CN105176086A - Oriented graphene/polymer composite system, and preparation method and application thereof - Google Patents

Abstract

An oriented graphene/polymer composite system, its preparation method and its application. The composite system includes: an orientation network component comprising at least graphene, wherein at least part of the graphene is arranged in a set orientation; and a matrix component compounded with the orientation network component; and the composite system is at least in a set direction The thermal conductivity is higher than the thermal conductivity in other directions; the preparation method includes: carrying out orientation treatment on the orientation network component, so that at least part of the graphene is arranged according to the set orientation to form an orientation network, and taking at least The matrix component of the polymer is composited with the oriented network component to form the composite system. The composite system of the present invention has high thermal conductivity and high electrical conductivity, can efficiently transfer heat in the required direction during use, has the characteristics of simplicity and high efficiency, is suitable for large-scale production, and has wide applications in high-efficiency heat conduction and heat dissipation prospect.

Description

Oriented graphene/polymer composite system, its preparation method and application

technical field

The invention relates to a graphene/polymer composite system, in particular to an oriented graphene/polymer composite system with high thermal conductivity, its preparation method and application, and belongs to the field of nanomaterial technology.

Background technique

With the development of science and technology and industrial production, people put forward higher requirements on the thermal conductivity of materials. Especially in the field of electrical and electronics, with the high-density integration and volume reduction of electronic components and circuits, materials with higher thermal conductivity are required. Graphene, as the thinnest two-dimensional carbon material, has a stable structure, a large specific surface area and excellent electrical, thermal and mechanical properties. Especially its excellent thermal conductivity (5000W/mK), it has a wide application prospect in the field of thermal conductivity materials.

The traditional preparation method of graphene/polymer thermally conductive composites is usually to blend and disperse graphene and polymer to achieve thermal conductivity. Therefore, its thermal conductivity is overly dependent on the content and degree of dispersion of graphene. This method requires a large amount of graphene, but usually when the graphene content in the polymer reaches about 15wt.%, the composite material cannot be formed, and this preparation method has high cost, large amount of addition and cannot meet the requirements of thermal conductivity.

Contents of the invention

An object of the present invention is to provide an oriented graphene/polymer composite system with high thermal conductivity, thereby overcoming the deficiencies in the prior art.

Another object of the present invention is to provide a method for preparing the oriented graphene/polymer composite system with high thermal conductivity.

Another object of the present invention is to provide the application of the oriented graphene/polymer composite system with high thermal conductivity.

For realizing the above-mentioned purpose of the invention, the present invention adopts following technical scheme:

A kind of oriented graphene/polymer composite system, comprising:

An orientation network component comprising at least graphene, wherein at least part of the graphene is arranged in a set orientation to form an orientation network,

And, a matrix component composited with said orientation network component;

Moreover, the thermal conductivity of the oriented graphene/polymer composite system at least in a set direction is higher than that in other directions.

Further, the matrix component includes a polymer, a polymer monomer or a composite system of a polymer and a high thermal conductivity material, and the orientation network component includes graphene or a graphene-high thermal conductivity material composite system.

As one of the more preferred schemes, all the graphenes in the composite system are arranged in a set orientation.

Further, the composite system contains 0.01-90wt% matrix component and 0.01-90wt% oriented network component.

Preferably, the radial dimension of the graphene is 10nm-1mm, the thickness is 0.34nm-1mm, and the number of layers is 1-100.

Further, the graphene can at least be selected from any one or more of graphene oxide, redox graphene, expanded exfoliated graphene, liquid phase dissociated graphene, N-doped graphene, three-dimensional graphene , and not limited to this.

Further, the polymer can at least be selected from polyaniline, polypyrrole, polythiophene, epoxy resin, silicone rubber, polyethylene, polypropylene, polyvinyl chloride, high-density polyethylene, polyvinylidene fluoride, polytetrafluoroethylene Any one of vinyl, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, phenolic resin, polymethyl methacrylate, polyamide, rubber resin, polyethylene glycol, polycarbonate, polyimide, nylon or A combination of two or more, and not limited thereto.

Further, the high thermal conductivity material can be at least selected from graphite, fullerene, carbon black, carbon nanotube, carbon nanotube fiber, carbon fiber, boron nitride, aluminum nitride, silicon carbide, zinc, aluminum, copper, silver , nickel, cadmium, iron, carbon steel, aluminum oxide, silicon, beryllium oxide, silicon nitride, magnesium oxide, or any combination of two or more, without limitation.

Preferably, the size of the high thermal conductivity material is 1nm-1mm, for example, if graphite is selected, its particle size is 10nm-1mm, if single-walled or multi-walled carbon nanotubes are selected, its length is 10nm-1cm, if If other carbon materials, metal or non-metal particles are selected, the particle size is 1nm-1mm.

