CN105482435B - Three-dimensional drape shape graphene radiating slurry, its preparation method and application - Google Patents

Abstract

The invention discloses a kind of three-dimensional drape shape graphene radiating slurry, its preparation method and application.The preparation method includes：Thin graphene is formed into porous graphene aggregation by solvent action, and drastically cooled after the heating, obtains three-dimensional drape shape graphene block；The three-dimensional drape shape graphene block is crushed, obtains three-dimensional drape shape graphene；The monomer of three-dimensional drape shape graphene and polymer and/or polymer is compound, form the radiating slurry.Present invention process is simple; it is easy to large-scale production; and; because employing three-dimensional drape shape graphene in gained three-dimensional drape shape graphene radiating slurry; the cooling surface area of composite is not only added, there can also be more thermal conducting paths in vertical direction so that radiating efficiency greatly improves; it can be widely applied to the product of the needs such as LED illumination, electric power, electronics, communication radiating.

Description

Three-dimensional wrinkled graphene heat dissipation slurry, its preparation method and application

technical field

The invention relates to a heat dissipation material and a preparation process thereof, in particular to a three-dimensional wrinkled graphene heat dissipation slurry and a preparation method thereof, belonging to the field of nanotechnology.

Background technique

With the trend of miniaturization and high integration of microelectronics technology, the operating frequency and power consumption of core devices such as chips and sensors have increased sharply, generating a lot of heat. In addition, the power of some power devices continues to increase, and the heat dissipation requirements for packaging are getting higher and higher. In the field of optoelectronic devices such as LEDs and lasers, poor heat conduction and heat dissipation will lead to an increase in the junction temperature of the device, thereby affecting efficiency and life. In consumer electronic products (batteries, mobile phones, etc.), due to the high energy storage and high calorific value of the product, if the heat cannot be transmitted out in time, the accumulation will cause local hot spots, resulting in unstable or even damaged product functions, which in turn will cause electronic products to fail. issues such as shortened lifespan. Engines, brake pads, and tires in the automotive and aerospace industries also have high requirements for heat conduction and heat dissipation.

Graphene, as an emerging two-dimensional carbon material, is expected to have important applications in heat dissipation due to its large specific surface area and excellent electrical, thermal and mechanical properties. However, although the existing graphene heat dissipation film has a thermal conductivity that is difficult for other metals to match in the horizontal direction, its thermal conductivity in the vertical direction is very low, generally only 5-20W/mK, and can even be regarded as an insulating material. hot material.

Contents of the invention

In view of the deficiencies in the prior art, the main purpose of the present invention is to provide a three-dimensional wrinkled graphene heat dissipation paste with good thermal conductivity in all directions and a preparation method thereof.

In order to realize the aforementioned object of the invention, the technical solutions adopted in the present invention include:

A preparation method for a three-dimensional wrinkled graphene heat dissipation slurry, comprising the steps of:

(1) Thin-layer graphene is formed into porous graphene aggregates through solvent action, and the temperature is dropped sharply after heating to obtain three-dimensional wrinkled graphene blocks;

(2) Pulverizing the three-dimensional wrinkled graphene block to obtain three-dimensional wrinkled graphene;

(3) Composite the three-dimensional wrinkled graphene with the polymer and/or the monomer of the polymer to form the heat dissipation paste.

Further, step (1) includes: heating the porous graphene aggregates to 50-500°C, and then rapidly transferring to an environment with a temperature of -200°C-0°C, and the cooling time is 5-60 s.

Further, the length and width of the three-dimensional wrinkled graphene are 0.01 μm-100 μm, the thickness is 1-100 layers, and the specific surface area is 100 m ² /g-900 m ² /g.

Further, the pulverization method used in step (2) may be selected from, but not limited to, any one of mechanical pulverization, jet pulverization, and ultrasonic pulverization.

Further, the step (3) includes: compounding the three-dimensional wrinkled graphene and the heat conduction additive with the polymer to form the heat dissipation paste.

