CN115073793A - Graphene heat-conducting film, preparation method thereof and heat-conducting gasket - Google Patents
Graphene heat-conducting film, preparation method thereof and heat-conducting gasket Download PDFInfo
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Classifications
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
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- 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
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- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- 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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- 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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
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Abstract
The scheme discloses a graphene heat-conducting film, a preparation method thereof and a heat-conducting gasket, wherein the method comprises the following steps: a. coating graphene oxide slurry on the surface of a base material; b. waiting for the surface layer of the coated graphene oxide slurry to be dried; c. arranging holes and/or grooves which do not penetrate through the surface layer on the dried surface layer, and continuously coating graphene oxide slurry on the dried surface layer; d. repeating the steps a to c, and drying all the graphene oxide slurry to obtain a graphene oxide film; e. and carrying out heat treatment on the graphene oxide film to obtain the graphene heat-conducting film. The prepared graphene heat-conducting film has a layered structure, the prepared thickness and the number of layers are controllable, and the obtained graphene heat-conducting film cannot be dispersed to form an integral structure.
Description
Technical Field
The invention relates to the technical field of heat conducting and radiating materials, in particular to a graphene heat conducting film, a preparation method thereof and a heat conducting gasket.
Background
Along with the development of science and technology, electronic equipment such as smart mobile phones, notebook computer that has high demand to the heat dissipation needs the better heat conduction gasket of thermal diffusivity, reduces the heat that the inside institute of electronic equipment distributed out, guarantees the normal operating of equipment. With the further improvement of the heat dissipation requirement of the electronic device, the requirements of the applied heat-conducting gasket are further upgraded.
Due to the excellent heat-conducting property of the graphene heat-conducting film, the graphene heat-conducting film is one of excellent materials for preparing the heat-conducting gasket. At present, the processes for preparing the heat conducting gasket by adopting the graphene heat conducting film mainly comprise two processes, namely, the graphene heat conducting film is connected by using an adhesive and longitudinally stacked into a whole, and the adopted heat conducting gasket is arranged along the thickness direction; secondly, the graphene heat-conducting film is bonded into an integral structure in the plane direction by utilizing the wrinkles and coating adhesives.
However, the graphene is easily delaminated inside, so that the obtained graphene thermal pad is easily cracked, because the graphene thermal conductive film has a densified structure, and the graphene thermal conductive film is difficult to be immersed in a matrix material such as a polymer. In contrast, patent documents CN112852159A, CN113147115A, CN113290958A, and CN113510979A adopt a graphene foam film to prepare a thermal pad, and pores inside the graphene foam are used to fill with a polymer, so as to achieve an effect of improving the internal bonding force of the thermal pad. However, since most of the pores inside the graphene foam film are closed pores with small sizes, great difficulty is added to the impregnation of a matrix material such as a polymer, and only a small amount of pores can be filled. Therefore, the obtained heat-conducting gasket always has the problems of poor mechanical property and easy cracking, and the wide application of the graphene heat-conducting gasket is limited.
Disclosure of Invention
One object of the present scheme is to provide a method for preparing a graphene thermal conductive film, where the prepared graphene thermal conductive film has a layered structure, the thickness and the number of layers of the prepared graphene thermal conductive film are controllable, and the obtained graphene thermal conductive film does not disperse and can form an integral structure.
Another object of the present disclosure is to provide a graphene thermal conductive film prepared by the above method.
A third object of the present invention is to provide a heat conductive gasket.
In order to achieve the purpose, the scheme is as follows:
a preparation method of a graphene heat conduction film comprises the following steps:
a. coating graphene oxide slurry on the surface of a base material;
b. waiting for the surface layer of the coated graphene oxide slurry to be dried;
c. arranging holes and/or grooves which do not penetrate through the surface layer on the dried surface layer, and continuously coating graphene oxide slurry on the dried surface layer;
d. repeating the steps a to c, and drying all the graphene oxide slurry to obtain a graphene oxide film;
e. and carrying out heat treatment on the graphene oxide film to obtain the graphene heat-conducting film.
Preferably, the base material is one or more of polyethylene terephthalate (PET), polypropylene (PP), Polyethylene (PE), polyvinyl chloride (PVC), Polytetrafluoroethylene (PTFE), copper foil, aluminum film and glass.
Preferably, the solid content of the graphene oxide slurry is 1 wt.% to 10 wt.%; preferably, the solid content of the graphene oxide slurry is 2-8 wt.%;
the solvent in the graphene oxide slurry is one or more of water, ethanol, methanol, N, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), toluene, xylene, ethyl acetate and acetone;
the thickness of the coated graphene oxide slurry is 5-300 mu m; the thickness of the coated graphene oxide slurry is preferably 50 to 200 μm.
If the thickness of the single-coated graphene oxide slurry is less than 5 micrometers, the dried film is too thin and is easy to crack; if the thickness of one-pass coating is larger than 300. mu.m, bubbles are easily generated inside.
