CN115029110A - Graphene composite heat-conducting film and preparation method thereof - Google Patents
Graphene composite heat-conducting film and preparation method thereof Download PDFInfo
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- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
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- H01L23/3738—Semiconductor materials
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Abstract
The invention relates to a preparation method of a graphene composite heat-conducting film, which comprises the following steps: mixing graphene and carbon fiber prepared by a physical stripping method with an organic solvent to prepare a graphene-carbon fiber mixed dispersion liquid; placing the graphene carbon fiber mixed dispersion liquid in a magnetic field, carrying out orientation treatment in the horizontal direction, and removing the organic solvent to prepare a graphene carbon fiber composite film; and clamping the graphene carbon fiber composite film between templates with smooth mirror surfaces for vacuum pressing to prepare the graphene carbon fiber composite film. According to the preparation method, the graphene prepared by a physical stripping method is used as a raw material, and the carbon fiber and the magnetic field are matched, so that the prepared graphene composite heat-conducting film has high heat-conducting coefficients in the horizontal direction and the vertical direction.
Description
Technical Field
The invention relates to the technical field of functional thin film materials, in particular to a graphene composite heat-conducting film and a preparation method thereof.
Background
With the development of mobile phones towards high performance and miniaturization, the heat productivity of chips is larger and is limited by narrow space, and heat is easy to gather to form hot spots, so that the chips cannot normally work, and therefore materials with higher transverse heat conductivity need to be adopted for carrying out uniform heating. For 4G mobile phones, the material is usually an artificial graphite heat dissipation film, which is prepared from a polyimide film as a raw material through carbonization, graphitization and calendaring processes. The artificial graphite heat dissipation film is limited by polyimide film raw materials, has limited thickness (less than 100 micrometers), and cannot cope with higher heat productivity of a 5G mobile phone chip. The graphene heat dissipation film can break through the limitation of thickness and meet the requirement of even heating of a 5G mobile phone chip, so that the graphene heat dissipation film is widely applied.
The graphene heat-conducting film is prepared by adopting the processes of pulping, coating, carbonizing, graphitizing and rolling. Due to the fact that the graphene oxide slurry contains rich oxygen-containing functional groups, the graphene oxide is easy to disperse in water, and stable high-solid-content slurry is obtained. In the slurry coating process, the graphene oxide is self-assembled into oriented arrangement through the hydrogen bond between sheets and the van der waals force action. At a higher temperature, the graphene oxide is reduced to graphene, and then the graphene oxide is graphitized to repair crystal lattices and is calendered to improve the density, so that the graphene heat-conducting film with oriented graphene arrangement is finally obtained.
Graphene is a thermally conductive anisotropic material that has ultra-high thermal conductivity (theoretically up to 5300 watts/m · degree) in the two-dimensional planar direction, but has low thermal conductivity, below 20 watts/m · degree, in the direction perpendicular to the two-dimensional planar direction. Therefore, the traditional graphene heat-conducting film with graphene in oriented arrangement has very high plane heat conductivity, but the heat conductivity in the vertical direction is very low, which results in that the heat-conducting capacity of the graphene heat-conducting film cannot be fully exerted.
Disclosure of Invention
Based on the above, one of the purposes of the present invention is to provide a preparation method of a graphene composite thermal conductive film having high thermal conductivity in both horizontal and vertical directions.
The preparation method of the graphene composite heat conduction film provided by the embodiment of the invention comprises the following steps:
mixing graphene and carbon fiber prepared by a physical stripping method with an organic solvent to prepare a graphene-carbon fiber mixed dispersion liquid;
placing the graphene carbon fiber mixed dispersion liquid in a magnetic field, performing orientation treatment in the horizontal direction, and removing the organic solvent to prepare a graphene carbon fiber composite film;
and clamping the graphene carbon fiber composite film between templates with smooth mirror surfaces for vacuum pressing to prepare the graphene composite heat-conducting film.
In one embodiment, the graphene prepared by the physical stripping method is a lamellar structure graphene with 5-20 layers obtained by physically stripping natural graphite or expanded graphite; and/or the sheet diameter of the graphene prepared by the physical stripping method is more than or equal to 10 microns.
In one embodiment, the physical stripping process comprises at least one of ultrasound, microwave, and sanding.
