CN116691084A - Graphene heat conduction film and preparation method thereof - Google Patents

Graphene heat conduction film and preparation method thereof Download PDF

Info

Publication number
CN116691084A
CN116691084A CN202310635127.XA CN202310635127A CN116691084A CN 116691084 A CN116691084 A CN 116691084A CN 202310635127 A CN202310635127 A CN 202310635127A CN 116691084 A CN116691084 A CN 116691084A
Authority
CN
China
Prior art keywords
graphene
parts
heat
agent
coupling agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310635127.XA
Other languages
Chinese (zh)
Inventor
吴兆启
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Liyue New Material Co ltd
Original Assignee
Shenzhen Liyue New Material Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen Liyue New Material Co ltd filed Critical Shenzhen Liyue New Material Co ltd
Priority to CN202310635127.XA priority Critical patent/CN116691084A/en
Publication of CN116691084A publication Critical patent/CN116691084A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K7/00—Constructional details common to different types of electric apparatus
    • H05K7/20—Modifications to facilitate cooling, ventilating, or heating
    • H05K7/2039—Modifications to facilitate cooling, ventilating, or heating characterised by the heat transfer by conduction from the heat generating element to a dissipating body
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/302—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a graphene heat conduction film and a preparation method thereof, wherein the graphene heat conduction film comprises the following raw materials in parts by weight: 25-40 parts of graphene; 13-20 parts of epoxy resin; 4-8 parts of glass fiber material; 1-3 parts of a dissolving agent; 10-17 parts of adhesive; 1-3 parts of a heat stabilizer; 0.5-2 parts of curing agent; 0.5-1 part of silane coupling agent; 17-24 parts of deionized water. According to the invention, graphene is taken as a raw material, and a proper amount of glass fiber material is added, so that the overall toughness of the graphene heat conduction film can be ensured while the dosage of graphene is reduced, and the production cost of the graphene heat conduction film is reduced. Proper amount of epoxy resin and heat stabilizer are added and matched with each other, so that the heat conducting performance of the graphene heat conducting film is improved, the graphene film formed by coating is subjected to multi-layer mutual bonding and calendaring through an adhesive to form the graphene heat conducting film, the structural strength and thickness of the product are improved, and the problems that the thickness of the existing graphene heat conducting film is thinner and the heat conductivity is not high are solved.