Preferably, the drying temperature of the graphene oxide slurry during drying is 40-150 ℃.
Some drying temperatures above 150 ℃ dry too quickly, easily causing film cracking.
Preferably, in step c, holes and/or grooves that do not penetrate through the surface layer are provided in the thickness direction of the graphene oxide film; the aperture of the hole is 10-40 μm, preferably 50-200 μm; the hole pitch of the holes is 500-2000 mu m, and preferably 800-1200 mu m; the length of the groove is 200-8000 mu m, preferably 500-5000 mu m; the width of the groove is 20-1000 μm, and preferably 100-800 μm; the groove pitch between the grooves is 500 to 2000 μm, and preferably 800 to 1000 μm.
If the size of the non-penetrating hole and/or the non-penetrating groove is too small, the connection effect between the adjacent two graphene films is poor, the graphene films are easy to disperse, and the graphene films cannot form a whole; if the size of the non-through holes and/or non-through grooves is too large, the graphene film has a less pronounced delamination effect.
Preferably, the heat treatment temperature in the step e is 2400 ℃ or higher, and preferably 2800 ℃ or higher.
In a second aspect, a graphene thermal conductive film is provided, which is prepared by any one of the preparation methods described above, and the prepared graphene thermal conductive film contains multilayer graphene, and a pore structure is formed between every two adjacent layers of graphene of the multilayer graphene, and the pore structure is a hole and/or a groove which does not penetrate through the graphene layer; meanwhile, at least one through hole penetrating through the multilayer graphene layers is formed in the multilayer graphene layers;
the thickness of the graphene heat conduction film is 10-200 mu m, and preferably the thickness of the graphene heat conduction film is 20-150 mu m; the thickness of the graphene layer is 0.5-5 mu m, and the thickness of the graphene layer is preferably 1-3 mu m.
If the thickness of the graphene heat-conducting film is less than 10 micrometers, the graphene heat-conducting film is poor in mechanical property and easy to break; if the thickness of the graphene thermal conductive film is greater than 200 μm, the graphene thermal conductive film is easily curled, wrinkled, and cracked.
If the thickness of the graphene layer is less than 0.5 μm, cracks are easily caused inside; if the thickness of the graphene layer is more than 5 μm, the layering effect is not obvious, and the graphene layer is not easy to combine with matrix materials such as high polymers and the like during application.
The utility model provides a graphite alkene heat conduction membrane's inside is connected by a plurality of thin layer graphite alkene membranes and constitutes, forms a plurality of great pore structures, and the inside hole of graphite alkene heat conduction membrane of this structure links to each other, can easily fill matrix materials such as polymer, realizes good cohesion. If the plurality of graphene thin layers are not connected, the plurality of graphene thin layers are dispersed and cannot form a whole; if the internal pores are not connected, the polymer matrix is difficult to fill due to the closed pore structure.
In a third aspect, a thermal conductive gasket is provided, which is prepared from the graphene thermal conductive film, and includes the following steps:
dipping the graphene heat-conducting film in an adhesive;
stacking the impregnated graphene heat-conducting films layer by layer into a block;
solidifying the obtained block;
and cutting the block body along the stacking direction to obtain the heat-conducting gasket.
In the impregnation step, the graphene film layers are impregnated with the adhesive.
In the curing step, heating curing or normal temperature curing is usually adopted, and the curing temperature is preferably 150 ℃ or lower.
When cutting, the cutting direction is cutting along the thickness direction of the stack; the cutting mode comprises linear cutting, laser cutting, ultrasonic cutting, blade cutting or freezing cutting; the thickness of the cut sheet is generally 0.1 to 5mm, preferably 0.25 to 2 mm.
Preferably, the adhesive comprises one or more of epoxy resin, phenolic resin, furfural resin, polyurethane, acrylic resin and organic silica gel; preferably, the adhesive is organic silica gel; more preferably, the adhesive is a liquid silicone; the liquid silicone rubber comprises one or more of polydimethylsiloxane, polydimethylcyclosiloxane, dimethyldiphenylpolysiloxane, alpha, omega-dihydroxypolydimethylsiloxane, alpha, omega-divinylpolydimethylsiloxane and alpha, omega-dihydroxypolymethyl (3,3, 3-trifluoropropyl) siloxane.
Preferably, the content of graphene in the heat conduction gasket is 25 wt.% to 75 wt.%; preferably, the content of the graphene is 35-65 wt.%.
The scheme has the following beneficial effects:
the method can prepare the graphene heat-conducting film with the thickness and the number of layers controllable and the layered structure; prepared by
The graphene heat conduction film cannot be dispersed to form an integral structure; when the prepared graphene heat-conducting membrane is used as a composite material reinforcement to prepare the heat-conducting gasket, the matrix material can be directly injected into the gap of the graphene heat-conducting membrane, so that the composite material is simple and convenient to prepare, and the prepared heat-conducting gasket has the advantages of better compactness, higher heat conductivity coefficient, favorable compressibility and compression resilience and wider applicability.