A preparation method of oriented graphene/polymer composite system, comprising:

providing an orientation network component comprising at least graphene, and making at least part of the graphene arranged in a set orientation to form an orientation network,

And, take at least the matrix component containing the polymer and the composite of the orientation network component to form the oriented graphene/polymer composite system, the thermal conduction of the oriented graphene/polymer composite system at least in the set direction The coefficient is higher than the thermal conductivity in other directions.

Further, the method of orientation treatment or the method of compounding the basic component and the orientation network component can be at least selected from ball milling, spin coating, solution blending, self-assembly, electrospinning, solution spinning, melting Any one or a combination of spinning, twin-screw extrusion, vacuum-assisted forming, vacuum filtration, and filtration methods, and is not limited thereto.

In one embodiment, the preparation method may further include: dispersing the orientation network component in a solvent, and then performing an orientation treatment, so that at least part of the graphene is arranged in a set orientation to form the orientation network component. network.

Further, the solvent can at least be selected from cyclohexane, acetone, acetonitrile, ethanol, water, N,N,-dimethylformamide, N-methylpyrrolidone, 1,2-dichloroethane, ether, Any one or more of tetrahydrofuran, chloroform, dichloromethane, toluene, xylene, and not limited thereto.

Application of any of the aforementioned oriented graphene/polymer composite systems in the preparation of thermally conductive materials.

Compared with the prior art, the advantages of the present invention include:

(1) The present invention forms an oriented network structure by orienting all or part of the graphene in the same direction, and composites the polymer or the polymer and the high thermal conductivity material with the oriented network structure by means of filling, etc., to form a graphene with high thermal conductivity and high electrical conductivity. A new type of heat-conducting composite system with characteristics, and the thermal conductivity of the composite system in at least one direction is higher than that in other directions, so when in use, heat can be efficiently transferred in the required direction, and it is efficient in heat conduction and heat dissipation It has broad application prospects.

(2) The preparation process of the oriented graphene/polymer composite system of the present invention has the characteristics of simplicity and high efficiency, and is suitable for large-scale production.

Description of drawings

Fig. 1 is a flow chart of the preparation process of an oriented graphene/polymer composite system in a typical embodiment of the present invention.

Fig. 2 is a SEM image of an oriented graphene/polymer composite system obtained in Example 2-1 of the present invention.

Figure 3 is the embodiment 1-1 (shown in S1-1), embodiment 1-2 (shown in S1-2), embodiment 2-1 (shown in S2-1) and embodiment 2-2 (shown in S2-1) of the present invention S2-2), embodiment 3-1 ((S3-1), embodiment 3-2 ((S3-2)) oriented graphene composite materials in the orientation direction and non-orientation direction The thermal conductivity diagram.

Detailed ways

In view of the many shortcomings of existing heat conduction products, such as the large amount of heat conduction filler added, but the heat conduction performance cannot meet the growing demand, the inventor of this case has provided a kind of oriented graphene/ A polymer composite system and a preparation method thereof. The composite system has high thermal conductivity and high electrical conductivity, and the thermal conductivity in at least one direction is higher than that in other directions, and the preparation method is simple and efficient.

Further, the oriented graphene/polymer composite system of the present invention mainly includes a matrix and an orientation network, wherein the matrix is mainly composed of polymer components, the orientation network is mainly formed by graphene, and the graphene contained in the network is based on All or part of the alignment in one direction.

As one of the more preferred embodiments, the oriented graphene/polymer composite system comprises 0.01-90wt% matrix component and 0.01-90wt% oriented network component.

Further, the orientation network component includes graphene or a composite system of graphene and high thermal conductivity materials.

Further, the matrix component includes a polymer or a polymer monomer or a composite system of a polymer and a high thermal conductivity material.

For example, in some embodiments:

The matrix component is a polymer or a polymer monomer, and the orientation network component (which can also be considered as a thermally conductive component, the same below) is graphene;

The matrix component is a polymer or a polymer monomer, and the orientation network component is a composite system of graphene and high thermal conductivity materials;

The matrix component is a composite system of polymer and high thermal conductivity material, and the orientation network component is graphene;

The matrix component is a composite system of polymer and high thermal conductivity material, and the orientation network component is a composite system of graphene and high thermal conductivity material.

The polymers, high thermal conductivity materials, graphene, etc. can be selected from but not limited to various materials mentioned above, and will not be repeated here.