Description

Graphene heat conduction film and preparation method thereof
Technical Field
The invention relates to the technical field of heat conducting films, in particular to a graphene heat conducting film and a preparation method thereof.
Background
Graphene (Graphene) is a kind of Graphene which is formed by sp 2 The new material with the hybridized connection carbon atoms closely stacked into a single-layer two-dimensional honeycomb lattice structure has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materiality, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered as a revolutionary material in the future.
Meanwhile, graphene has very good heat conduction performance. The thermal conductivity of the pure defect-free single-layer graphene is as high as 5300W/mK, and the thermal conductivity of the pure defect-free single-layer graphene is the highest carbon material, which is higher than that of single-wall carbon nanotubes (3500W/mK) and multi-wall carbon nanotubes (3000W/mK). When it is used as carrier, the heat conductivity coefficient can be 600W/mK. In addition, the ballistic thermal conductivity of graphene can shift the lower limit of the ballistic thermal conductivity of carbon nanotubes per circumference and length downward.
Along with the heat generated by the light source, the battery and the like in the using process of electronic appliances such as mobile phones, computers and the like, the generated heat needs to be conducted rapidly in time to realize heat dissipation. If an effective heat dissipation is not achieved, the basic functions of functional components such as chips, light sources and batteries are permanently damaged. In the prior art, the heat dissipation parts of the electronic equipment are mostly realized by heat dissipation sheets of metal copper, metal aluminum, steel and the like, and the weight of the terminal product is increased due to inconvenient installation caused by large mass of metal materials.
Therefore, how to use graphene to prepare the heat conducting film becomes a technical problem of heat dissipation in electronic equipment at present, and the graphene heat conducting film obtained at present is thinner in thickness and low in heat conductivity, and cannot be suitable for use of terminal products.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a graphene heat conduction film and a preparation method thereof, wherein resin and glass fiber materials are adopted to strengthen the toughness of the graphene heat conduction film, and the graphene heat conduction film with multiple density layers is formed by coating, bonding and calendering the surface of a flexible substrate so as to solve the problems in the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the graphene heat conduction film comprises the following raw materials in parts by weight:
25-40 parts of graphene; 13-20 parts of epoxy resin; 4-8 parts of glass fiber material; 1-3 parts of a dissolving agent; 10-17 parts of adhesive; 1-3 parts of a heat stabilizer; 0.5-2 parts of curing agent; 0.5-1 part of silane coupling agent; 17-24 parts of deionized water.
As still further scheme of the invention, the graphene heat-conducting film comprises the following raw materials in parts by weight: 32 parts of graphene; 17 parts of epoxy resin; 6 parts of glass fiber material; 2 parts of a dissolving agent; 14 parts of adhesive; 2 parts of a heat stabilizer; 1.3 parts of curing agent; 0.8 parts of a coupling agent; and 20 parts of deionized water.
As a further scheme of the invention, the dissolving agent consists of one or more of 0.5-3mol/L hydrochloric acid, 0.5-3mol/L nitric acid, 0.5-3mol/L sulfuric acid and 0.5-3mol/L hydrofluoric acid according to any ratio.
As a further scheme of the invention, the adhesive is polyurethane adhesive.
As a further scheme of the invention, the heat stabilizer is any one of a copper salt stabilizer, a calcium-zinc composite stabilizer, cuprous iodide or hydrotalcite.
As a further scheme of the invention, the curing agent is any one of polyamide, dicyandiamide, tetrahydrophthalic anhydride and ammonium sulfate.
As a further scheme of the invention, the coupling agent is a silane coupling agent, wherein the silane coupling agent is one or more of gamma-aminopropyl triethoxysilane, KH-550 aminosilane coupling agent and KH-570 silane coupling agent.
A preparation method of a graphene heat conduction film comprises the following steps:
1) Weighing graphene, epoxy resin, glass fiber material, a dissolving agent, a viscose agent, a heat stabilizer, a curing agent, a coupling agent and deionized water according to parts by weight for standby;
2) Uniformly dispersing graphene, a dissolving agent and a coupling agent in deionized water to form uniform graphene slurry, and adding the graphene slurry and a glass fiber material into a high-speed mixer for primary mixing to obtain a graphene mixture;
3) Adding epoxy resin, a curing agent and a heat stabilizer into the graphene mixture, and performing ultrasonic treatment to uniformly disperse to form graphene gel;
4) Coating the graphene gel on the surface of a flexible substrate, wherein the coating thickness is 1-3mm, and vacuum drying to obtain a graphene film;
5) And coating the obtained at least two layers of graphene films with an adhesive in an inert atmosphere, placing the graphene films in an oven, and calendering for multiple times to form the graphene heat-conducting film.
As a further scheme of the invention, the flexible substrate is one of polypropylene, terylene and polypropylene; in the step 4), the coating speed of the graphene gel coated on the surface of the flexible substrate is 1-3m/min; the vacuum drying temperature is 70-95deg.C and the vacuum drying time is 25-30min.