Detailed Description
Embodiments of the present solution are described in further detail below. It is clear that the described embodiments are only a part of the embodiments of the present solution, and not an exhaustive list of all embodiments. It should be noted that, in the present embodiment, the features of the embodiment may be combined with each other without conflict.
It should be understood that the term "and/or" as used herein is merely a relationship that describes an associated object, meaning that three relationships may exist, e.g., a and/or B, may represent: a exists alone, A and B exist simultaneously, and B exists alone.
The application scenario of the conventional graphene heat-conducting film needs that the graphene heat-conducting film is compact enough and is not layered, but the conventional graphene heat-conducting film is often accompanied by the risk of layering for various reasons, and the layering referred to herein is uncontrollable layering inside the graphene heat-conducting film and is often randomly divided into 2-3 layers.
The application discloses graphite alkene heat conduction membrane, this graphite alkene heat conduction membrane inside contains multilayer graphite alkene layer, and both interconnect exist a plurality of pore structure between these graphite alkene layers, and the connection between the graphite alkene layer is realized through the hole that sets up between graphite alkene layer and run through, and a plurality of pore structure between the graphite alkene layer then set up on graphite alkene layer not run through the hole and/or the groove on graphite alkene layer.
The graphene heat-conducting film has a layered structure and can be divided into multiple layers by control; the thickness of each layer can be regulated and controlled through the thickness of each coating; at least one region for connecting the adjacent two graphene layers is arranged between the two graphene layers, so that the integrity and the non-easy dispersion of the graphene heat conduction film are ensured.
The graphene heat-conducting film prepared by the application has a pore structure, so that the graphene heat-conducting film can be easily filled with polymer and other matrix materials, and good bonding force between the polymer materials and graphene is realized. And (3) bonding and stacking the graphene heat conduction films filled with the macromolecules layer by layer to form a composite block, and cutting the composite block into sheets along the stacking direction to obtain the graphene heat conduction gasket. The graphene heat-conducting gasket prepared by the scheme has the advantages of high longitudinal heat-conducting property, good mechanical property and difficulty in cracking.
A preparation method of a graphene heat conduction film comprises the following steps:
a. coating graphene oxide slurry on the surface of a base material;
b. waiting for the surface layer of the coated graphene oxide slurry to be dried;
c. arranging holes and/or grooves which do not penetrate through the surface layer on the dried surface layer, and continuously coating graphene oxide slurry on the dried surface layer;
d. repeating the steps a to c, and drying all the graphene oxide slurry to obtain a graphene oxide film;
e. and carrying out heat treatment on the graphene oxide film to obtain the graphene heat-conducting film.
A preparation method of a heat-conducting gasket comprises the following steps:
f. dipping the graphene heat-conducting film in an adhesive;
g. stacking the impregnated graphene heat conduction films layer by layer into a block;
h. solidifying the obtained block;
i. and cutting the block body along the stacking direction to obtain the heat-conducting gasket.
In one embodiment, the material of the substrate coated with the graphene oxide slurry is one or more of polyethylene terephthalate, polypropylene, polyethylene, polyvinyl chloride, polytetrafluoroethylene, copper foil, aluminum film and glass.
In one embodiment, the graphene oxide slurry used for coating has a solid content of 1 wt.% to 10 wt.%; preferably, the graphene oxide slurry has a solid content of 2 wt.% to 8 wt.%, such as 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.%, 4 wt.%, 4.5 wt.%, 5 wt.%, 5.5 wt.%, 6 wt.%, 6.5 wt.%, 7 wt.%, 7.5 wt.%, or 8 wt.%.
In one embodiment, the solvent for dispersing the graphene oxide in the graphene oxide slurry for coating is one or more of water, ethanol, methanol, N-dimethylformamide, N-methylpyrrolidone, toluene, xylene, ethyl acetate, and acetone.
In one embodiment, the thickness of the coating is 5-300 μm when the graphene oxide slurry is coated; preferably, the coating has a thickness of 50 to 200. mu.m, such as 50. mu.m, 55. mu.m, 60. mu.m, 65. mu.m, 70. mu.m, 75. mu.m, 80. mu.m, 85. mu.m, 90. mu.m, 95. mu.m, 100. mu.m, 110. mu.m, 120. mu.m, 130. mu.m, 140. mu.m, 150. mu.m, 160. mu.m, 170. mu.m, 180. mu.m, 190. mu.m or 200. mu.m.
In one embodiment, the coated graphene oxide slurry is dried at a temperature of 40-150 ℃.
In one embodiment, holes and/or grooves which do not penetrate through the surface layer of the dried graphene oxide slurry are arranged along the thickness direction of the graphene oxide film; the pores have a pore size of 10 to 40 μm, preferably 50 to 200 μm, such as 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm or 200 μm.
In one embodiment, the holes and/or grooves are disposed along the thickness direction of the graphene oxide film, and the holes have a hole pitch of 500 to 2000 μm, preferably 800 to 1200 μm, such as 800 μm, 900 μm, 1000 μm, 1100 μm or 1200 μm, and do not penetrate through the surface layer of the dried graphene oxide slurry.
In one embodiment, the graphene oxide film is provided with holes and/or grooves along the thickness direction thereof, which do not penetrate through the surface layer of the dried graphene oxide slurry, and the grooves are formed to have a length of 200 to 8000 μm, preferably 500 to 5000 μm, such as 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, 1000 μm, 1500 μm, 2000 μm, 2500 μm, 3000 μm, 3500 μm, 4000 μm, 4500 μm, or 5000 μm.
In one embodiment, the graphene oxide film is provided with holes and/or grooves along the thickness direction thereof, wherein the holes and/or grooves do not penetrate through the surface layer of the dried graphene oxide slurry, and the width of the grooves is 20-1000 μm, preferably 100-800 μm, such as 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, or 800 μm.
In one embodiment, holes and/or grooves which do not penetrate through the surface layer of the dried graphene oxide slurry are arranged along the thickness direction of the graphene oxide film, the groove pitch of the grooves is 500-2000 μm, and the groove pitch between the grooves is preferably 800-1000 μm, such as 800 μm, 850 μm, 900 μm, 950 μm or 1000 μm.
In one embodiment, the heat treatment temperature in step e is 2400 ℃ or higher, preferably 2800 ℃ or higher.
In one embodiment, the prepared graphene thermal conductive film contains multilayer graphene, and a pore structure is formed between two adjacent layers of graphene of the multilayer graphene, wherein the pore structure is a hole and/or a groove which does not penetrate through the graphene layers; meanwhile, through holes penetrating through the multiple graphene layers are formed among the multiple graphene layers.
In one embodiment, the thickness of the prepared graphene thermal conductive film is 10-200 μm, preferably 20-150 μm, such as 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm or 150 μm.
In one embodiment, the graphene layer in the graphene thermal conductive film has a thickness of 0.5-5 μm, preferably 1-3 μm, such as 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2.0 μm, 2.1 μm, 2.2 μm, 2.3 μm, 2.4 μm, 2.5 μm, 2.6 μm, 2.7 μm, 2.8 μm, 2.9 μm or 3.0 μm.
In one embodiment, the adhesive used in step f comprises one or more of epoxy resin, phenolic resin, furfural resin, polyurethane, acrylic resin and silicone; preferably, the adhesive is organic silica gel; more preferably, the adhesive is a liquid silicone; the liquid silicone gum includes one or more of polydimethylsiloxane, dimethyldiphenylpolysiloxane, alpha, omega-dihydroxypolydimethylsiloxane, alpha, omega-divinylpolydimethylsiloxane, and alpha, omega-dihydroxypolymethyl (3,3, 3-trifluoropropyl) siloxane.
In one embodiment, the graphene layers of the graphene thermal conductive film are impregnated with an adhesive.
In one embodiment, the curing in step h is usually a heating curing or a normal temperature curing, and the curing temperature is preferably below 150 ℃.
In one embodiment, the cutting direction in step i is cutting in the thickness direction of the stack; the cutting mode is not limited, and linear cutting, laser cutting, ultrasonic cutting, blade cutting or freezing cutting is preferably adopted; the sheet thickness is generally 0.1 to 5mm, preferably 0.25 to 2 mm.
The method is illustrated by the following specific examples.
In the following embodiments and comparative examples, liquid silica gel is used as an adhesive to prepare the heat-conducting gasket, in order to reflect the comparison effect, the thickness of slices of the following embodiments is 1mm, and the application thermal resistance and compression resilience of the slices are tested;
testing the thermal diffusion coefficient of the graphene film with reference to ASTM E1461; testing the specific heat capacity of the graphene film with reference to ASTM E1269-2018; testing the density of the graphene film according to GB 4472-1984; testing the thermal conductivity coefficient and the application thermal resistance (the sum of intrinsic thermal resistance and contact thermal resistance of the upper surface and the lower surface) of the thermal conductive gasket under the condition of 40psi by referring to ASTM D5470; the thermal gasket was tested for compression resilience under 50% strain for 30min according to ASTM D575. The heat conductivity coefficient calculation formula is as follows:
the thermal conductivity of the graphene with the laminated void structure is calculated by adopting a formula shown in a formula (1):
K＝λ·C p ·ρ (1)
in the formula (1), the reaction mixture is,
k-thermal conductivity, in W/(m.K);
lambda-thermal diffusion coefficient in mm 2 /s；
C p Specific heat capacity, in J/kg/K;
po-density in g/cm 3 。
The steps for preparing the graphene thermal conductive pad in examples 1 to 5 are the same, except that the graphene film thickness, the graphene layer thickness, the solvent in the graphene oxide slurry, the material of the substrate, the solid content of the graphene oxide slurry, and the drying surface layer of the coated graphene oxide slurry are provided with holes or grooves, the size of the holes and the size of the grooves, the hole pitch, the groove pitch, the drying temperature of the graphene oxide film, and the thermal treatment temperature, regardless of the holes or the grooves.