Wherein, the polymer may be selected from but not limited to polyaniline, polypyrrole, polythiophene, epoxy resin, silicone rubber, polyethylene, polypropylene, polyvinyl chloride, high-density polyethylene, polyvinylidene fluoride, polytetrafluoroethylene Any of vinyl fluoride, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, phenolic resin, polymethyl methacrylate, polyamide, rubber resin, polyethylene glycol, polycarbonate, polyimide, nylon or a combination of two or more.

Wherein, the thermal conductivity additive can be selected from but not limited to 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.

Wherein, the graphite preferably adopts particles with a particle diameter of 10nm-1mm, the carbon nanotube preferably adopts a single-wall or multi-wall carbon tube with a length of 10nm-1cm, and other carbon materials, metal or non-metallic materials preferably adopt Particles with a particle size of 1 nm-1 mm.

Further, the three-dimensional wrinkled graphene heat dissipation slurry comprises 0.01-90 wt% matrix component and 0.01-90wt% filler component, the matrix component includes polymer, and the filler component includes three-dimensional wrinkled graphite alkene.

Further, the filler component also includes thermal conductivity additives.

The three-dimensional wrinkled graphene heat dissipation slurry prepared by any one of the aforementioned methods.

Application of any of the aforementioned three-dimensional wrinkled graphene heat dissipation pastes in the preparation of optical devices, electronic devices or optoelectronic devices.

For example, the three-dimensional wrinkled graphene heat dissipation paste can be applied to the heat dissipation of devices such as mobile phones, computers, light emitting diodes, and electronic device packaging materials.

Compared with the prior art, the advantages of the present invention include: by using three-dimensional wrinkled graphene as a component of the heat dissipation coating, due to the existence of wrinkles in the graphene material, not only the surface area of the composite material is increased, but the heat dissipation efficiency is also improved. It can also form more heat conduction paths in the vertical direction, so that the heat dissipation efficiency in the vertical direction is greatly improved, so that the three-dimensional wrinkled graphene heat dissipation coating can obtain a thermal conductivity in the vertical direction that is comparable to that in the horizontal direction. Direction of heat dissipation can solve the problem of heat dissipation in optical devices, electronic devices or optoelectronic devices, and has been widely used in the field of heat dissipation materials.

Description of drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only These are some embodiments described in the present invention. Those skilled in the art can also obtain other drawings based on these drawings without creative work.

Fig. 1 is the preparation process flowchart of a kind of three-dimensional wrinkled graphene heat dissipation slurry in a typical embodiment of the present invention;

Fig. 2 is the scanning electron micrograph of a kind of three-dimensional wrinkled graphene in embodiment 1;

3 is a heat dissipation curve of a three-dimensional wrinkled graphene heat dissipation paste in Example 1.

specific implementation plan

The technical solutions in the embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

Referring to Fig. 1, in a typical embodiment of the present invention, the preparation method of this three-dimensional wrinkled graphene heat dissipation slurry comprises: forming porous graphene aggregates with thin-layer graphene through the action of solvent, heating to high temperature, and then sharply Cool to form a wrinkled graphene block, and then obtain a three-dimensional wrinkled graphene powder by ball milling, pulverization, etc., and prepare by compounding the three-dimensional wrinkled graphene or the three-dimensional wrinkled graphene with other thermally conductive additive composite materials and polymer binders Thermal paste.

The technical solution of the present invention will be explained in more detail below in conjunction with the accompanying drawings and a preferred embodiment.

Embodiment 1 The preparation process of the three-dimensional wrinkled graphene heat dissipation slurry includes:

1) After heating 1 g of thin-layer graphene powder to 200°C, it is quickly put into liquid nitrogen to form graphene blocks, and jet crushed to form three-dimensional wrinkled graphene (see Figure 2 for its morphology), with a specific surface area of 400 ㎡/g, then added to 28 g polyurethane solution, mechanically stirred for 15 minutes, then added 5 g of phosphorus flake graphite and continued to mechanically stir for 45 minutes to obtain the heat dissipation slurry. The thermal conductivity of the obtained heat dissipation slurry in the vertical and horizontal directions Both are 45 W/(m K).