In one embodiment, the carbon fiber has a diameter of 7 to 10 micrometers and a length of 50 to 300 micrometers; and/or the mass ratio of the graphene prepared by the physical stripping method to the carbon fiber is (10-20): 1.
in one embodiment, the organic solvent comprises one or more of ethanol, diethyl ether, isopropanol, and acetone; and/or the solid content of the graphene carbon fiber mixed dispersion liquid is 0.5 wt% -2 wt%.
In one embodiment, the strength of the magnetic field is 5-20 tesla; and/or in a magnetic field, the liquid level height of the graphene carbon fiber mixed dispersion liquid is 1.5-10 cm.
In one embodiment, the vacuum pressing pressure is 20 tons to 1000 tons for 2 minutes to 30 minutes.
In one embodiment, the magnetic field is applied by a magnetic field orienting device, and the magnetic field orienting device comprises a power supply (1), two coils (2) and (3) which are connected with the power supply and distributed at intervals, an electric heating plate (4) positioned between the two coils (2) and (3), and a mold (5) placed on the electric heating plate (4); the two coils (2) and (3) have the same radius and are arranged oppositely; the central connecting line of the two coils (2) and (3) is superposed with the central axis of the mould (5); and during pressing, the graphene carbon fiber composite film and the template are placed in a forming groove of the mold (5).
The invention further provides a graphene composite heat-conducting film, which is prepared by adopting the preparation method of the graphene composite heat-conducting film.
In one embodiment, the thickness of the graphene composite heat conduction film is 60-300 microns; and/or the planar thermal conductivity of the graphene composite thermal conductive film is more than or equal to 1350W/m.degree; and/or the vertical thermal conductivity of the graphene composite heat-conducting film is more than or equal to 25W/m.degree.
Compared with the prior art, the invention has the following advantages and beneficial effects:
according to the preparation method of the graphene composite heat-conducting film, graphene is used as a raw material by a physical stripping method, and carbon fibers and a magnetic field are matched, so that the graphene and the carbon fibers are high in horizontal orientation degree and high in density, the carbon fibers are located between graphene sheet layers and can play a role in heat conduction bridging, and the prepared graphene composite heat-conducting film has high heat conductivity in the horizontal direction and the vertical direction.
Drawings
FIG. 1 is a schematic view of a magnetic field orienting device;
reference numerals:
1: a power source; 2 and 3: a coil; 4: an electric hot plate; 5: and (5) a mould.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. The following is a description of the preferred embodiments of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Reference herein to numerical intervals is deemed to be continuous, unless otherwise stated, and includes both the minimum and maximum values of that range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
The temperature parameter herein is not particularly limited, and is allowed to be either constant temperature treatment or treatment within a certain temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
An embodiment provides a preparation method of a graphene composite heat-conducting film, which comprises the following steps:
s110: mixing the graphene and the carbon fiber prepared by the physical stripping method with an organic solvent to prepare the graphene-carbon fiber mixed dispersion liquid.
In one embodiment, the graphene prepared by the physical exfoliation method is a lamellar graphene with 5-20 layers obtained by physically exfoliating natural graphite or expanded graphite. In some specific examples, the lamellar structure graphene may be obtained with 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 layers, preferably, the number of graphene layers is between 7 and 15, and more preferably, between 9 and 11.
In one example, the sheet size of the graphene prepared by the physical stripping method is greater than or equal to 10 microns, such as greater than or equal to 12 microns, greater than or equal to 15 microns, greater than or equal to 18 microns, or greater than or equal to 20 microns, and preferably, the sheet size of the graphene is not greater than 100 microns.
In one example, the graphene prepared by the physical stripping method does not contain a heteroatom.
The heteroatom is one or more of oxygen atom, nitrogen atom and hydrogen atom. In one example, the physical stripping method includes at least one of ultrasound, microwave, and sanding.
In one example, the carbon fibers have a diameter of 7 to 10 micrometers. Specifically, the diameter of the above carbon fiber may be 7 micrometers, 8 micrometers, 9 micrometers, or 10 micrometers.