As a further aspect of the present invention, in step 5) Wherein the inert atmosphere is one or more of argon, nitrogen, helium and hydrogen; carrying out multiple time delay, and carrying out calendaring for 2-10 times in a flat pressing mode of controlling the pressure to be 70-75MPa for 5min for one time in an inert atmosphere so as to compact the gas between the expanded graphene heat conducting films; and rolling under 30MPa until the density of the graphene heat-conducting film is 2.5g/cm 3 。
As a further scheme of the invention, in the step 5), when the graphene heat-conducting film is placed in an oven, the temperature in the oven is raised to 110 ℃, and the graphene heat-conducting film is formed by heat preservation and multiple calendaring.
Compared with the prior art, the invention has the beneficial effects that:
according to the graphene heat conduction film prepared by the method, graphene is used as a raw material, and a proper amount of glass fiber material is added, so that the overall toughness of the graphene heat conduction film can be ensured while the dosage of graphene is reduced, and the production cost of the graphene heat conduction film is reduced. Proper amount of epoxy resin and heat stabilizer are added and matched with each other, so that the heat conducting performance of the graphene heat conducting film is improved, the graphene film formed by coating is subjected to multi-layer mutual bonding and calendaring through an adhesive to form the graphene heat conducting film, the structural strength and thickness of the product are improved, and the problems that the thickness of the existing graphene heat conducting film is thinner and the heat conductivity is not high are solved.
In order to more clearly illustrate the structural features and efficacy of the present invention, the invention will be described in detail below with reference to specific examples.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the specific embodiments.
Example 1
The embodiment of the invention provides a graphene heat conduction film, which comprises the following raw materials in parts by weight:
25 parts of graphene; 13 parts of epoxy resin; 4 parts of glass fiber material; 1 part of a dissolving agent; 10 parts of adhesive; 1 part of a heat stabilizer; 0.5 part of curing agent; 0.5 parts of silane coupling agent; 17 parts of deionized water.
In this example, the dissolving agent is 3mol/L hydrochloric acid.
In this embodiment, the adhesive is a polyurethane adhesive; the heat stabilizer is a copper salt stabilizer; the curing agent is polyamide; the coupling agent is a silane coupling agent, wherein the silane coupling agent is gamma-aminopropyl triethoxysilane.
A preparation method of a graphene heat conduction film comprises the following steps:
1) Weighing graphene, epoxy resin, glass fiber material, a dissolving agent, a viscose agent, a heat stabilizer, a curing agent, a coupling agent and deionized water according to parts by weight for standby;
2) Uniformly dispersing graphene, a dissolving agent and a coupling agent in deionized water to form uniform graphene slurry, and adding the graphene slurry and a glass fiber material into a high-speed mixer for primary mixing to obtain a graphene mixture;
3) Adding epoxy resin, a curing agent and a heat stabilizer into the graphene mixture, and performing ultrasonic treatment to uniformly disperse to form graphene gel;
4) Coating the graphene gel on the surface of a flexible substrate, wherein the coating thickness is 1-3mm, the coating speed is 1-3m/min, and the graphene gel is dried in vacuum, wherein the temperature of the vacuum drying is 70-95 ℃ and the time is 25-30min, so that a graphene film is obtained;
5) And coating the obtained at least two layers of graphene films with an adhesive in an inert atmosphere, placing the graphene films in an oven, and calendering for multiple times to form the graphene heat-conducting film.
In this embodiment, the flexible substrate is polypropylene; the inert atmosphere is argon; carrying out multiple time delay, and carrying out calendaring for 5 times in a flat pressing mode that the pressure is controlled to be 70MPa for 5min for one time under inert atmosphere so as to compact gas between the expanded graphene heat conducting films; and rolling under 30MPa until the density of the graphene heat-conducting film is 2.5g/cm 3 。
In the step 5), when the graphene heat-conducting film is placed in an oven, the temperature in the oven is raised to 110 ℃, and the graphene heat-conducting film is formed by heat preservation and multiple calendaring.
Example 2
The embodiment of the invention provides a graphene heat conduction film, which comprises the following raw materials in parts by weight:
30 parts of graphene; 15 parts of epoxy resin; 5 parts of glass fiber material; 1.5 parts of a dissolving agent; 12 parts of adhesive; 1.2 parts of a heat stabilizer; 0.8 parts of curing agent; 0.6 parts of silane coupling agent; 19 parts of deionized water.
In this example, the dissolving agent was prepared from 2.4 mol/L hydrochloric acid, 2.4 mol/L nitric acid, and 2.4 mol/L hydrofluoric acid at a ratio of 1:1:1 ratio.
In this embodiment, the adhesive is a polyurethane adhesive; the heat stabilizer is a calcium-zinc composite stabilizer.
In this embodiment, the curing agent is dicyandiamide; the coupling agent is a silane coupling agent, wherein the silane coupling agent is KH-550 amino silane coupling agent.
A preparation method of a graphene heat conduction film comprises the following steps:
1) Weighing graphene, epoxy resin, glass fiber material, a dissolving agent, a viscose agent, a heat stabilizer, a curing agent, a coupling agent and deionized water according to parts by weight for standby;