Further, the preparation method of a kind of oriented graphene/polymer composite system of the present invention can comprise:

Taking the orientation network component containing at least graphene and performing orientation treatment, so that at least part of the graphene is arranged according to the set orientation to form an orientation network,

And, the matrix component containing at least polymer is combined with the oriented network component to form the oriented graphene/polymer composite system.

Referring to Figure 1, it is a typical preparation process of oriented graphene/polymer composite system.

Wherein, the manner of the orientation treatment can at least be selected from but not limited to ball milling, spin coating, solution blending, layer-by-layer self-assembly, electrospinning, solution spinning, melt spinning, twin-screw extrusion, vacuum assisted forming , vacuum filtration, filtration, etc. in one or several ways.

Wherein, the method of compounding the matrix component and the orientation network component, for example, the method of filling the orientation network with the matrix component can be selected from but not limited to melt processing, ball milling, solution blending, electrospinning, solution spinning Silk, melt spinning, soaking, twin-screw extrusion, vacuum-assisted molding, mill mixing, vacuum filtration, filtration, etc. one or more methods.

The oriented graphene/polymer composite system of the present invention can adopt methods known in the industry, for example, various methods such as electricity, chemistry or physics can be used to make thermally conductive films, thermally conductive pads, thermally conductive pastes, thermally conductive adhesives, thermally conductive resins, etc. , the shape can be film type, flat type, arc type, round tube type or other special shapes, etc., to meet various special requirements under different conditions of use, for example, it can be applied in computer chips, light-emitting diodes, device packaging, mobile phones, heat exchange Heat conduction and heat dissipation of devices such as devices.

Embodiment 1 Preparation of Oriented Graphene/Copper/Silicone Rubber High Thermal Conductivity Composite Material

1-1) Add 1g graphene and 0.5g copper powder to 250ml DMF, mix evenly at room temperature, let stand at room temperature for 48 hours, then let stand at 80°C for 24 hours, then add silicone rubber dropwise to saturation After curing at 80°C for 12 hours, a thermally conductive composite material can be obtained, which can be processed into a thermally conductive pad.

) Add 1g of graphene to 250ml of DMF, mix evenly at room temperature, let stand at room temperature for 48 hours, then let stand at 80°C for 24 hours, then add 20g of silicone rubber and 2g of aluminum powder, mix evenly at room temperature, mechanically stir After 15 minutes, silicone rubber was added dropwise and cured at 80°C for 12 hours at saturation to obtain a thermally conductive composite material. The compound is processed into a thermal pad.

Comparative Example 1-1 1g of graphene, 0.5g of copper powder and 10g of silicone rubber were mixed in 250ml of DMF and cured at 80°C for 12 hours to obtain a thermally conductive composite material with a thermal conductivity of 1.1W/mK.

Comparative Example 2-1 1g of graphene, 2g of aluminum powder and 10g of silicone rubber were stirred and mixed in 250ml of DMF, and cured at 80°C for 12 hours to obtain a thermally conductive composite material with a thermal conductivity of 1.6W/mK.

Embodiment 2 Preparation of Oriented Graphene/Epoxy Resin Thermally Conductive Composite Material

2-1) Add 1g of graphene to 250ml of NMP, mix evenly at room temperature, filter at room temperature, and then stand at 80°C for 24 hours to form an aligned graphene network. Add 25g of curing agent to 20g of epoxy resin and mechanically stir for 15 minutes, then let it stand in vacuum for 1 hour, then add it dropwise into the oriented graphene network, and cure it at 80°C for 24 hours when it is saturated, to obtain a thermally conductive composite material. It can be processed into thermal conductive resin.

) Add 1g of graphene to 250ml of NMP, mix evenly at room temperature, filter at room temperature, and then stand at 80°C for 24 hours to form an aligned graphene network. Take another 1g of graphite and add it to 20g of epoxy resin, stir mechanically for 15 minutes, add 25g of curing agent, continue to stir for 45 minutes, leave it in vacuum for 1 hour, then add it dropwise into the oriented graphene network, and solidify at 80°C when it is saturated After 24 hours, a heat-conducting composite material can be obtained, which can be processed into a heat-conducting resin.

Comparative Example 2-1 1g of graphene, 20g of epoxy resin and 25g of curing agent were mechanically stirred and mixed in 250ml of NMP, and cured at 80°C for 24 hours to obtain a thermally conductive composite material with a thermal conductivity of 0.5W/mK.

Comparative Example 2-2 1g of graphene, 1g of graphite, 20g of epoxy resin and 25g of curing agent were mechanically stirred and mixed in 250ml of DMF, and cured at 80°C for 24 hours to obtain a thermally conductive composite material with a thermal conductivity of 0.8W/mK.