The steps for preparing the graphene thermal conductive film in each example and comparative example are as follows:
a. coating graphene oxide slurry on the surface of a base material;
b. waiting for the surface layer of the coated graphene oxide slurry to dry;
c. arranging holes and/or grooves which do not penetrate through the surface layer on the dried surface layer, and continuously coating graphene oxide slurry on the dried surface layer;
d. repeating the steps a to c, and drying all the graphene oxide slurry to obtain a graphene oxide film;
e. and carrying out heat treatment on the graphene oxide film to obtain the graphene heat-conducting film.
The steps for preparing the thermal conductive gasket according to the examples and the comparative examples are as follows:
f. dipping the graphene heat-conducting film in an adhesive;
g. stacking the impregnated graphene heat-conducting films layer by layer into a block;
h. solidifying the obtained block;
i. and cutting the block body along the stacking direction to obtain the heat-conducting gasket.
Example 1
In this embodiment, the thickness of the graphene thermal conductive film is 10 μm, the thickness of the graphene layer in the graphene thermal conductive film is 0.5 μm, the solvent in the graphene oxide slurry is water, the substrate is PET, the solid content of the graphene oxide slurry is 1 wt.%, non-penetrating grooves with a length of 500 μm and a width of 100 μm are arranged on the drying surface layer of the coated graphene oxide slurry, the groove pitch is 500 μm, the drying temperature for forming the graphene oxide film is normal temperature, and the temperature for performing thermal treatment on the graphene oxide film is 3000 ℃;
the liquid silica gel used by the heat-conducting gasket is polydimethylsiloxane, and the mass percentage of the graphene in the heat-conducting gasket is 75 wt.%.
Through testing, the performance of the graphene film is as follows:
thermal diffusivity: 493.13mm 2 /s；
Specific heat capacity: 0.71J/kg/K;
density: 0.34g/cm 3 ；
Coefficient of thermal conductivity: 119.04W/(m.K);
the performance of the obtained graphene heat-conducting gasket is as follows:
coefficient of thermal conductivity: 29.23W/(m.K);
application of thermal resistance: 0.303K cm 2 /W；
Compression ratio: 70.13 percent;
compression rebound resilience: 73.02 percent.
Example 2
In this embodiment, the thickness of the graphene thermal conductive film is 200 μm, the thickness of the graphene layer in the graphene thermal conductive film is 5 μm, the solvent in the graphene oxide slurry is ethanol, the base material is PP, the solid content of the graphene oxide slurry is 10 wt.%, non-penetrating grooves with a length of 8000 μm and a width of 800 μm are arranged on the drying surface layer of the coated graphene oxide slurry, the groove pitch is 1000 μm, the drying temperature for forming the graphene oxide film is normal temperature, and the temperature for performing thermal treatment on the graphene oxide film is 2500 ℃;
the liquid silica gel used by the heat-conducting stone gasket is polydimethylsiloxane, and the mass percentage of the graphene in the heat-conducting gasket is 25 wt.%;
through testing, the performance of the graphene film is as follows:
thermal diffusivity: 453.23mm 2 /s；
Specific heat capacity: 0.74J/kg/K;
density: 0.30g/cm 3 ；
Coefficient of thermal conductivity: 100.62W/(m.K);
the performance of the obtained graphene heat-conducting gasket is as follows:
coefficient of thermal conductivity: 25.23W/(m.K);
application of thermal resistance: 0.366K cm 2 /W；
Compression ratio: 82.50 percent;
compression rebound resilience: 83.22 percent.
Example 3
In this embodiment, the thickness of the graphene thermal conductive film is 20 μm, the thickness of the graphene layer in the graphene thermal conductive film is 1 μm, the solvent in the graphene oxide slurry is methanol, the base material is PE, the solid content of the graphene oxide slurry is 2 wt.%, non-penetrating holes with a diameter of 50 μm are formed in the drying surface layer of the coated graphene oxide slurry, the hole pitch is 800 μm, the drying temperature for forming the graphene oxide film is normal temperature, and the temperature for performing thermal treatment on the graphene oxide film is 2500 ℃;
liquid silica gel used by the heat-conducting gasket is dimethyl diphenyl polysiloxane, and the mass percentage of graphene in the heat-conducting gasket is 35 wt.%;
through testing, the performance of the graphene film is as follows:
thermal diffusivity: 589.47mm 2 /s；
Specific heat capacity: 0.72J/kg/K;
density: 0.31g/cm 3 ；
Coefficient of thermal conductivity: 131.56W/(m.K);
the performance of the obtained graphene heat-conducting gasket is as follows:
coefficient of thermal conductivity: 37.23W/(m.K);
application of thermal resistance: 0.291K cm 2 /W；
Compression ratio: 75.00 percent;
compression rebound resilience: 71.33 percent.