2) Uniformly dispersing graphene, a dissolving agent and a coupling agent in deionized water to form uniform graphene slurry, and adding the graphene slurry and a glass fiber material into a high-speed mixer for primary mixing to obtain a graphene mixture;
3) Adding epoxy resin, a curing agent and a heat stabilizer into the graphene mixture, and performing ultrasonic treatment to uniformly disperse to form graphene gel;
4) Coating the graphene gel on the surface of a flexible substrate, wherein the coating thickness is 1-3mm, the coating speed is 1-3m/min, and the graphene gel is dried in vacuum, wherein the temperature of the vacuum drying is 70-95 ℃ and the time is 25-30min, so that a graphene film is obtained;
5) And coating the obtained at least two layers of graphene films with an adhesive in an inert atmosphere, placing the graphene films in an oven, and calendering for multiple times to form the graphene heat-conducting film.
In this embodiment, the flexible substrate is dacron; the idler is provided withThe air atmosphere is nitrogen; carrying out multiple time delay, and carrying out calendaring for 4 times in a flat pressing mode of controlling the pressure to be 72MPa for 5min for one time in an inert atmosphere so as to compact the gas between the expanded graphene heat conducting films; and rolling under 30MPa until the density of the graphene heat-conducting film is 2.5g/cm 3 。
In the step 5), when the graphene heat-conducting film is placed in an oven, the temperature in the oven is raised to 110 ℃, and the graphene heat-conducting film is formed by heat preservation and multiple calendaring.
Example 3
The embodiment of the invention provides a graphene heat conduction film, which comprises the following raw materials in parts by weight:
32 parts of graphene; 17 parts of epoxy resin; 6 parts of glass fiber material; 2 parts of a dissolving agent; 14 parts of adhesive; 2 parts of a heat stabilizer; 1.3 parts of curing agent; 0.8 parts of a coupling agent; and 20 parts of deionized water.
In this example, the dissolving agent is 3mol/L sulfuric acid.
In this embodiment, the adhesive is a polyurethane adhesive; the heat stabilizer is cuprous iodide.
In this embodiment, the curing agent is tetrahydrophthalic anhydride; the coupling agent is a silane coupling agent, wherein the silane coupling agent is KH-570 silane coupling agent.
A preparation method of a graphene heat conduction film comprises the following steps:
1) Weighing graphene, epoxy resin, glass fiber material, a dissolving agent, a viscose agent, a heat stabilizer, a curing agent, a coupling agent and deionized water according to parts by weight for standby;
2) Uniformly dispersing graphene, a dissolving agent and a coupling agent in deionized water to form uniform graphene slurry, and adding the graphene slurry and a glass fiber material into a high-speed mixer for primary mixing to obtain a graphene mixture;
3) Adding epoxy resin, a curing agent and a heat stabilizer into the graphene mixture, and performing ultrasonic treatment to uniformly disperse to form graphene gel;
4) Coating the graphene gel on the surface of a flexible substrate, wherein the coating thickness is 1-3mm, the coating speed is 1-3m/min, and the graphene gel is dried in vacuum, wherein the temperature of the vacuum drying is 70-95 ℃ and the time is 25-30min, so that a graphene film is obtained;
5) And coating the obtained at least two layers of graphene films with an adhesive in an inert atmosphere, placing the graphene films in an oven, and calendering for multiple times to form the graphene heat-conducting film.
In this embodiment, the flexible substrate is polypropylene; the inert atmosphere is helium; carrying out multiple time delay, and carrying out calendaring for 5 times in a flat pressing mode of controlling the pressure to be 75MPa for 5min for one time in an inert atmosphere so as to compact the gas between the expanded graphene heat conducting films; and rolling under 30MPa until the density of the graphene heat-conducting film is 2.5g/cm 3 。
In the step 5), when the graphene heat-conducting film is placed in an oven, the temperature in the oven is raised to 110 ℃, and the graphene heat-conducting film is formed by heat preservation and multiple calendaring.
Example 4
The embodiment of the invention provides a graphene heat conduction film, which comprises the following raw materials in parts by weight:
35 parts of graphene; 18 parts of epoxy resin; 7 parts of glass fiber material; 2.5 parts of a dissolving agent; 16 parts of adhesive; 2.5 parts of a heat stabilizer; 1.5 parts of curing agent; 0.8 parts of silane coupling agent; 22 parts of deionized water.
In this example, the dissolution agent was 2.5 mol/L hydrofluoric acid.
In this embodiment, the adhesive is a polyurethane adhesive; the heat stabilizer is hydrotalcite.
In this embodiment, the curing agent is ammonium sulfate; the coupling agent is a silane coupling agent, wherein the silane coupling agent is KH-550 amino silane coupling agent.
A preparation method of a graphene heat conduction film comprises the following steps:
1) Weighing graphene, epoxy resin, glass fiber material, a dissolving agent, a viscose agent, a heat stabilizer, a curing agent, a coupling agent and deionized water according to parts by weight for standby;
2) Uniformly dispersing graphene, a dissolving agent and a coupling agent in deionized water to form uniform graphene slurry, and adding the graphene slurry and a glass fiber material into a high-speed mixer for primary mixing to obtain a graphene mixture;
3) Adding epoxy resin, a curing agent and a heat stabilizer into the graphene mixture, and performing ultrasonic treatment to uniformly disperse to form graphene gel;