Embodiment 3 Preparation of oriented graphene/magnesia/acrylic resin thermally conductive composite material

3-1) Add 1g of graphene to 100ml of acrylic acid, stir mechanically for 30 minutes, spin-coat at a speed of 2000rpm, and obtain a thermally conductive composite material after spin-coating for 10 minutes. The compound is processed into a thermally conductive adhesive.

) Add 1g of graphene and 0.5g of magnesium oxide into 100ml of acrylic acid, stir mechanically for 30 minutes, spin-coat at a speed of 2000rpm, and spin-coat for 10 minutes to obtain a thermally conductive composite material. The compound is processed into a thermally conductive adhesive.

It should be understood that the above descriptions, drawings and embodiments cannot be interpreted as limiting the design ideas of the present invention. Those who have the same knowledge in the field of knowledge of the present invention can improve the technical idea of the present invention in various forms, and such improvements and changes should also belong to the protection scope of the present invention.

Claims (10)

1. a composite system of oriented graphene/polymer, is characterized in that comprising: an orientation network component comprising at least graphene, wherein at least part of the graphene is arranged in a set orientation to form an orientation network, And, a matrix component composited with said orientation network component; Moreover, the thermal conductivity of the oriented graphene/polymer composite system at least in a set direction is higher than that in other directions. 2. oriented graphene/polymer composite system according to claim 1, is characterized in that described matrix component comprises polymer, polymer monomer or the composite system of polymer and high thermal conductivity material, and described oriented network group It contains graphene or graphene-high thermal conductivity material composite system. 3. The oriented graphene/polymer composite system according to any one of claims 1-2, characterized in that all the graphenes in the composite system are arranged according to the set orientation. 4. The oriented graphene/polymer composite system according to any one of claims 1-3, characterized in that the composite system comprises 0.01-90wt% matrix component and 0.01-90wt% oriented network component. 5. the oriented graphene/polymer composite system according to any one of claims 1-3, characterized in that the radial dimension of the graphene is 10nm-1mm, and the thickness is 0.34nm-1mm, and the Graphene is at least selected from any one of graphene oxide, redox graphene, expanded exfoliated graphene, liquid phase dissociated graphene, N-doped graphene, and three-dimensional graphene. 6. oriented graphene/polymer composite system according to claim 2, is characterized in that described polymer is at least selected from polyaniline, polypyrrole, polythiophene, epoxy resin, silicon rubber, polyethylene, polypropylene, Polyvinyl chloride, high-density polyethylene, polyvinylidene fluoride, polytetrafluoroethylene, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, phenolic resin, polymethyl methacrylate, polyamide, rubber resin, polyethylene glycol , polycarbonate, polyimide, nylon in any one or a combination of two or more. 7. Oriented graphene/polymer composite system according to claim 2, is characterized in that described high thermal conductivity material is at least selected from graphite, fullerene, carbon black, carbon nanotube, carbon nanotube fiber, carbon fiber, nitrogen Any one or both of boron nitride, aluminum nitride, silicon carbide, zinc, aluminum, copper, silver, nickel, cadmium, iron, carbon steel, aluminum oxide, silicon, beryllium oxide, silicon nitride, and magnesium oxide A combination of the above, and the size of the high thermal conductivity material is 1nm-1mm. 8. A preparation method for oriented graphene/polymer composite system, characterized in that it comprises: providing an orientation network component comprising at least graphene, and making at least part of the graphene arranged in a set orientation to form an orientation network, And, take at least the matrix component containing the polymer and the composite of the orientation network component to form the oriented graphene/polymer composite system, the thermal conduction of the oriented graphene/polymer composite system at least in the set direction The coefficient is higher than the thermal conductivity in other directions; Wherein, the way of the orientation treatment or the way of compounding the matrix component and the orientation network component is at least selected from ball milling, spin coating, solution blending, self-assembly, electrospinning, solution spinning, melt spinning , twin-screw extrusion, vacuum-assisted molding, vacuum filtration, any of the filtration methods. 9. according to the preparation method of the described orientation graphene/polymer composite system of claim 8, it is characterized in that comprising: described orientation network component is dispersed in solvent, then carries out orientation treatment, makes wherein at least part graphene Arranging according to a set orientation to form the orientation network; Wherein, the solvent is at least selected from cyclohexane, acetone, acetonitrile, ethanol, water, N,N,-dimethylformamide, N-methylpyrrolidone, 1,2-dichloroethane, ether, tetrahydrofuran, Any of chloroform, dichloromethane, toluene, and xylene. 10. The application of the oriented graphene/polymer composite system described in any one of claims 1-9 in the preparation of thermally conductive materials.