Example 4
In the embodiment, the thickness of a graphene heat-conducting film is 90 μm, the thickness of a graphene layer in the graphene heat-conducting film is 2 μm, a solvent in a graphene oxide slurry solvent is DMF, a base material is PVC, the solid content of the graphene oxide slurry is 5 wt.%, non-penetrating holes with the diameter of 120 μm are arranged on a drying surface layer of the coated graphene oxide slurry, the hole pitch is 1000 μm, the drying temperature for forming the graphene oxide film is 80 ℃, and the temperature for performing heat treatment on the graphene oxide film is 3100 ℃;
the liquid silica gel used by the heat-conducting gasket is alpha, omega-dihydroxy polydimethylsiloxane, and the mass percentage of the graphene in the heat-conducting gasket is 50 wt.%;
through testing, the performance of the graphene film is as follows:
thermal diffusivity: 747.22mm 2 /s；
Specific heat capacity: 0.71J/kg/K;
density: 0.32g/cm 3 ；
Coefficient of thermal conductivity: 169.77W/(m.K);
the performance of the obtained graphene heat-conducting gasket is as follows:
coefficient of thermal conductivity: 42.67W/(m.K);
application of thermal resistance: 0.251 K.cm 2 /W；
Compression ratio: 77.12 percent;
compression rebound resilience: 80.07 percent.
Example 5
In the embodiment, the thickness of the graphene heat-conducting film is 150 μm, the thickness of the graphene layer in the graphene heat-conducting film is 3 μm, the solvent in the graphene oxide slurry is toluene, the base material is PTFE, the solid content of the graphene oxide slurry is 8 wt.%, non-penetrating holes with the diameter of 200 μm are arranged on the drying surface layer of the coated graphene oxide slurry, the hole spacing is 1200 μm, the drying temperature for forming the graphene oxide film is 100 ℃, and the heat treatment temperature for the graphene oxide film is 3400 ℃;
the liquid silica gel used by the heat-conducting gasket is alpha, omega-divinyl polydimethylsiloxane, and the mass percentage of the graphene in the heat-conducting gasket is 65 wt.%;
through testing, the performance of the graphene film is as follows:
thermal diffusivity: 701.52mm 2 /s；
Specific heat capacity: 0.70J/kg/K;
density: 0.33g/cm 3 ；
Coefficient of thermal conductivity: 162.05W/(m.K);
the performance of the obtained graphene heat-conducting gasket is as follows:
coefficient of thermal conductivity: 40.13W/(m.K);
application of thermal resistance: 0.269K · cm 2 /W；
Compression ratio: 76.22 percent;
compression rebound resilience: 77.51 percent.
Comparative example 1
In the comparative example, the thickness of the graphene thermal conductive film is 90 μm, the thickness of the graphene layer in the graphene thermal conductive film is 2 μm, the solvent in the graphene oxide slurry is DMF, the substrate is PVC, the solid content of the graphite oxide slurry is 0.5 wt.%, non-penetrating holes with the diameter of 120 μm are arranged on the drying surface layer of the coated graphene oxide slurry, the hole pitch is 1000 μm, the drying temperature for forming the graphene oxide film is 80 ℃, and the temperature for performing thermal treatment on the graphene oxide film is 3100 ℃;
the liquid silica gel used by the heat-conducting gasket is alpha, omega-dihydroxy polydimethylsiloxane, and the mass percentage of the graphene in the heat-conducting gasket is 50 wt.%;
through testing, the performance of the graphene film is as follows:
thermal diffusivity: 372.15mm 2 /s；
Specific heat capacity: 0.71J/kg/K;
density: 0.28g/cm 3 ；
Coefficient of thermal conductivity: 73.98W/(m.K);
the performance of the obtained graphene heat-conducting gasket is as follows:
coefficient of thermal conductivity: 19.79W/(m.K);
application of thermal resistance: 0.375 K.cm 2 /W；
Compression ratio: 78.67 percent;
compression rebound resilience: 71.22 percent;
the solid content of the slurry is too low, the prepared graphene film is too thin and is easy to break in the stacking process, the directional arrangement in the prepared graphene heat-conducting gasket is unstable, and the heat-conducting coefficient is low.
Comparative example 2
In the comparative example, the thickness of the graphene heat-conducting film is 90 μm, the thickness of the graphene layer in the graphene heat-conducting film is 2 μm, the solvent in the graphene oxide slurry is DMF, the base material is PVC, the solid content of the graphene oxide slurry is 25 wt.%, non-penetrating holes with the diameter of 120 μm are arranged on the drying surface layer of the coated graphene oxide slurry, the hole pitch is 1000 μm, the drying temperature for forming the graphene oxide film is 80 ℃, and the temperature for performing heat treatment on the graphene oxide film is 3100 ℃;
the liquid silica gel used by the heat-conducting gasket is alpha, omega-dihydroxy polydimethylsiloxane, and the mass percentage of the graphene in the heat-conducting gasket is 50 wt.%;
through testing, the performance of the graphene film is as follows:
thermal diffusivity: 479.14mm 2 /s；
Specific heat capacity: 0.74J/kg/K;
density: 0.30g/cm 3 ；
Coefficient of thermal conductivity: 106.37W/(m.K);
the performance of the obtained graphene thermal conductive gasket is as follows:
coefficient of thermal conductivity: 25.31W/(m.K);
application of thermal resistance: 0.343K cm 2 /W；
Compression ratio: 75.67 percent.
Compression rebound resilience: 73.22 percent;
the solid content of the slurry is too high, the prepared graphene film is too thick, the layering effect is not obvious, the bonding effect with the adhesive in the prepared graphene heat-conducting gasket is not good, and the gasket is easy to crack.
Comparative example 3
In the comparative example, the thickness of the graphene heat-conducting film is 90 μm, the thickness of the graphene layer in the graphene heat-conducting film is 2 μm, the solvent in the graphene oxide slurry is DMF, the substrate is PVC, the solid content of the graphene oxide slurry is 5 wt.%, non-penetrating holes with the diameter of 120 μm are arranged on the drying surface layer of the coated graphene oxide slurry, the hole spacing is 1000 μm, the drying temperature for forming the graphene oxide film is 80 ℃, and the heat treatment temperature for the graphene oxide film is 3100 ℃;
the liquid silica gel used by the heat-conducting gasket is alpha, omega-dihydroxy polydimethylsiloxane, and the mass percentage of the graphene in the heat-conducting gasket is 10 wt.%;
through testing, the performance of the graphene film is as follows:
thermal diffusivity: 747.22mm 2 /s；
Specific heat capacity: 0.71J/kg/K;
density: 0.32g/cm 3 ；
Coefficient of thermal conductivity: 169.77W/(m.K);
the performance of the obtained graphene heat-conducting gasket is as follows:
coefficient of thermal conductivity: 12.36W/(m.K);
application of thermal resistance: 0.495K cm 2 /W；
Compression ratio: 88.33 percent;
compression rebound resilience: 81.34 percent;
the graphene is low in proportion, the adhesive is high in proportion, and the heat conducting performance of the gasket is poor.
Comparative example 4
In the comparative example, the thickness of the graphene heat-conducting film is 90 μm, the thickness of the graphene layer in the graphene heat-conducting film is 2 μm, the solvent in the graphene oxide slurry is DMF, the substrate is PVC, the solid content of the graphene oxide slurry is 5 wt.%, non-penetrating holes with the diameter of 120 μm are arranged on the drying surface layer of the coated graphene oxide slurry, the hole spacing is 1000 μm, the drying temperature for forming the graphene oxide film is 80 ℃, and the heat treatment temperature for the graphene oxide film is 3100 ℃;
the liquid silica gel used by the heat-conducting gasket is alpha, omega-dihydroxy polydimethylsiloxane, and the mass percentage of the graphene in the heat-conducting gasket is 90 wt.%;
through testing, the performance of the graphene film is as follows:
thermal diffusivity: 747.22mm 2 /s；
Specific heat capacity: 0.71J/kg/K;
density: 0.32g/cm 3 ；
Coefficient of thermal conductivity: 169.77W/(m.K);
the content of the adhesive is too low, and the graphene heat-conducting gasket is not shaped.
In the embodiment of the invention, the adopted liquid silica gel is taken as a representative of the adhesive, and other types of adhesives are also applicable.
According to the embodiment 4 and the comparative examples 3 and 4, it can be known that the higher the content of graphene in the gasket is, the better the thermal conductivity coefficient of the prepared graphene gasket is, but the content of graphene exceeds the preferable range, and the content of the adhesive is lower, so that the prepared graphene heat-conducting film reinforced heat-conducting gasket has insufficient internal bonding force, can cause cracking and delamination of a sample, even the sample is not formed, and has too high content of the adhesive, and can cause too poor performance of the prepared sample; according to the example 4, the comparative examples 1 and 2, the solid content of the slurry is too low, so that the graphene film is too thin, the prepared gasket is poor in directional arrangement, and the heat conduction effect is insufficient; the solid content is too high, the layering effect is not obvious, and the gasket is easy to crack. According to embodiments, the performance of the prepared graphene film and the graphene gasket enhanced therewith is optimal when various parameters satisfy the preferred ranges.
The graphene heat conduction membrane that has the layered structure of this application preparation is regarded as reinforcing material with the above-mentioned preparation to the heat conduction gasket, and its layered structure is convenient for impregnate between layer and bonds for cohesion between graphene heat conduction membrane and the base member material is better, has significantly reduced graphene heat conduction membrane reinforcing heat conduction gasket's easy fracture and the problem of layering in practical application.
Because can fully impregnate the binder between the graphite alkene heat conduction membrane, the structure is more compact, consequently the compressibility and the compression resilience performance of the heat conduction gasket that is prepared by the graphite alkene heat conduction membrane of this application preparation are good.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. A preparation method of a graphene heat conduction film is characterized by comprising the following steps:
a. coating graphene oxide slurry on the surface of a base material;
b. waiting for the surface layer of the coated graphene oxide slurry to be dried;
c. arranging holes and/or grooves which do not penetrate through the surface layer on the dried surface layer, and continuously coating graphene oxide slurry on the dried surface layer;
d. repeating the steps a to c, and drying all the graphene oxide slurry to obtain a graphene oxide film;
e. and carrying out heat treatment on the graphene oxide film to obtain the graphene heat-conducting film.
2. The method according to claim 1, wherein the substrate is made of one or more of polyethylene terephthalate, polypropylene, polyethylene, polyvinyl chloride, polytetrafluoroethylene, copper foil, aluminum film and glass.
3. The preparation method according to claim 1, wherein the solid content of the graphene oxide slurry is 1 wt.% to 10 wt.%; preferably, the solid content of the graphene oxide slurry is 2-8 wt.%;
the solvent in the graphene oxide slurry is one or more of water, ethanol, methanol, N, N-dimethylformamide, N-methylpyrrolidone, toluene, xylene, ethyl acetate and acetone;
the thickness of the coated graphene oxide slurry is 5-300 mu m; the thickness of the coated graphene oxide slurry is preferably 50 to 200 μm.
4. The preparation method according to claim 1, wherein the drying temperature of the graphene oxide slurry during drying is 40-150 ℃.
5. The production method according to claim 1, wherein in step c, holes and/or grooves that do not penetrate through the surface layer are provided in the thickness direction of the graphene oxide film; the aperture of the hole is 10-40 μm, preferably 50-200 μm; the hole pitch of the holes is 500-2000 mu m, and preferably 800-1200 mu m; the length of the groove is 200-8000 mu m, preferably 500-5000 mu m; the width of the groove is 20-1000 μm, and preferably 100-800 μm; the groove pitch between the grooves is 500 to 2000 μm, and preferably 800 to 1000 μm.
6. The method according to claim 1, wherein the heat treatment temperature in step e is 2400 ℃ or higher, preferably 2800 ℃ or higher.
7. A graphene thermal conduction film prepared by the preparation method of any one of claims 1 to 6, wherein the prepared graphene thermal conduction film contains multilayer graphene, and a pore structure is formed between every two adjacent layers of graphene of the multilayer graphene, and the pore structure is pores and/or grooves which do not penetrate through the graphene layers; meanwhile, at least one through hole penetrating through the multilayer graphene layers is formed in the multilayer graphene layers;
the thickness of the graphene heat conduction film is 10-200 mu m, and preferably the thickness of the graphene heat conduction film is 20-150 mu m; the thickness of the graphene layer is 0.5-5 mu m, and the thickness of the graphene layer is preferably 1-3 mu m.
8. A thermal conductive gasket prepared from the graphene thermal conductive film according to claim 7, comprising the following steps:
dipping the graphene heat-conducting film in an adhesive;
stacking the impregnated graphene heat-conducting films layer by layer into a block;
solidifying the obtained block;
and cutting the block body along the stacking direction to obtain the heat-conducting gasket.
9. The gasket of claim 8, wherein the adhesive comprises one or more of epoxy, phenolic, furfural, polyurethane, acrylic, and silicone; preferably, the adhesive is organic silica gel; more preferably, the adhesive is a liquid silicone; the liquid silicone gum includes one or more of polydimethylsiloxane, dimethyldiphenylpolysiloxane, alpha, omega-dihydroxypolydimethylsiloxane, alpha, omega-divinylpolydimethylsiloxane, and alpha, omega-dihydroxypolymethyl (3,3, 3-trifluoropropyl) siloxane.
10. The heat transfer gasket of claim 8, wherein the mass percent of graphene in the heat transfer gasket is 25-75 wt.%; preferably, the mass percentage of the graphene is 35-65 wt.%.
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| CN116715231B (en) * | 2023-04-26 | 2024-01-30 | 中国科学院国家空间科学中心 | A method of transferring graphene film to grid |
| CN118853100A (en) * | 2024-06-26 | 2024-10-29 | 广州巨湾技研有限公司 | Graphene composite thermal conductive film and preparation method thereof |
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