4) Coating the graphene gel on the surface of a flexible substrate, wherein the coating thickness is 1-3mm, the coating speed is 1-3m/min, and the graphene gel is dried in vacuum, wherein the temperature of the vacuum drying is 70-95 ℃ and the time is 25-30min, so that a graphene film is obtained;
5) And coating the obtained at least two layers of graphene films with an adhesive in an inert atmosphere, placing the graphene films in an oven, and calendering for multiple times to form the graphene heat-conducting film.
In this embodiment, the flexible substrate is dacron; the inert atmosphere is hydrogen; carrying out multiple time delay, and carrying out calendaring for 10 times in a flat pressing mode of controlling the pressure to be 70MPa for 5min for one time in an inert atmosphere so as to compact the gas between the expanded graphene heat conducting films; and rolling under 30MPa until the density of the graphene heat-conducting film is 2.5g/cm 3 。
In the step 5), when the graphene heat-conducting film is placed in an oven, the temperature in the oven is raised to 110 ℃, and the graphene heat-conducting film is formed by heat preservation and multiple calendaring.
Example 5
The embodiment of the invention provides a graphene heat conduction film, which comprises the following raw materials in parts by weight:
40 parts of graphene; 20 parts of epoxy resin; 8 parts of glass fiber material; 3 parts of a dissolving agent; 17 parts of adhesive; 3 parts of a heat stabilizer; 2 parts of curing agent; 1 part of a silane coupling agent; 24 parts of deionized water.
In this example, the dissolving agent consisted of 0.5 mol/L hydrochloric acid, 0.5 mol/L nitric acid, 0.5 mol/L sulfuric acid, 0.5 mol/L hydrofluoric acid in a 1:1:1 ratio.
In this embodiment, the adhesive is a polyurethane adhesive; the heat stabilizer is a calcium-zinc composite stabilizer.
In this embodiment, the curing agent is a polyamide; the coupling agent is a silane coupling agent, wherein the silane coupling agent is gamma-aminopropyl triethoxysilane.
A preparation method of a graphene heat conduction film comprises the following steps:
1) Weighing graphene, epoxy resin, glass fiber material, a dissolving agent, a viscose agent, a heat stabilizer, a curing agent, a coupling agent and deionized water according to parts by weight for standby;
2) Uniformly dispersing graphene, a dissolving agent and a coupling agent in deionized water to form uniform graphene slurry, and adding the graphene slurry and a glass fiber material into a high-speed mixer for primary mixing to obtain a graphene mixture;
3) Adding epoxy resin, a curing agent and a heat stabilizer into the graphene mixture, and performing ultrasonic treatment to uniformly disperse to form graphene gel;
4) Coating the graphene gel on the surface of a flexible substrate, wherein the coating thickness is 1-3mm, the coating speed is 1-3m/min, and the graphene gel is dried in vacuum, wherein the temperature of the vacuum drying is 70-95 ℃ and the time is 25-30min, so that a graphene film is obtained;
5) And coating the obtained at least two layers of graphene films with an adhesive in an inert atmosphere, placing the graphene films in an oven, and calendering for multiple times to form the graphene heat-conducting film.
In this embodiment, the flexible substrate is polypropylene; the inert atmosphere is argon; carrying out multiple time delay, and carrying out calendaring for 2 times in a flat pressing mode of controlling the pressure to be 75MPa for 5min for one time in an inert atmosphere so as to compact the gas between the expanded graphene heat conducting films; and rolling under 30MPa until the density of the graphene heat-conducting film is 2.5g/cm 3 。
In the step 5), when the graphene heat-conducting film is placed in an oven, the temperature in the oven is raised to 110 ℃, and the graphene heat-conducting film is formed by heat preservation and multiple calendaring.
And (3) effect verification:
the graphene heat-conducting films prepared in examples 1-5 were subjected to adhesion and heat conductivity coefficient tests, wherein the adhesion test is referred to GB/T9286-1998, the heat conductivity coefficient test is referred to GB/T22588-2008, and the graphene heat-conducting films sold in the market are used as a control group, and the detection results are as follows.
Table 1 graphene thermally conductive film test results
Wherein, the single thermal conductivity coefficient is W/(m.K); as can be seen from table 1, the graphene heat-conducting film prepared by the method has excellent adhesive force, reaching level 0; the heat conductivity coefficient is far higher than that of the graphene heat conducting film sold in the market.
From the results, the graphene heat-conducting film prepared by the method takes graphene as a raw material, and a proper amount of glass fiber material is added, so that the overall toughness of the graphene heat-conducting film can be ensured while the dosage of graphene is reduced, and the production cost of the graphene heat-conducting film is reduced. Proper amount of epoxy resin and heat stabilizer are added and matched with each other, so that the heat conducting performance of the graphene heat conducting film is improved, the graphene film formed by coating is subjected to multi-layer mutual bonding and calendaring through an adhesive to form the graphene heat conducting film, the structural strength and thickness of the product are improved, and the problems that the thickness of the existing graphene heat conducting film is thinner and the heat conductivity is not high are solved.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.