In one example, the carbon fibers have a length of 50 to 300 micrometers. Specifically, the carbon fibers may have a length of 50 micrometers, 60 micrometers, 70 micrometers, 80 micrometers, 90 micrometers, 100 micrometers, 120 micrometers, 140 micrometers, 160 micrometers, 180 micrometers, 200 micrometers, 220 micrometers, 240 micrometers, 260 micrometers, 280 micrometers, or 300 micrometers.
In one example, the mass ratio of the graphene prepared by the physical stripping method to the carbon fiber is (10-20): 1. specifically, the mass ratio of the graphene prepared by the physical stripping method to the carbon fiber may be 10: 1. 11: 1. 12: 1. 13: 1. 14: 1. 15: 1. 16: 1. 17: 1. 18: 1. 19: 1 or 20: 1.
in one example, the organic solvent includes one or more of ethanol, diethyl ether, isopropanol, and acetone.
In one example, the graphene carbon fiber mixed dispersion has a solid content of 0.5 wt% to 2 wt%. Specifically, the solid content of the graphene carbon fiber mixed dispersion may be 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, or 2 wt%, and preferably, the solid content of the graphene carbon fiber mixed dispersion is between 1 wt% and 1.5 wt%.
S120: placing the graphene carbon fiber mixed dispersion liquid in a magnetic field, carrying out orientation treatment in the horizontal direction, and removing the organic solvent to prepare a graphene carbon fiber composite film;
in one example, the strength of the magnetic field is 5 tesla to 20 tesla, and specifically, the strength of the magnetic field may be 5 tesla, 6 tesla, 7 tesla, 8 tesla, 9 tesla, 10 tesla, 11 tesla, 12 tesla, 13 tesla, 14 tesla, 15 tesla, 16 tesla, 17 tesla, 18 tesla, 19 tesla, or 20 tesla, and preferably, the strength of the magnetic field is between 10 tesla to 15 tesla.
In one example, the liquid level height of the graphene-carbon fiber mixed dispersion in the magnetic field is 1.5 cm to 10 cm, and specifically, the liquid level height may be 1.5 cm, 2.5 cm, 3.5 cm, 4.5 cm, 5.5 cm, 6.5 cm, 7.5 cm, 8.5 cm, 9 cm, or 10 cm.
In one example, the vacuum pressing is performed at a pressure of 20 tons to 1000 tons for 2 minutes to 30 minutes. Specifically, the pressure of the above vacuum pressing may be 20 tons, 50 tons, 100 tons, 150 tons, 200 tons, 300 tons, 400 tons, 500 tons, 600 tons, 700 tons, 800 tons, 900 tons, or 1000 tons, and the time may be 30 minutes, 25 minutes, 20 minutes, 15 minutes, 10 minutes, 5 minutes, or 2 minutes.
In one example, the magnetic field is applied by a magnetic field orienting device, which comprises a power supply 1, two coils 2 and 3 connected with the power supply and distributed at intervals, an electric heating plate 4 positioned between the two coils 2 and 3, and a mold 5 placed on the electric heating plate 4; the two coils 2 and 3 have the same radius and are arranged oppositely; the central connecting line of the two coils 2 and 3 is superposed with the central axis of the mould 5.
In one example, the two sides of the electric heating plate 4 are provided with fixing brackets, and the fixing brackets are provided with fixing grooves which are electrically connected with a power supply.
In one example, when the two coils 2 and 3 are energized, a magnetic field is formed along the direction of the line connecting the centers of the two coils, and the magnetic field passes through a mold 5 which is arranged on an electric hot plate 4 and is provided with a graphene carbon fiber mixed dispersion liquid.
In one example, under the action of a magnetic field, the graphene is arranged along the direction of the magnetic field, i.e. in the horizontal direction.
In one example, when the electric heating plate is electrified and heated, and the solvent is volatilized, the graphene carbon fiber composite film in the horizontal orientation arrangement is obtained. The graphene-carbon fiber composite film is fluffy because of the existence of vacancies inside the graphene-carbon fiber composite film, which are left after a large amount of solvent is volatilized.
In one example, the mold 5 is made of stainless steel and has a molding groove, and the surface of the molding groove is plated with fluorine.
In one example, the depth of the molding groove is set according to a target thickness of the prepared graphene thermal conductive film.
In one example, the forming groove has a depth of 1.5 cm to 10 cm.