2) After heating 5 g of thin-layer graphene powder to 200 °C, quickly put it into liquid nitrogen to form a graphene block, jet mill to form the three-dimensional wrinkled graphene in Figure 2, and then add it to 60 g of epoxy resin, After mechanical stirring for 15 minutes, add 20 g of alumina, continue stirring for 45 minutes, add 60 g of curing agent and stir for 15 minutes to obtain a heat dissipation paste. Please refer to Figure 3 for the heat dissipation performance of the heat dissipation paste.

The process of the invention is simple and easy for large-scale production. The obtained three-dimensional wrinkled graphene heat dissipation paste has good heat dissipation effect and can be widely used in LED lighting, electric power, electronics, communication and other products requiring heat dissipation.

It should be noted that, in this article, without further restrictions, the elements defined by the statement "comprising a..." do not exclude the existence of additional of the same elements.

The foregoing is only a specific embodiment of the present invention. It should be pointed out that for those of ordinary skill in the art, some improvements and modifications can also be made without departing from the principle of the present invention. It should be regarded as the protection scope of the present invention.

Claims (12)

1. a kind of preparation method of three-dimensional drape shape graphene radiating slurry, it is characterised in that comprise the following steps：

（1）Thin graphene is formed into porous graphene aggregation by solvent action, then porous graphene aggregation is heated To 50~500 DEG C, then it is transferred quickly in the environment that temperature is -200 DEG C~0 DEG C, cool time is 5-60 s, is obtained three-dimensional Accordion graphene block；

（2）The three-dimensional drape shape graphene block is crushed, obtains three-dimensional drape shape graphene；

（3）The monomer of three-dimensional drape shape graphene and polymer and/or polymer is compound, form the radiating slurry.

2. the preparation method of three-dimensional drape shape graphene radiating slurry according to claim 1, it is characterised in that described three The length and width dimensions for tieing up accordion graphene are 0.01 μm~100 μm, and thickness is 1~100 layer, and specific surface area is 100 m²/g-900 m²/g。

3. the preparation method of three-dimensional drape shape graphene radiating slurry according to claim 1, it is characterised in that step （2）The breaking method of middle use includes any of mechanical crushing, air-flow crushing, Ultrasonic Pulverization.

4. the preparation method of three-dimensional drape shape graphene radiating slurry according to claim 1, it is characterised in that step （3）Including：Three-dimensional drape shape graphene and heat conduction additive are compounded to form the radiating slurry with polymer.

5. the preparation method of three-dimensional drape shape graphene radiating slurry according to claim 4, it is characterised in that described poly- Compound includes polyaniline, polypyrrole, polythiophene, epoxy resin, polyethylene, polypropylene, polyvinyl chloride, Kynoar, poly- four PVF, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, phenolic resin, polymethyl methacrylate, polyamide, rubber Any of resin, polyethylene glycol, makrolon, polyimides or two or more combinations.

6. the preparation method of three-dimensional drape shape graphene radiating slurry according to claim 4, it is characterised in that described to lead Hot additive include graphite, fullerene, carbon black, CNT, carbon fiber, boron nitride, aluminium nitride, carborundum, zinc, aluminium, copper, Any of silver, nickel, cadmium, iron, carbon steel, aluminum oxide, silicon, beryllium oxide, silicon nitride, magnesia or two or more combinations.

7. the preparation method of three-dimensional drape shape graphene radiating slurry according to claim 6, it is characterised in that the stone Ink uses particle of the particle diameter for 10nm-1mm, and the CNT uses single wall or more wall carbon pipe of the length for 10 nm-1cm, and Other carbon materials, metal or nonmetallic materials use particle of the particle diameter for 1 nm-1mm.

8. the preparation method of three-dimensional drape shape graphene radiating slurry according to claim 1, it is characterised in that described three Dimension accordion graphene radiating slurry includes 0.01-90 wt% matrix components and 0.01-90 wt% filler components, described matrix group Subpackage contains polymer, and the filler component includes three-dimensional drape shape graphene.

9. the three-dimensional drape shape graphene radiating slurry prepared using method any one of claim 1-8.

10. application of the three-dimensional drape shape graphene radiating slurry in optics is prepared described in claim 9.

11. application of the three-dimensional drape shape graphene radiating slurry in electronic device is prepared described in claim 9.

12. application of the three-dimensional drape shape graphene radiating slurry in photoelectric device is prepared described in claim 9.