Claims (10)

1. The graphene heat conduction film is characterized by comprising the following raw materials in parts by weight:
25-40 parts of graphene; 13-20 parts of epoxy resin; 4-8 parts of glass fiber material; 1-3 parts of a dissolving agent; 10-17 parts of adhesive; 1-3 parts of a heat stabilizer; 0.5-2 parts of curing agent; 0.5-1 part of silane coupling agent; 17-24 parts of deionized water.
2. The graphene thermal conductive film according to claim 1, wherein the graphene thermal conductive film comprises the following raw materials in parts by weight: 32 parts of graphene; 17 parts of epoxy resin; 6 parts of glass fiber material; 2 parts of a dissolving agent; 14 parts of adhesive; 2 parts of a heat stabilizer; 1.3 parts of curing agent; 0.8 parts of a coupling agent; and 20 parts of deionized water.
3. The graphene heat-conducting film according to claim 1 or 2, wherein the dissolving agent is composed of one or more of 0.5-3mol/L hydrochloric acid, 0.5-3mol/L nitric acid, 0.5-3mol/L sulfuric acid, and 0.5-3mol/L hydrofluoric acid in an arbitrary ratio.
4. The graphene thermal film according to claim 1 or 2, wherein the adhesive is a polyurethane adhesive.
5. The graphene thermal conductive film according to claim 1 or 2, wherein the heat stabilizer is any one of a copper salt stabilizer, a calcium-zinc composite stabilizer, cuprous iodide, or hydrotalcite.
6. The graphene heat-conducting film according to claim 1 or 2, wherein the curing agent is any one of polyamide, dicyandiamide, tetrahydrophthalic anhydride, and ammonium sulfate.
7. The graphene heat-conducting film according to claim 1 or 2, wherein the coupling agent is a silane coupling agent, wherein the silane coupling agent is one or more of gamma-aminopropyl triethoxysilane, KH-550 aminosilane coupling agent, KH-570 silane coupling agent.
8. A method for preparing a graphene thermal conductive film according to any one of claims 1 to 7, comprising the steps of:
1) Weighing graphene, epoxy resin, glass fiber material, a dissolving agent, a viscose agent, a heat stabilizer, a curing agent, a coupling agent and deionized water according to parts by weight for standby;
2) Uniformly dispersing graphene, a dissolving agent and a coupling agent in deionized water to form uniform graphene slurry, and adding the graphene slurry and a glass fiber material into a high-speed mixer for primary mixing to obtain a graphene mixture;
3) Adding epoxy resin, a curing agent and a heat stabilizer into the graphene mixture, and performing ultrasonic treatment to uniformly disperse to form graphene gel;
4) Coating the graphene gel on the surface of a flexible substrate, wherein the coating thickness is 1-3mm, and vacuum drying to obtain a graphene film;
5) And coating the obtained at least two layers of graphene films with an adhesive in an inert atmosphere, placing the graphene films in an oven, and calendering for multiple times to form the graphene heat-conducting film.
9. The method for preparing a graphene heat-conducting film according to claim 8, wherein the flexible substrate is one of polypropylene, polyester and polypropylene; in the step 4), the coating speed of the graphene gel coated on the surface of the flexible substrate is 1-3m/min; the vacuum drying temperature is 70-95deg.C and the vacuum drying time is 25-30min.
10. The method of preparing a graphene thermal conductive film according to claim 8, wherein in step 5), the inert atmosphere is one or more of argon, nitrogen, helium, and hydrogen; carrying out multiple time delay, and carrying out calendaring for 2-10 times in a flat pressing mode of controlling the pressure to be 70-75MPa for 5min under inert atmosphere so as to compact the gas between the expanded graphene heat conducting films; and rolling under 30MPa until the density of the graphene heat-conducting film is 2.5g/cm 3 。
CN202310635127.XA 2023-05-31 2023-05-31 Graphene heat conduction film and preparation method thereof Pending CN116691084A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310635127.XA CN116691084A (en) 2023-05-31 2023-05-31 Graphene heat conduction film and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310635127.XA CN116691084A (en) 2023-05-31 2023-05-31 Graphene heat conduction film and preparation method thereof

