness of the graphene foam block is 30-250mm, preferably the thickness of the graphene foam block is 50-150mm, and the thickness of the graphene foam block is lower than 30mm, which is not beneficial to the preparation of the heat conducting fin and the heat conducting gasket; the thickness of the graphene foam block is higher than 250mm, so that the heat conduction block is easy to crack.
According to a second aspect of the invention, the fibers of the fiber array have a spacing of 1-20mm, less than 1mm, which is too small to facilitate subsequent coating; and if the thickness is higher than 20mm, the graphene is too loose, layering can occur in a partial area of the obtained graphene block, cracking easily occurs in the heat conduction gasket obtained by cutting, and the mechanical property can be obviously reduced.
Preferably, the fibers of the array of fibers have a spacing of 5-10mm.
According to a second aspect of the invention, the fibers of the array of fibers have a diameter of 5-50 microns, below 5 microns, and are not easily arranged in a whole array; above 50 microns, the strength stability of the fiber itself is reduced, and a uniform mechanical reinforcing effect cannot be achieved.
Preferably, the fibers of the fiber array have a diameter of 8-20 microns.
According to a second aspect of the present invention, the fibers of the fiber array are at least one of graphite fibers, graphene fibers, carbon nanotube fibers, carbon fibers and polyolefin fibers.
According to a second aspect of the invention, the fibers of the fiber array are individual fibers or/and bundles of fibers.
According to a second aspect of the invention, the fibers of the fiber array are untreated fibers or oxidized fibers.
Preferably, the oxygen atoms of the oxidized fiber are present in an amount of 5wt.% to 35wt.%, less than 5%, and the oxidized fiber has properties similar to those of untreated fiber; if the oxidation degree is higher than 35%, the oxidation degree is too deep, so that the mechanical properties of the fiber are obviously reduced, and the graphene heat-conducting foam block is not suitable for preparing.
Further preferably, the oxygen atoms of the oxidized fiber are present in a ratio of 6wt.% to 15wt.%.
According to a third aspect of the present invention, there is provided a method for producing a thermally conductive sheet, comprising:
cutting the graphene foam block along the direction parallel to the fiber to obtain a heat conducting sheet;
preferably, the cutting mode is at least one of wire cutting, laser cutting, ultrasonic cutting, blade cutting, freezing cutting, vibration cutting and ultrasonic-freezing cutting.
According to a fourth aspect of the present invention, there is provided a thermally conductive sheet comprising a plurality of graphene layers and a fiber array, the plurality of graphene layers being aligned in a direction perpendicular to the fiber array;
according to the fourth aspect of the present invention, the thickness of the thermally conductive sheet is not less than 0.3mm, preferably, the thickness of the thermally conductive sheet is 0.5 to 1mm, for example, the cutting thickness is less than 0.3mm, the general cutting manner is difficult to achieve, and the internal carbon fiber array is easily damaged.
According to a fifth aspect of the present invention, there is provided a method for preparing a graphene thermal pad, comprising:
immersing the heat conducting sheet into a high molecular polymer, and curing to obtain a graphene heat conducting gasket;
preferably, the high molecular polymer is immersed in the heat conductive sheet by vacuum impregnation, normal pressure impregnation or high pressure impregnation; further preferably, the vacuum degree of the vacuum impregnation is 0.095 to 0.099MPa; further preferably, the pressure of the high pressure impregnation is 0.5 to 10MPa; when the vacuum degree of vacuum impregnation is lower than 0.095MPa or the pressure of high-pressure impregnation is lower than 0.5MPa, the vacuum impregnation is not greatly different from the normal-pressure impregnation effect; when the vacuum degree of vacuum impregnation is higher than 0.099MPa or the pressure of high-pressure impregnation is higher than 10MPa, the common equipment is difficult to realize, and the cost for meeting the condition is too high.
Preferably, the curing is heat curing or normal temperature curing; further preferably, the curing is heating and curing, and even further preferably, the curing temperature is 60-150 ℃, and when the curing temperature is lower than 60 ℃, the curing time is too slow; when the curing temperature is higher than 150 ℃, the heat conduction block is easy to expand so as to cause cracking.
Preferably, the high molecular polymer is at least one of epoxy resin, phenolic resin, furfural resin, polyurethane, acrylic resin, polybutene and organic silica gel;
preferably, the high molecular polymer is organic silica gel;
preferably, the high molecular polymer is at least one of polydimethylsiloxane, alpha, omega-dihydroxypolydimethylsiloxane, polydiphenylsiloxane, alpha, omega-dihydroxypolymethyl3, 3-trifluoropropyl siloxane, cyanosiloxysilane and alpha, omega-diethylpolydimethylsiloxane.
According to a sixth aspect of the present invention, there is provided a graphene heat conductive gasket comprising the above-described heat conductive sheet and a high molecular polymer impregnated into the graphene heat conductive gasket.
Preferably, the content of the high molecular polymer is 10wt.% to 60wt.%, less than 10wt.%, which is equivalent to the effect of non-impregnation; above 60wt.%, the heat conducting properties are severely affected, further preferably the high molecular polymer content is 20wt.% to 50wt.%.
According to a seventh aspect of the present invention, there is provided an arrangement for arranging an array of fibres on a substrate, the arrangement comprising a substrate and a tie rod, the substrate and tie rod being provided with a plurality of holes, respectively, the fibres passing through one or more holes of the substrate or/and tie rod and out of the other hole or holes of the substrate or/and tie rod to form an array of fibres.
The fiber is seamlessly inserted into the graphene heat-conducting gasket and combined with the stacked graphene layer by layer to form an integral structure, the graphene foam block, the heat-conducting sheet and the graphene heat-conducting gasket have complete integral structure, the fiber insertion process does not have tapping operation, the damage to structural stability is avoided, the mechanical reinforcing effect on the graphene heat-conducting gasket can be realized, the structure of the graphene heat-conducting gasket can be ensured not to be damaged, and meanwhile, the requirement for preparing gaskets with various thickness sizes can be met.
According to the invention, the transverse direction of graphene is converted into the longitudinal direction by using a layer-by-layer stacking mode, so that the longitudinal heat conductivity is improved, the heat conductivity is further enhanced by arranging fibers in a plurality of graphene layers, the mechanical property is improved, and the cracking phenomenon of graphene foam blocks and graphene heat conduction gaskets is prevented.
According to the graphene heat-conducting gasket, the fiber array which is vertically arranged with the graphene layers is arranged in the graphene heat-conducting gasket, and the fibers are seamlessly inserted into the graphene heat-conducting gasket and are tightly combined with the stacked graphene layers layer by layer to be composited into a stable whole.
The preparation method adopts a preparation mode of combining the fiber array and the graphene, and stably enhances the bonding force between graphite layers.
According to the invention, the influence of carbon fibers on the coating can be avoided by adopting a horizontal coating mode, and the directional arrangement of the final graphene is maintained through coating, pulling up and drying;
when the graphene foam block is further pressed and densified, the fibers can be bent along with pressing and are tightly combined in the graphene foam block, and the reinforcing effect is not affected.
The graphene heat conduction gasket prepared by the preparation method has the advantages of high orientation, high heat conduction, no cracking and the like, can be prepared into gaskets with different thicknesses, and is wide in application.
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:
FIG. 1 is a schematic view of one embodiment of a graphene foam block according to the present invention;
FIG. 2 is a schematic view of one embodiment of a thermally conductive sheet according to the present invention;
FIG. 3 is a schematic view of an embodiment of an arrangement according to the invention;
fig. 4 is a schematic diagram of one embodiment of a method of applying graphene oxide slurry in a lay-flat direction 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. 1 is a schematic view of one embodiment of a graphene foam block according to the present invention, and as shown in fig. 1, the graphene foam block includes a plurality of graphene layers and a fiber array, and the plurality of graphene layers are aligned in a direction perpendicular to the fiber array. The graphene layer is formed by highly oriented arrangement of graphene along the direction vertical to the fiber array, and a layered structure with highly ordered arrangement is formed inside.