S130: and (3) clamping the graphene carbon fiber composite film between templates with smooth mirror surfaces, and performing vacuum pressing to prepare the graphene carbon fiber composite film.
In one example, the graphene carbon fiber composite film and the template are placed in a forming groove of the mold 5 during pressing.
In one example, the graphene carbon fiber composite film has a density of 1.8 g/cc to 2 g/cc after vacuum pressing. Because of high degree of horizontal orientation and high density of graphene, the prepared graphene composite heat-conducting film has very high heat conductivity in the horizontal direction, and the carbon fibers are positioned between the graphene sheet layers and can play a role in heat conduction bridging, and the prepared graphene composite heat-conducting film has higher heat conductivity coefficients in the horizontal direction and the vertical direction.
In one example, the preparation method of the graphene thermal conductive film comprises the following steps:
1. mixing the laminated graphene with 5-20 layers, sheet diameter larger than or equal to 10 microns, carbon fiber with diameter of 7-10 microns and length of 50-300 microns, which are prepared by a physical stripping method, with one or more organic solvents of ethanol, ether, isopropanol and acetone, and performing ultrasonic treatment to obtain graphene carbon fiber mixed dispersion liquid;
the graphene prepared by the physical stripping method is obtained by subjecting natural graphite or expanded graphite to ultrasonic treatment, microwave treatment or sanding.
The mass ratio of the graphene to the carbon fiber prepared by the physical stripping method is (10-20): 1.
the solid content of the graphene carbon fiber mixed dispersion liquid is 0.5-2 wt%.
2. Transferring the graphene carbon fiber mixed dispersion liquid into a magnetic field orientation device, wherein the liquid level height is 1.5-10 cm, carrying out orientation treatment in the horizontal direction, enabling graphene to be arranged in an oriented manner along the horizontal direction under the action of a magnetic field with the strength of 5-20 Tesla, and heating to completely volatilize a solvent, thereby obtaining the graphene carbon fiber composite film.
The magnetic field is applied by a magnetic field orientation device shown in fig. 1, which comprises a power supply 1, two coils 2 and 3 connected with the power supply and distributed at intervals, an electric heating plate 4 positioned between the two coils 2 and 3, and a mold 5 placed on the electric heating plate 4; the two coils 2 and 3 have the same radius and are arranged oppositely; the central connecting line of the two coils 2 and 3 is superposed with the central axis of the mould 5. After the two coils 2 and 3 are electrified, a magnetic field is formed along the central connecting line direction of the two coils, and the magnetic field passes through a die 5 which is positioned on an electric hot plate 4 and is provided with the graphene carbon fiber mixed dispersion liquid. The two sides of the electric heating plate 4 are provided with fixing supports, fixing grooves are arranged on the fixing supports, and the fixing grooves are electrically connected with a power supply. The die 5 is made of stainless steel and is provided with a forming groove, and the surface of the forming groove is plated with fluorine. The depth of the forming groove is 1.5 cm-10 cm.
3. And clamping the graphene carbon fiber composite film between templates with smooth mirror surfaces, stacking the templates in a mold 5, and performing vacuum pressing for 2 to 30 minutes under the pressure of 20 to 1000 tons through a vacuum flat press to obtain the graphene carbon fiber composite film.
An embodiment also provides a graphene composite heat conduction film prepared by the preparation method of the graphene composite heat conduction film.
In one example, the thickness of the graphene composite heat conduction film is 60-300 micrometers.
In one example, the density of the graphene composite heat conduction film is 1.8 g/cc to 2 g/cc.
In one example, the planar thermal conductivity of the graphene composite thermal conductive film is more than or equal to 1350W/m.degree.
In one example, the vertical thermal conductivity of the graphene composite thermal conductive film is more than or equal to 25W/m.degree.
According to the preparation method of the graphene composite heat-conducting film, graphene is used as a raw material by a physical stripping method, and carbon fibers and a magnetic field are matched, so that the graphene and the carbon fibers are high in horizontal orientation degree and high in density, the carbon fibers are located between graphene sheet layers and can play a role in heat conduction bridging, and the prepared graphene composite heat-conducting film has high heat conductivity in the horizontal direction and the vertical direction.
The following are specific examples.
Example 1: preparation of graphene composite heat-conducting film
The preparation method of the graphene composite heat-conducting film comprises the following steps:
1. mixing 5 layers of lamellar graphene with the sheet diameter of 10 microns, carbon fibers with the diameter of 7 microns and the length of 50 microns, which are prepared by a physical stripping method, with ethanol, and performing ultrasonic treatment to obtain a graphene-carbon fiber mixed dispersion liquid with the solid content of 2 wt%;
the graphene prepared by the physical stripping method is obtained by performing ultrasonic treatment on natural graphite or expanded graphite.
The mass ratio of the graphene prepared by the physical stripping method to the carbon fiber is 20: 1.
2. and transferring the graphene carbon fiber mixed dispersion liquid into a magnetic field orientation device, wherein the height of the liquid level is 1.5 cm, enabling graphene and carbon fibers to be oriented and arranged along the horizontal direction under the action of a magnetic field with the strength of 5 Tesla, and heating to completely volatilize the solvent to obtain the graphene carbon fiber composite film.
The magnetic field is applied by a magnetic field orienting device shown in fig. 1, which comprises a power supply 1, two coils 2 and 3 connected with the power supply and distributed at intervals, an electric heating plate 4 positioned between the two coils 2 and 3, and a mold 5 placed on the electric heating plate 4; the two coils 2 and 3 have the same radius and are arranged oppositely; the central connecting line of the two coils 2 and 3 is superposed with the central axis of the mould 5. After the two coils 2 and 3 are electrified, a magnetic field is formed along the central connecting line direction of the two coils, and the magnetic field passes through a die 5 which is positioned on an electric hot plate 4 and is provided with the graphene carbon fiber mixed dispersion liquid. The two sides of the electric heating plate 4 are provided with fixing supports, fixing grooves are arranged on the fixing supports, and the fixing grooves are electrically connected with a power supply. The die 5 is made of stainless steel and is provided with a forming groove, and the surface of the forming groove is plated with fluorine. The depth of the forming groove is 1.5 cm.
3. And clamping the graphene carbon fiber composite film between templates with smooth mirror surfaces, stacking the templates in a mold 5, and performing vacuum pressing for 10 minutes under the pressure of 50 tons by using a vacuum flat press to obtain the graphene carbon fiber composite heat-conducting film.
Example 2: preparation of graphene composite heat-conducting film
The preparation method of the graphene composite heat-conducting film comprises the following steps:
1. mixing 20 layers of lamellar graphene with the sheet diameter of 100 microns, which is prepared by a physical stripping method, carbon fibers with the diameter of 10 microns and the length of 300 microns with acetone, and performing ultrasonic treatment to obtain a graphene-carbon fiber mixed dispersion liquid with the solid content of 0.5 wt%;
the graphene prepared by the physical stripping method is obtained by carrying out ultrasonic treatment on natural graphite or expanded graphite.
The mass ratio of the graphene prepared by the physical stripping method to the carbon fiber is 10: 1.
2. and transferring the graphene carbon fiber mixed dispersion liquid into a magnetic field orientation device, wherein the liquid level height is 10 cm, under the action of a magnetic field with the strength of 20 Tesla, enabling graphene and carbon fibers to be oriented and arranged along the horizontal direction, and heating to completely volatilize the solvent to obtain the graphene carbon fiber composite film.
The magnetic field is applied by a magnetic field orientation device shown in fig. 1, which comprises a power supply 1, two coils 2 and 3 connected with the power supply and distributed at intervals, an electric heating plate 4 positioned between the two coils 2 and 3, and a mold 5 placed on the electric heating plate 4; the two coils 2 and 3 have the same radius and are arranged oppositely; the central connecting line of the two coils 2 and 3 is superposed with the central axis of the mould 5. After the two coils 2 and 3 are electrified, a magnetic field is formed along the direction of the central connecting line of the two coils, and the magnetic field passes through a die 5 which is positioned on an electric hot plate 4 and is provided with the graphene carbon fiber mixed dispersion liquid. The two sides of the electric heating plate 4 are provided with fixing supports, fixing grooves are formed in the fixing supports, and the fixing grooves are electrically connected with a power supply. The die 5 is made of stainless steel and is provided with a forming groove, and the surface of the forming groove is plated with fluorine. The depth of the molding groove is 10 cm.