Publications (1)

Publication Number Publication Date
CN116691084A true CN116691084A (en) 2023-09-05

Family

ID=87836687

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310635127.XA Pending CN116691084A (en) 2023-05-31 2023-05-31 Graphene heat conduction film and preparation method thereof

Country Status (1)

Country Link
CN (1) CN116691084A (en)

Similar Documents

Publication Publication Date Title
CN106853966B (en) Utilize the method for graphene doping polyamic acid resin preparation high thermal conductivity graphite film
Dong et al. A Stretchable Electromagnetic Interference Shielding Fabric with Dual‐Mode Passive Personal Thermal Management
Li et al. Highly oriented graphite aerogel fabricated by confined liquid-phase expansion for anisotropically thermally conductive epoxy composites
CN103922324A (en) Preparation method of graphite film with high heat conductivity
Wu et al. Design of interconnected carbon fiber thermal management composites with effective EMI shielding activity
CN110229361B (en) High-filling flexible boron nitride composite film material, high-filling flexible boron nitride copper-clad plate and preparation method thereof
CN102592749A (en) Method of surface self-assembly of graphene/polyimide transparent electric conduction film
CN110364738A (en) One type graphene anode composite collector and its preparation method and application
CN111471299B (en) Heat-conducting and insulating polyimide nano composite film and preparation method thereof
CN104057653A (en) Graphite membrane/metal composite cooling fin and preparation method thereof
CN111471300A (en) Heat-conducting polyimide insulating film and preparation method thereof
CN110845752B (en) Composite graphene heat-conducting film with bionic structure and preparation thereof
CN113421866B (en) Graphene cooling fin with three-dimensional structure and ultrahigh vertical heat conduction coefficient for semiconductor component and manufacturing method thereof
WO2020006719A1 (en) Aramid fiber electrode and preparation method therefor
CN110145728B (en) Enhanced heat dissipation composite structure and preparation method thereof
CN109763321B (en) Conductive graphene/silver composite aramid fiber tow and preparation method thereof
Xie et al. Boron nitride nanosheets modified with polydopamine and polyimide nanofibers as flexible thermal management materials
CN116691084A (en) Graphene heat conduction film and preparation method thereof
CN106219532A (en) A kind of nanometer carbon pipe array/graphite composite heat conduction film and preparation method thereof
KR101912878B1 (en) Manufacturing method of Heat conduction sheet for graphite using heat-emiting
CN110964219B (en) Nano cellulose membrane with high thermal conductivity and preparation method thereof
CN104804205A (en) Preparation method of polymer/carbon tube composite film material with anisotropy
EP4429424A1 (en) Carbon material and use thereof
CN111132513A (en) Preparation method of flexible graphene nano composite heat dissipation film
CN114133735A (en) graphene-PI film and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination