CN110282974B - Oriented magnetic carbon fiber graphene composite membrane and preparation method and application thereof - Google Patents
Oriented magnetic carbon fiber graphene composite membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a magnetic carbon fiber graphene composite membrane in oriented arrangement, and a preparation method and application thereof. The preparation method comprises the steps of carrying out magnetic loading on carbon fibers, then carrying out ultrasonic dispersion on magnetic carbon fiber powder in a solvent, pouring the magnetic carbon fiber powder into a suction filtration funnel with magnets with opposite magnetic poles fixed on two sides, standing, carrying out suction filtration to form a film after the magnetic carbon fibers are stabilized under the action of a magnetic field, taking the composite film off a filter membrane, putting the composite film into a mold, pressurizing, putting the composite film into a tubular furnace, adding protective gas, heating to 1000-1500 ℃, and carrying out heat preservation to obtain the magnetic carbon fiber graphene composite film. The magnetic carbon fibers are distributed in the graphene sheet layers in parallel under the action of an external magnetic field, and the parallelism rate reaches 85% -95%. The carbon fibers in the composite film enhance the mechanical property of the composite film, effectively separate graphene sheets in the composite film, improve the quality of the sheets and increase the heat-conducting property of the composite film.
Description
Technical Field
The invention relates to the technical field of heat conduction materials, in particular to a preparation method and application of a magnetic carbon fiber graphene composite film in oriented arrangement. The oriented magnetic carbon fiber graphene composite film can be applied to heat dissipation of high-power electronic components, LEDs and battery packs.
Background
In the general heat dissipation mode of the high heat flow density system in the prior art, metal fins such as copper and aluminum are obtained by machining, and the fins are installed at a heat source. Because the thermal conductivity of metal is only hundreds of W/mK, high-quality and large-volume fins are often needed to achieve the heat dissipation requirement, and the total weight of the system is increased, so that more volume is occupied.
In the field of heat conduction, graphene becomes a high-heat-conduction nano carbon material following diamond and carbon nano tubes, and the in-plane heat conductivity of the nano carbon material reaches 5300W/mK. However, the original graphene obtained by mechanical exfoliation, liquid phase exfoliation, oxidation-reduction, chemical vapor deposition and other methods has excellent properties mostly based on nanometer scale and has no high commercial value, and most of graphene products are made of graphene as a base material or a filler factor to be made into a composite material to exert the excellent properties of graphene. In a thermal management system, the composite material prepared from the graphene has the characteristics of high thermal conductivity, strong stability, good mechanical property, light weight and the like, so that the composite material becomes an important means for solving the problem of heat dissipation of high-integration electronic components. Compared with the traditional heat conduction material, the novel composite heat conduction material needs to have higher heat conductivity and lighter weight, and needs to have certain flexibility. The carbon-carbon composite heat conduction material is light in weight, the heat conductivity and the mechanical strength of the carbon-carbon composite heat conduction material are closely related to the micro appearance of the carbon-carbon composite heat conduction material, and the mechanical property and the heat conduction effect of the carbon-carbon composite heat conduction material can be improved by adjusting the internal structure of the carbon-carbon composite heat conduction material.
The TGC series multilayer high-thermal-conductivity graphite film is produced by carbon source science and technology limited and is mainly applied to civil high-end electronic devices, chip materials for LEDs, radiators for industrial devices, first walls of nuclear fusion reactors and the like. The preparation method of the TGC series products generally needs to adopt polyimide, polyamide and other high molecular films as precursors, firstly carries out carbonization at 600-1000 ℃, graphitization at 2600-3200 ℃ and heat preservation, and then finally obtains the products through rolling, the process is complex and has huge energy consumption, and meanwhile, the products are formed by stacking graphene films, so that the interlayer slip phenomenon is obvious when the products are subjected to tensile stress, the tensile strength is lower, and the heat conductivity is obviously reduced along with the increase of the stacking layers of the graphene.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an oriented magnetic carbon fiber graphene composite film and a preparation method thereof, wherein the tensile strength of the composite film along the carbon fiber direction reaches 35-37MPa, and the thermal conductivity exceeds 600W/mK.
The invention also aims to provide application of the directionally-arranged magnetic carbon fiber graphene composite film in LED heat dissipation.