3. And clamping the graphene carbon fiber composite film between templates with smooth mirror surfaces, stacking the graphene carbon fiber composite film in a mold 5, and performing vacuum pressing for 30 minutes under the pressure of 1000 tons through a vacuum flat press to obtain the graphene carbon fiber composite heat-conducting film.
Comparative example 1: preparation of graphene composite heat-conducting film
Comparative example 1 differs from example 1 in that: the graphene prepared by the physical stripping method in the embodiment 1 is replaced by graphene oxide, and the graphene composite heat-conducting film is prepared by adopting the traditional processes of pulping, coating, carbonizing, graphitizing and calendering, wherein the specific preparation method comprises the following steps:
1. mixing graphene oxide and carbon fibers with the diameter of 7 microns and the length of 50 microns according to a mass ratio of 20: 1, dispersing in deionized water, adding ammonia water to adjust the pH value to 7.5, and stirring in vacuum to obtain graphene oxide carbon fiber mixed slurry with the solid content of 4 wt%;
2. treating the graphene oxide carbon fiber mixed slurry for 30 minutes by a high-pressure homogenizer under the pressure of 500MPa, so as to improve the dispersion stability of the graphene oxide carbon fiber mixed slurry;
3. coating the graphene oxide carbon fiber mixed slurry on a substrate through a coating machine, controlling the thickness to be 1.5 cm, baking for 1 hour at 90 ℃ through a tunnel furnace, and then rolling to obtain a graphene oxide carbon fiber film;
4. cutting the graphene oxide carbon fiber film into sheets, and then placing the sheets in a vacuum drying oven to be treated for 5 hours at 150 ℃ to obtain a partially reduced graphene oxide carbon fiber film;
5. placing the partially reduced graphene oxide carbon fiber film in a carbonization furnace to be treated for 6 hours at 1500 ℃, and then treating the film for 10 hours at 3000 ℃ in a graphitization furnace to obtain a graphene carbon fiber film;
6. placing a smooth-mirror-surface stainless steel sheet between every two graphene carbon fiber films, stacking the stainless steel sheets in a grinding tool, and vacuumizing and pressing the stainless steel sheets for 10 minutes under the pressure of 50 tons through a vacuum flat press to obtain the graphene composite heat-conducting film.
Comparative example 2: preparation of graphene composite heat-conducting film
Comparative example 2 differs from example 2 in that: the graphene prepared by the physical stripping method in the embodiment 2 is replaced by graphene oxide, and the graphene composite heat-conducting film is prepared by adopting the traditional processes of pulping, coating, carbonizing, graphitizing and calendering, wherein the specific preparation method comprises the following steps:
1. mixing graphene oxide and carbon fibers with the diameter of 10 micrometers and the length of 300 micrometers according to the mass ratio of 10: 1, dispersing in deionized water, adding ammonia water to adjust the pH value to 7.5, and stirring in vacuum to obtain graphene oxide carbon fiber mixed slurry with the solid content of 4 wt%;
2. treating the graphene oxide carbon fiber mixed slurry for 30 minutes by a high-pressure homogenizer under the pressure of 500MPa, so as to improve the dispersion stability of the graphene oxide carbon fiber mixed slurry;
3. coating the graphene oxide carbon fiber mixed slurry on a base material through a coating machine, controlling the thickness to be 10 cm, baking the graphene oxide carbon fiber mixed slurry for 1 hour at 90 ℃ through a tunnel furnace, and then rolling the graphene oxide carbon fiber mixed slurry to obtain a graphene oxide carbon fiber film;
4. cutting the graphene oxide carbon fiber film into sheets, and then placing the sheets in a vacuum drying oven to be processed for 5 hours at 150 ℃ to obtain a partially reduced graphene oxide carbon fiber film;
5. placing the partially reduced graphene oxide carbon fiber film in a carbonization furnace for 6 hours at 1500 ℃, and then treating the film in a graphitization furnace for 10 hours at 3000 ℃ to obtain a graphene carbon fiber film;
6. placing a smooth-mirror-surface stainless steel sheet between every two graphene carbon fiber films, stacking the stainless steel sheets in a grinding tool, and vacuumizing and pressing the stainless steel sheets for 30 minutes under the pressure of 1000 tons through a vacuum flat press to obtain the graphene composite heat-conducting film.