Fig. 2 is a schematic view of an embodiment of the heat conductive sheet according to the present invention, which is obtained by cutting the above-described graphene foam block in a direction parallel to the fiber direction, and which includes graphene layers aligned in the thickness direction and a fiber array perpendicular to the graphene layers, as shown in fig. 2.
Fig. 3 is a schematic view of an embodiment of the arrangement according to the present invention, as shown in fig. 3, the arrangement comprises a base material 10 and a pull rod 20, and a plurality of holes are correspondingly formed in the base material and the pull rod.
The method for forming the fiber array by using the arrangement device comprises the following steps: the fibers penetrate through the hole or holes of the base material or/and the pull rod and penetrate out of the other hole or holes of the base material or/and the pull rod to form a fiber array.
As shown in fig. 3, the plurality of holes includes a plurality of first holes for initial penetration of the fibers and a plurality of second holes having one end penetrating the fibers and the other end penetrating the fibers.
In the following embodiments, the preparation method of the fiber array reinforced graphene heat-conducting pad includes a plurality of the following steps:
(1) Arranging a fiber array on a substrate;
(2) As shown in fig. 4, the fibers were laid flat on the substrate in the direction of coating, and then coated in the direction of laying flat;
(3) After coating, the fiber is pulled up again (as shown in fig. 3), an array is formed along the direction perpendicular to the coating direction, the graphene oxide slurry can be naturally leveled, and the grooves formed after the fiber is pulled up are filled;
(4) Drying while maintaining the above state;
(5) Repeating the steps (2) - (4), and stripping the base material to obtain graphene oxide blocks with required thickness;
(6) Carrying out heat treatment on the graphene oxide block to obtain a graphene foam block;
(7) Pressing the graphene foam block;
(8) Cutting the graphene foam block along the direction parallel to the fiber to obtain a heat conducting sheet;
(9) And immersing the heat conducting sheet into a high-molecular polymer, and curing to obtain the graphene heat conducting gasket.
The surface of the fiber used on the surface of the fiber can be oxidized or not treated at all; the oxidation treatment can be performed by adopting air and/or oxygen, or can be performed by sulfuric acid, nitric acid, aqua regia, potassium permanganate, hydrogen peroxide and mixtures thereof; the oxygen atoms on the surface of the fiber subjected to oxidation treatment account for 5% -35%; preferably 6% -15%. The oxidized fiber and the graphene oxide are subjected to chemical reaction to generate chemical bonds, so that the fiber and the graphene oxide are tightly combined.
The heat-conducting gasket fiber is seamlessly inserted into the heat-conducting gasket and combined with the graphene stacked layer by layer to form an integral structure.
The test method of the heat conducting fin or the graphene heat conducting pad obtained in each embodiment comprises the following steps:
testing the applied thermal resistance (the sum of the intrinsic thermal resistance of the sample and the contact thermal resistance of the upper and lower surfaces) of the sample by ASTM D5470;
the samples were tested for transverse and longitudinal thermal diffusivity by ASTM E1461;
specific heat capacity was tested by ASTM E1269-2018;
the density was tested by GB 4472-1984;
the thermal conductivity is calculated using the following formula:
K＝λ·C p ·ρ
k-coefficient of thermal conductivity, unit W/(m.K);
lambda-thermal diffusivity, unit mm 2 /s；
C p Specific heat capacity, unit J/g/K;
ρ -Density in g/cm 3 ；
Testing transverse tensile property of a sample by using GB T1040.3-2006, wherein the length and width dimensions of the sample are 100X 10mm;
the samples were tested for longitudinal compressibility and compression resilience using ASTM D395, respectively for the compressibility of the samples at 40psi pressure, and for the resilience after 30 minutes after the samples were compressed to 50% strain.
Example 1
In this embodiment, the preparation process and parameters of the graphene heat-conducting pad include:
the fiber is carbon fiber with the diameter of 5 μm; the fiber spacing in the fiber array is 1mm; the surface of the fiber is subjected to oxidation treatment, and the oxygen content is 5wt.%;
the graphene oxide slurry used had a solids content of 1.5wt.%; the thickness of each coating is 0.6mm; the heat treatment temperature is 2400 ℃; the heat treatment time is 2 hours;
in the embodiment, the graphene foam block is not pressed; the slicing mode is linear cutting;
the high molecular polymer adopts polydimethyl cyclosiloxane, and is immersed under high pressure of 3MPa; the curing temperature is 70 ℃; the content of the high molecular polymer after impregnation curing is 20wt.%;
the thickness of the graphene heat conduction gasket is 0.3mm;
through testing, the obtained graphene heat conduction gasket has the following relevant performances:
density: 0.77g/cm 3 ；
Longitudinal thermal conductivity: 75.35W/(mK);
lateral thermal conductivity: 28.55W/(mK);
applying thermal resistance: 0.722K cm 2 /W；
Transverse tensile strength: 2.91MPa;
longitudinal compression ratio: 45.33%;
longitudinal spring rate: 65.62%.
Example 2
In this embodiment, the preparation process and parameters of the graphene heat-conducting pad include:
the fiber is carbon fiber with the diameter of 15 μm; the fiber spacing in the fiber array is 15mm; the surface of the fiber is subjected to oxidation treatment, and the oxygen content is 35wt.%;
the graphene oxide slurry used had a solids content of 9wt.%; the thickness of each coating is 10mm; the heat treatment temperature is 2800 ℃; the heat treatment time is 5 hours;
in the embodiment, the graphene foam block is not pressed; the slicing mode is linear cutting;
the high polymer adopts polydimethyl cyclosiloxane, adopts vacuum impregnation, and has the vacuum degree of 0.088MPa; the curing temperature is 150 ℃; the content of the high molecular polymer after impregnation curing was 50wt.%;
the thickness of the graphene heat conduction gasket is 2mm;
through testing, the obtained graphene heat conduction gasket has the following relevant performances:
density: 0.6g/cm 3 ；
Longitudinal thermal conductivity: 53.35W/(mK);
lateral thermal conductivity: 13.79W/(mK);
applying thermal resistance: 1.125K cm 2 /W；
Transverse tensile strength: 2.13MPa;
longitudinal compression ratio: 41.33%;
longitudinal spring rate: 74.62%.
Example 3
In this embodiment, the preparation process and parameters of the graphene heat-conducting pad include:
the fiber is graphite fiber with diameter of 8 μm; the fiber spacing in the fiber array is 5mm; the surface of the fiber was subjected to an oxidation treatment with an oxygen content of 6wt.%;
the graphene oxide slurry used had a solids content of 3wt.%; the thickness of each coating is 2mm; the heat treatment temperature is 2900 ℃; the heat treatment time is 6 hours;
pressing the graphene foam block, wherein the density of the pressed graphene foam block is 1.1g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The slicing mode is laser cutting;
the high molecular polymer adopts polydimethyl cyclosiloxane, and is immersed under high pressure of 3MPa; the curing temperature is 120 ℃; the content of the high molecular polymer after impregnation curing is 20wt.%;
the thickness of the graphene heat conduction gasket is 0.5mm;
through testing, the obtained graphene heat conduction gasket has the following relevant performances:
density: 1.1g/cm 3 ；
Longitudinal thermal conductivity: 70.98W/(mK);
lateral thermal conductivity: 25.66W/(mK);
applying thermal resistance: 0.778K cm 2 /W；
Transverse tensile strength: 3.53MPa;
longitudinal compression ratio: 46.73%;
longitudinal spring rate: 67.35%.
Example 4
In this embodiment, the preparation process and parameters of the graphene heat-conducting pad include:
the fiber is carbon fiber with diameter of 20 μm; the fiber spacing in the fiber array is 10mm; the surface of the fiber is subjected to oxidation treatment, and the oxygen content is 15wt.%;
the graphene oxide slurry used had a solids content of 6wt.%; the thickness of each coating is 6mm; the heat treatment temperature is 3000 ℃; the heat treatment time is 7 hours;
pressing the graphene foam block, wherein the density of the pressed graphene foam block is 1.7g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The slicing mode is linear cutting;
the high molecular polymer adopts polydimethyl cyclosiloxane, and is immersed under high pressure of 7MPa; the curing temperature is 120 ℃; the content of the high molecular polymer after impregnation curing was 42wt.%;
the thickness of the graphene heat conduction gasket is 1mm;
through testing, the obtained graphene heat conduction gasket has the following relevant performances:
density: 1.7g/cm 3 ；
Longitudinal thermal conductivity: 75.86W/(mK);
lateral thermal conductivity: 23.51W/(mK);
applying thermal resistance: 0.856K cm 2 /W；
Transverse tensile strength: 3.92MPa;
longitudinal compression ratio: 40.83%;
longitudinal spring rate: 70.57%.
Example 5
In this embodiment, the preparation process and parameters of the graphene heat-conducting pad include:
the fiber is carbon fiber with diameter of 10 μm; the fiber spacing in the fiber array is 2mm; the surface of the fiber was treated with an oxygen content of 9wt.%;
the graphene oxide slurry used had a solids content of 5wt.%; the thickness of each coating is 3mm; the heat treatment temperature is 3000 ℃; the heat treatment time is 6 hours;
pressing the graphene foam block, wherein the density of the pressed graphene foam block is 1.5g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The slicing mode is linear cutting;
the high polymer adopts polydimethylsiloxane, and is impregnated in vacuum under the condition of 0.080MPa of vacuum degree, and then is impregnated under the pressure of 6.6 MPa; the curing temperature is 130 ℃; the content of the high molecular polymer after impregnation curing was 40wt.%;
the thickness of the graphene heat conduction gasket is 0.6mm;
through testing, the relative performance of the graphene heat-conducting gasket is as follows:
density: 1.5g/cm 3 ；
Longitudinal thermal conductivity: 86.59W/(mK);
lateral thermal conductivity: 31.51W/(mK);
applying thermal resistance: 0.685K cm 2 /W；
Transverse tensile strength: 4.67MPa;
longitudinal compression ratio: 32.65%;
longitudinal spring rate: 52.33%.
Example 6
In this embodiment, the preparation process and parameters of the heat conducting strip include:
the fiber is graphite fiber with the diameter of 9 μm; the fiber spacing in the fiber array is 7mm; the surface of the fiber was treated with an oxygen content of 8wt.%;
the graphene oxide slurry used had a solids content of 4wt.%; the thickness of each coating is 3mm; the heat treatment temperature is 2900 ℃; the heat treatment time is 6 hours;
pressing the graphene foam block, wherein the density of the pressed graphene foam block is 1.1g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The slicing mode is linear cutting;
the high molecular polymer dipping treatment is not carried out;
the thickness of the heat conducting fin is 0.5mm;
the relevant properties of the obtained thermally conductive sheet were tested as follows:
density: 1.1g/cm 3 ；
Longitudinal thermal conductivity: 77.83W/(mK);
lateral thermal conductivity: 29.35W/(mK);
applying thermal resistance: 0.726K cm 2 /W；
Transverse tensile strength: 1.47MPa;
longitudinal compression ratio: 25.22%;
longitudinal spring rate: 51.76%.
Example 7
In this comparative example, the preparation process and parameters of the thermally conductive sheet were the same as those of example 6 except that the solid content of the graphene oxide slurry used was 8wt.%;
through testing, the relevant performance of the heat conducting fin is as follows:
density: 1.1g/cm 3 ；
Longitudinal thermal conductivity: 81.63W/(mK);
lateral thermal conductivity: 33.15W/(mK);
applying thermal resistance: 0.713K cm 2 /W；
Transverse tensile strength: 1.04MPa;
longitudinal compression ratio: 19.53%;
longitudinal spring rate: 38.78%.
As can be seen from the data in examples 6 and 7, when the solid content of the graphene oxide slurry used is too large (more than 6 wt.%), the transverse tensile strength of the resulting thermally conductive sheet is significantly reduced, and the mechanical properties are significantly reduced.
Comparative example 1
In this comparative example, the relevant process and parameters were the same as in example 3 except that the fiber spacing in the fiber array was 15mm;
the obtained graphene heat conduction gasket is cracked, and the related performance of the graphene heat conduction gasket is as follows through tests:
density: 1.1g/cm 3 ；
Longitudinal thermal conductivity: 53.69W/(mK);
lateral thermal conductivity: 23.56W/(mK);
applying thermal resistance: 0.862K cm 2 /W；
Transverse tensile strength: 0.852MPa;
longitudinal compression ratio: 35.13%;
longitudinal spring rate: 47.35%.
By combining the data in the embodiment 3 and the comparative example 1, it can be seen that when the fiber array spacing is too large (greater than 10 mm), the internal binding force of the obtained graphene foam block is poor, layering can occur in a part of areas, cracking easily occurs in the graphene heat-conducting gasket obtained by cutting, and the mechanical property can be remarkably reduced.
Comparative example 2
In this embodiment, the preparation process and parameters of the graphene heat-conducting pad include:
the fiber is carbon fiber with diameter of 18 μm; the fiber spacing in the fiber array is 10mm; the surface of the fiber is subjected to oxidation treatment, and the oxygen content is 12wt.%;
the graphene oxide slurry used had a solids content of 6wt.%; the thickness of each coating is 6mm; the heat treatment temperature is 1900 ℃; the heat treatment time is 7 hours;
pressing the graphene foam block, wherein the density of the pressed graphene foam block is 1.6g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The slicing mode is linear cutting;
the high molecular polymer adopts polydimethyl cyclosiloxane, and is immersed under high pressure of 7MPa; curing temperature is 120 ℃; the content of the high molecular polymer after impregnation curing was 40wt.%;
the thickness of the graphene heat conduction gasket is 1mm;
through testing, the obtained graphene heat conduction gasket has the following relevant performances:
density: 1.6g/cm 3 ；
Longitudinal thermal conductivity: 49.31W/(mK);
lateral thermal conductivity: 19.76W/(mK);
applying thermal resistance: 0.983K cm 2 /W；
Transverse tensile strength: 3.63MPa;
longitudinal compression ratio: 41.09%;
longitudinal spring rate: 68.87%.
As can be seen from the data in example 4 and comparative example 2, when the heat treatment temperature is lower than 2400 ℃, the heat treatment is incomplete, which affects the heat conductive property of the heat conductive pad.
Comparative example 3
In this embodiment, the preparation process and parameters of the graphene heat-conducting pad include:
the fiber is carbon fiber with diameter of 10 μm; the fiber spacing in the fiber array is 3mm; the surface of the fiber is subjected to oxidation treatment, and the oxygen content is 10wt.%;
the graphene oxide slurry used had a solids content of 7wt.%; the thickness of each coating is 5mm; the heat treatment temperature is 2950 ℃; the heat treatment time is 6 hours;
pressing the graphene foam block, wherein the density of the pressed graphene foam block is 1.4g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The slicing mode is linear cutting;
the high polymer adopts polydimethylsiloxane, and is impregnated in vacuum under the condition that the vacuum degree is 0.099MPa, and then is impregnated under the pressure of 10MPa; curing temperature is 130 ℃; the content of high molecular polymer after impregnation was 75wt.%;
the thickness of the graphene heat conduction gasket is 0.6mm;
through testing, the obtained graphene heat conduction gasket has the following relevant performances:
density: 1.4g/cm 3 ；
Longitudinal thermal conductivity: 51.59W/(mK);
lateral thermal conductivity: 18.74W/(mK);
applying thermal resistance: 1.262K cm 2 /W；
Transverse tensile strength: 4.15MPa;
longitudinal compression ratio: 27.27%;
longitudinal spring rate: 58.31%.
As can be seen from the data in example 3 and comparative example 3, when the content of the high molecular polymer exceeds a certain value (60 wt.%) in the process of immersing the thermally conductive sheet further into the high molecular polymer, the thermal conductivity coefficients of the graphene thermally conductive pad in the lateral and longitudinal directions are significantly reduced, and the thermal resistance is also large, so that the influence on the thermal conductivity is large.
Comparative example 4
In this comparative example, the relevant process and parameters were the same as in example 5 except that the fiber array was not vertically aligned with the graphene layer (the fiber array was 60 ° from the substrate);
through testing, the graphene heat conduction gasket has the following related performances:
density: 1.5g/cm 3 ；
Longitudinal thermal conductivity: 75.12W/(mK);
lateral thermal conductivity: 27.65W/(mK);
applying thermal resistance: 0.703K cm 2 /W；
Transverse tensile strength: 3.81MPa;
longitudinal compression ratio: 29.67%;
longitudinal spring rate: 47.94%.
It can be seen from the data in example 5 and comparative example 4 that when the fiber array is not vertically aligned with the graphene layer, the thermal and mechanical properties of the resulting graphene thermal pad are reduced compared to those of the graphene thermal pad in which the fiber array is vertically aligned with the graphene layer.
The fiber and the graphene are tightly combined and seamlessly inserted into the graphite layer, microcracks at the joint of the fiber and the graphene can be eliminated by tightly combining the fiber and the graphene, and the graphene is highly oriented in the graphene foam block, so that the graphene has high heat conduction performance along the arrangement direction. The coating mode is improved, and the graphene foam block with good integrity can be obtained. The graphene foam block has a stable structure, and can be prepared into graphene heat-conducting gaskets with different thicknesses and good compression performance. The graphene heat conduction gasket is not easy to crack, and is excellent in mechanical property and good in heat uniformity in the transverse direction.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that the present invention is not limited to the preferred embodiments, and modifications may be made to the technical solutions described in the foregoing embodiments or equivalents may be substituted for some of the technical features thereof. 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 (42)

1. The preparation method of the graphene foam block is characterized by comprising the following steps of:
arranging a fiber array on a substrate, wherein the fiber of the fiber array is at least one of graphite fiber, graphene fiber, carbon nano-tube fiber, carbon fiber and polyolefin fiber;
leveling the array of fibers on the substrate along the coating direction;
coating graphene oxide slurry along the laying direction;
after coating, the fiber array is pulled up along the direction perpendicular to the coating direction, and drying treatment is carried out;
repeating the steps of coating, pulling up and drying to obtain graphene oxide blocks;
and carrying out heat treatment on the graphene oxide block to obtain a graphene foam block.
2. The method of manufacturing according to claim 1, characterized in that the graphene oxide slurry has a solids content of 1.5wt.% to 9wt.%.
3. The method of preparing according to claim 2, characterized in that the graphene oxide slurry has a solids content of 3wt.% to 6wt.%.
4. The method according to claim 1, wherein in the step of coating the graphene oxide slurry in the lay-flat direction, the thickness of each coating is 0.5 to 10mm.
5. The method of claim 4, wherein each coating has a thickness of 2-6mm.
6. The method according to claim 1, wherein the drying treatment is normal temperature drying or heat drying.
7. The method according to claim 6, wherein the drying treatment is heat drying.
8. The method according to claim 7, wherein the heating temperature is 40 to 150 ℃.
9. The method according to claim 1, wherein in the step of heat-treating the graphene oxide block, the temperature of the heat treatment is not less than 2400 ℃; the heat treatment time is more than or equal to 2 hours.
10. The method of claim 9, wherein the temperature of the heat treatment is greater than or equal to 2800 ℃; the heat treatment time is more than or equal to 5 hours.
11. The method of manufacturing according to claim 1, further comprising: and pressing the graphene foam block.
12. The method of claim 11, wherein the density of the graphene foam block after pressing is 0.8-2.2g/cm 3 。
13. The method of claim 12, wherein the density of the graphene foam block after pressing is 1.0-1.8g/cm 3 。
14. The method of claim 1, wherein the fibers of the array of fibers have a spacing of 1-20 mm.
15. The method of claim 14, wherein the fibers of the array of fibers have a spacing of 5-10mm.
16. The method of claim 1, wherein the fibers of the array of fibers have a diameter of 5 to 50 microns.
17. The method of claim 16, wherein the fibers of the array of fibers have a diameter of 8-20 microns.
18. The method of claim 1, wherein the fibers of the fiber array are individual fibers or/and fiber bundles.
19. The method of claim 1, wherein the fibers of the fiber array are untreated fibers or oxidized fibers.
20. The method of claim 19, wherein the oxidized fiber has an oxygen atom ratio of 5wt.% to 35wt.%.
21. The method of claim 20, wherein the oxygen atoms of the oxidized fiber are present in a ratio of 6wt.% to 15wt.%.
22. A graphene foam block prepared by the preparation method of any one of claims 1 to 21.
23. The graphene foam block according to claim 22 wherein the graphene foam block has a thickness of 30-250mm.
24. The graphene foam block according to claim 23 wherein the graphene foam block has a thickness of 50-150mm.
25. A method for producing a heat conductive sheet, comprising:
cutting the graphene foam block prepared by the preparation method of any one of claims 1 to 21 along a direction parallel to the fiber to obtain the heat conducting sheet.
26. The method of claim 25, wherein the cutting is at least one of wire cutting, laser cutting, ultrasonic cutting, blade cutting, freeze cutting, vibration cutting, and ultrasonic-freeze cutting.
27. A thermally conductive sheet, characterized by being produced by the production method according to claim 25 or 26.
28. The thermally conductive sheet of claim 27, wherein the thermally conductive sheet has a thickness of not less than 0.3mm.
29. The thermally conductive sheet of claim 28, wherein the thermally conductive sheet has a thickness of 0.5-1mm.
30. The preparation method of the graphene heat conduction gasket is characterized by comprising the following steps of:
immersing the heat conducting sheet prepared by the preparation method of claim 25 or 26 into a high molecular polymer, and curing to obtain the graphene heat conducting gasket.
31. The method of claim 30, wherein the high molecular weight polymer is impregnated into the thermally conductive sheet by vacuum impregnation, normal pressure impregnation or high pressure impregnation.
32. The method according to claim 31, wherein the vacuum degree of vacuum impregnation is 0.095 to 0.099MPa.
33. The method of claim 32, wherein the high pressure impregnation is at a pressure of 0.5 to 10MPa.
34. The method of claim 30, wherein the curing is heat curing or ambient temperature curing.
35. The method of claim 34, wherein the curing is heat curing.
36. The method of claim 35, wherein the curing temperature is 60 to 150 ℃.
37. The method of claim 30, wherein the high molecular polymer is at least one of epoxy resin, phenolic resin, furfural resin, polyurethane, acrylic resin, polybutene, and silicone.
38. The method of claim 37, wherein the high molecular polymer is a silicone gel.
39. The method according to claim 38, 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.
40. A graphene heat-conducting gasket, which is characterized by comprising a heat-conducting sheet prepared by the preparation method of claim 25 or 26 and a high-molecular polymer immersed in the graphene heat-conducting gasket.
41. The graphene thermal pad according to claim 40, wherein the high molecular polymer is present in an amount of 10wt.% to 60wt.%.
42. The graphene thermal pad of claim 41, wherein the high molecular polymer is present in an amount of 20wt.% to 50wt.%.
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