The graphene composite heat-conducting films prepared in examples 1 to 2 and comparative examples 1 to 2 were subjected to thickness and heat conductivity tests, and the test results are shown in table 1 below. The test standard of the thermal conductivity test is ASTM E1461.
TABLE 1 thickness and thermal conductivity test results
As can be seen from table 1 above, the vertical coefficients of the graphene composite thermal conductive films of examples 1 to 2 are equivalent to those of comparative examples 1 to 2, and the horizontal thermal conductivity is significantly higher than those of comparative examples 1 to 2. Specifically, it can be seen from the data of example 1 and comparative example 1, and the data of example 2 and comparative example 2 that, by using graphene prepared by a physical stripping method as a raw material and cooperating with carbon fibers and a magnetic field, the obtained graphene and carbon fibers have high horizontal orientation degree and high density, the carbon fibers are located between graphene sheet layers and can play a role in thermal conduction bridging, and the prepared graphene composite thermal conductive film has high thermal conductivity in both horizontal and vertical directions. In addition, the preparation method of the graphene composite heat-conducting film does not need carbonization and graphitization treatment, and is few in preparation process, low in equipment requirement and lower in product cost.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a graphene composite heat-conducting film is characterized by comprising the following steps:
mixing graphene and carbon fiber prepared by a physical stripping method with an organic solvent to prepare a graphene-carbon fiber mixed dispersion liquid;
placing the graphene carbon fiber mixed dispersion liquid in a magnetic field, carrying out orientation treatment in the horizontal direction, and removing the organic solvent to prepare a graphene carbon fiber composite film;
and clamping the graphene carbon fiber composite film between templates with smooth mirror surfaces for vacuum pressing to prepare the graphene composite heat-conducting film.
2. The method for preparing the graphene composite heat-conducting film according to claim 1, wherein the graphene prepared by the physical exfoliation method is a lamellar structure graphene with 5-20 layers obtained by physically exfoliating natural graphite or expanded graphite; and/or the sheet diameter of the graphene prepared by the physical stripping method is more than or equal to 10 microns.
3. The method according to claim 2, wherein the physical peeling process comprises at least one of ultrasound, microwave and sanding.
4. The method for preparing the graphene composite heat-conducting film according to claim 1, wherein the carbon fibers have a diameter of 7 to 10 micrometers and a length of 50 to 300 micrometers; and/or the mass ratio of the graphene prepared by the physical stripping method to the carbon fiber is (10-20): 1.
5. the method according to claim 1, wherein the organic solvent comprises one or more of ethanol, diethyl ether, isopropanol, and acetone; and/or the solid content of the graphene carbon fiber mixed dispersion liquid is 0.5-2 wt%.
6. The method according to claim 1, wherein the magnetic field has a strength of 5 tesla to 20 tesla; and/or in a magnetic field, the liquid level height of the graphene carbon fiber mixed dispersion liquid is 1.5-10 cm.
7. The method for preparing the graphene composite thermal conductive film according to claim 1, wherein the pressure of the vacuum pressing is 20 tons to 1000 tons, and the time is 2 minutes to 30 minutes.
8. The method for preparing the graphene composite heat-conducting film according to any one of claims 1 to 7, wherein the magnetic field is applied through a magnetic field orienting device, and the magnetic field orienting device comprises a power supply (1), two coils (2) and (3) which are connected with the power supply and distributed at intervals, an electric heating plate (4) positioned between the two coils (2) and (3), and a mold (5) placed on the electric heating plate (4); the two coils (2) and (3) have the same radius and are arranged oppositely; the central connecting line of the two coils (2) and (3) is superposed with the central axis of the mould (5); and during pressing, the graphene carbon fiber composite film and the template are placed in a forming groove of the mold (5).
9. A graphene composite heat-conducting film, which is prepared by the preparation method of the graphene composite heat-conducting film according to any one of claims 1 to 8.
10. The graphene composite thermal conductive film according to claim 9, wherein the thickness of the graphene composite thermal conductive film is 60 to 300 micrometers; and/or the planar thermal conductivity of the graphene composite thermal conductive film is more than or equal to 1350W/m.degree; and/or the vertical thermal conductivity of the graphene composite heat-conducting film is more than or equal to 25W/m.degree.
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