According to the invention, carbon fiber frameworks which are arranged in parallel are constructed through external magnetic field guidance, graphene oxide is deposited on the frameworks, and the composite membrane material is obtained through a low-temperature thermal reduction mode. Meanwhile, the preparation method effectively adjusts the fiber orientation of the chopped carbon fibers, only low-temperature carbonization is carried out in the preparation process, the hot-pressing graphitization process is avoided, and the energy consumption in the preparation process is effectively reduced. In order to improve the overall performance of the graphene film,
according to the preparation method, the graphene sheets are separated by introducing the magnetic carbon fibers which are arranged in an oriented mode, so that interlayer phonon scattering generated by graphene stacking is reduced, meanwhile, the magnetic carbon fibers are used as good reinforcements, so that the tensile strength of the graphene film is increased, the preparation process does not need graphitization treatment, and the energy consumption in the preparation process is reduced. The high-heat-conductivity and high-strength composite film prepared by the invention provides a better solution for heat dissipation of high-power electronic components, LEDs and battery packs.
The composite film prepared by the invention has high thermal conductivity, light weight and small volume, and the quality of the heat dissipation material and the volume occupied by the heat dissipation material required for achieving the same heat dissipation effect are obviously reduced by attaching the composite film on the surface of a heat source as a temperature equalization material.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a magnetic carbon fiber graphene composite film in oriented arrangement comprises the following steps:
1) magnetic loading of carbon fibers: adding the carbon fiber into a dispersing agent, stirring, performing ultrasonic treatment, performing vacuum filtration, and drying; stirring and refluxing the dried solid and the first mixed solution in an oil bath at the temperature of 80-90 ℃, diluting, performing suction filtration in deionized water, washing with water until the filtrate is neutral, and drying; mixing the dried solid with the second mixed solution, soaking, dropwise adding an alkaline solution into an oil bath at 80-90 ℃ until a large amount of precipitate is generated, standing, performing suction filtration and water washing by using deionized water until the filtrate is neutral, and drying to obtain magnetic carbon fiber powder; the first mixed solution is obtained by mixing nitric acid and sulfuric acid according to the mass ratio of 1:1-3: 2; the second mixed solution is ferric chloride solution and ferrous chloride solution, wherein Fe3+With Fe2+The mass ratio of (A) to (B) is 2:1-3: 1;
2) preparing a magnetic carbon fiber graphene oxide composite membrane: ultrasonically dispersing magnetic carbon fiber powder in a solvent, pouring the ultrasonic dispersion into a suction filtration funnel with magnets with opposite magnetic poles fixed on two sides for standing, after the magnetic carbon fiber is stabilized under the action of a magnetic field, carrying out suction filtration and washing, dropwise adding a graphene oxide dispersion liquid with the concentration of 2-6mg/ml, continuously carrying out suction filtration until a film is formed, and drying;
3) thermal reduction of the composite membrane: and taking the composite membrane off the filter membrane, putting the composite membrane into a mold, pressurizing, putting the mold into a tubular furnace, adding protective gas, heating to 1000-1500 ℃, and preserving heat to obtain the magnetic carbon fiber graphene composite membrane.
For further achieving the object of the present invention, preferably, in step 1), the dispersant is at least one of acetone, methanol and phenol; the alkaline solution is at least one of ammonium hydroxide, sodium hydroxide and potassium hydroxide;
in the step 2), the magnet is a ferrite magnet, a samarium-cobalt alloy magnet or a rubidium-cesium alloy magnet; the graphene oxide dispersion liquid is prepared by improving a Hummers method.
Preferably, in step 1), controllingProduction of carbon fiber and Fe produced3O4The mass ratio of (A) to (B) is 2:1-5: 1.
Preferably, in the step 1), the carbon fiber is 10-40 parts by weight, and the dispersant is 1000-1200 parts by weight.
Preferably, in step 1), all drying is carried out at a temperature of 50-70 ℃ to a constant weight; in the step 1), adding a dispersing agent into the carbon fiber and stirring for 36-48 h; the ultrasonic treatment time is 1-2 h; the standing time is 1-2 h; the stirring reflux time is 6-8h, and the soaking time is 12-24 h.
Preferably, in the step 2), the mass ratio of the magnetic carbon fiber to the graphene oxide is 1:3-1: 20; the solvent is N-methyl pyrrolidone or N, N-dimethylformamide; the ultrasonic dispersion time is 10-20 minutes; the standing time is 10-20 minutes, and the drying is carried out under the condition of vacuum drying at the temperature of 50-60 ℃ to constant weight.
Preferably, in the step 3), the pressure for pressurizing is 10-50 MPa; the protective gas is argon or nitrogen; the temperature is increased to 1000-1500 ℃ from room temperature at the temperature increasing rate of 3-5 ℃/min; the heat preservation time is 2-3 h.
The thickness of the obtained oriented magnetic carbon fiber graphene composite membrane is 50-220 mu m, the heat conductivity coefficient is 600-800W/mK, and the tensile strength in the direction parallel to the carbon fibers is 35-37 MPa.
Preferably, the composite membrane consists of magnetic carbon fibers and graphene, wherein the content of the magnetic carbon fibers is 10-40% and the content of the graphene is 60-90% in percentage by mass; the diameter of the composite membrane is 40-80 mm; the magnetic carbon fibers are distributed in the graphene sheet layers in parallel under the action of an external magnetic field, and the parallelism rate reaches 85% -95%.
The oriented magnetic carbon fiber graphene composite film is applied to LED heat dissipation.
In the step 3), the die is realized by fixing two ceramic plates or graphite plates through high-temperature screws.
The invention uses coprecipitation for reference to prepare magnetic Fe3O4Method of fluid, magnetic Fe3O4The particles are loaded on the carbon fibers, the carbon fibers are arranged in the magnetic field in the same orientation under the guidance of an external magnetic field to form a framework, graphene oxide is deposited in the carbon fiber framework, and the oriented magnetic carbon fiber graphene composite membrane is obtained through low-temperature thermal reduction. As the carbon fiber has good mechanical property, the carbon fiber and the graphene form a coating structure in the composite film, and the nano Fe is loaded on the surface of the carbon fiber3O4The particles increase the surface roughness of the carbon fibers and reduce the possible slippage between the carbon fibers and the graphene, so that the tensile strength and flexibility of the composite membrane are enhanced. Meanwhile, the carbon fibers effectively separate the sheets of the graphene, so that phonon leakage in the heat transfer process is reduced, and the heat conductivity of the composite membrane is improved.
Compared with the prior art, the invention has the following advantages and effects:
the invention uses magnetic Fe3O4The particles are loaded on the carbon fibers, the carbon fibers are arranged in the magnetic field in the same orientation under the guidance of an external magnetic field to form a parallel framework, and then the oriented magnetic carbon fiber graphene composite membrane is obtained by depositing graphene oxide and carrying out thermal reduction. On one hand, the tensile strength of the composite membrane along the carbon fiber direction is effectively enhanced by the magnetic carbon fibers in the oriented arrangement, so that the tensile strength reaches 35-37 MPa. On the other hand, the magnetic carbon fibers are distributed in different thicknesses of the graphene sheet layers, so that the graphene sheet layers are effectively separated, heat transfer of graphene is mainly realized through phonon transmission, and with the increase of the number of the graphene sheet layers, scattering and leakage phenomena of phonons between the layers are obviously increased, so that the thermal conductivity of the graphene is reduced. Therefore, due to the increase of the interlayer spacing of the graphene sheets, phonon scattering and leakage between layers are reduced, the heat conduction performance of the composite film is improved, and the heat conductivity of the composite film is over 600W/mK. Compared with TGC series multilayer high heat conduction graphite films, the invention increases the heat conduction performance and the mechanical property of the composite film due to the addition of the magnetic carbon fiber, avoids graphitization with huge energy consumption, and effectively reduces the production cost.
Drawings
FIG. 1 is a scanning electron microscope image of example 1, in which magnetic ferroferric oxide-containing nanoparticles are wrapped on the surface of carbon fibers.
Fig. 2 is a scanning electron microscope image of the magnetic carbon fiber graphene composite film in the oriented arrangement in example 1.
Fig. 3 is a diagram of a mold used for the thermal reduction of the oriented magnetic carbon fiber graphene composite film in example 1.
Shown in fig. 3: screw 1, ceramic plate 2, complex film 3, nut 4.
Detailed description of the preferred embodiments
For a better understanding of the present invention, the following description is given in conjunction with the accompanying drawings and examples, which are not intended to limit the scope of the present invention in any way.
Example 1
A preparation method of a magnetic carbon fiber graphene composite film in oriented arrangement comprises the following steps:
1) and (3) magnetic loading of the carbon fiber, namely adding 30 parts of the carbon fiber into 1000 parts of acetone by weight, stirring for 48 hours, performing ultrasonic treatment for 1 hour, performing vacuum filtration, and drying the solid at 70 ℃ to constant weight. Adding the dried carbon fiber into a glassware, adding 500 parts of a mixed solution of nitric acid and sulfuric acid with a mass ratio of 3:2, stirring and refluxing for 6 hours in an oil bath at 90 ℃, diluting, performing suction filtration and washing with deionized water in a suction filtration funnel until the filtrate is neutral, and drying at 60 ℃ to constant weight. Adding the dried solid into a glass ware, and respectively adding 150 parts of deionized water and the prepared ferric chloride solution and ferrous chloride solution, and ensuring that m (Fe) is m3 +):m(Fe2+) 2:1, m (carbon fiber): m (Fe)3O4) And (3) 1:1, soaking for 12h, dropwise adding 20 parts of sodium hydroxide into an oil bath at 90 ℃, standing for 2h, performing suction filtration and water washing on the filtrate in a suction filtration funnel by using deionized water until the filtrate is neutral, and performing vacuum drying at 60 ℃ until the weight is constant to finally obtain the magnetic carbon fiber powder. Where m denotes mass. As shown in fig. 1, which is a scanning electron microscope topography of magnetic carbon fiber, a large amount of ferroferric oxide nanoparticles are generated and attached to the surface of the carbon fiber after the alkaline solution is added.
2) Preparing a magnetic carbon fiber graphene oxide composite membrane: dispersing the prepared magnetic carbon fiber powder in 500 parts by weight of N-methylpyrrolidone, carrying out ultrasonic treatment for 10 minutes, pouring the mixture into a suction filtration funnel with magnets with opposite magnetic poles fixed on two sides, standing for 10 minutes, carrying out suction filtration and washing after the magnetic carbon fiber is stabilized under the action of a magnetic field, dropwise adding 60 parts of graphene oxide dispersion liquid with the concentration of 6mg/ml, continuing suction filtration until a film is formed, and carrying out vacuum drying at the temperature of 60 ℃ until the weight is constant. The graphene oxide dispersion liquid is prepared by improving a Hummers method. The selected magnet is a rubidium and cesium alloy magnet.
3) And taking the composite membrane off the filter membrane, putting the composite membrane into a die (shown in figure 3), applying a pressure of 50MPa, putting the die into a tube furnace, taking argon as protective gas, raising the temperature to 1500 ℃ at a temperature rise rate of 5 ℃/min, and preserving the temperature for 2 hours to obtain the magnetic carbon fiber graphene composite membrane. As shown in fig. 2, which is a scanning electron microscope image of the magnetic carbon fiber graphene composite film, in the reduced composite film, carbon fibers arranged in parallel are distributed in different layer thicknesses of graphene and are tightly wrapped by the graphene.
Fig. 3 is a diagram of a mold used for the thermal reduction of the oriented magnetic carbon fiber graphene composite film in example 1. As shown in fig. 3, the composite film 2 is placed between two ceramic plates 2 having an optical hole and the nut 4 and the screw 1 are coupled to compress the ceramic plates 2 through the optical hole as shown in fig. 3.
Example 2
A preparation method of a magnetic carbon fiber graphene composite film in oriented arrangement comprises the following steps:
1) and (3) magnetic loading of carbon fibers, namely adding 40 parts of carbon fibers into 1200 parts of methanol, stirring for 36 hours, carrying out ultrasonic treatment for 2 hours, carrying out vacuum filtration, and drying the solid at 65 ℃ to constant weight. Adding the dried carbon fiber into a glassware, adding 500 parts of a mixed solution of nitric acid and sulfuric acid with a ratio of 1:1, stirring and refluxing for 7 hours in an oil bath at 80 ℃, diluting, performing suction filtration and washing with deionized water in a suction filtration funnel until the filtrate is neutral, and drying at 50 ℃ to constant weight. Adding the dried solid into a glass ware, respectively adding 100 parts of deionized water and the prepared ferric trichloride solution and ferrous chloride solution, and ensuring that m (Fe)3+):m(Fe2+) 3:1, m (carbon fiber): m (Fe)3O4) Soaking for 18h under the condition of 4:1, dropwise adding 30 parts of potassium hydroxide into an oil bath at the temperature of 80 ℃, standing for 2h, performing suction filtration and water washing on the filtrate in a suction filtration funnel by using deionized water until the filtrate is neutral, and performing vacuum drying at the temperature of 50 ℃ until the weight is constant to finally obtain the magnetic carbon fiber powder.
2) The preparation method of the magnetic carbon fiber graphene oxide composite membrane comprises the steps of dispersing prepared magnetic carbon fiber powder in 600 parts of N-methyl pyrrolidone for 15 minutes through ultrasound, pouring the magnetic carbon fiber powder into a suction filtration funnel with magnets with opposite magnetic poles fixed on two sides, standing for 15 minutes, after the magnetic carbon fiber is stabilized under the action of a magnetic field, performing suction filtration and washing, dropwise adding 80 parts of graphene oxide dispersion liquid with the concentration of 5mg/ml, continuing the suction filtration until a membrane is formed, and performing vacuum drying at the temperature of 60 ℃ until the constant weight is achieved. The graphene oxide dispersion liquid is prepared by improving a Hummers method. The selected magnet is samarium cobalt magnet.
3) And taking the composite membrane off the filter membrane, putting the composite membrane into a mold, applying a pressure of 30MPa, putting the mold into a tubular furnace, taking argon as protective gas, raising the temperature to 1200 ℃ at a heating rate of 5 ℃/min, and preserving the temperature for 3h to obtain the magnetic carbon fiber graphene composite membrane. The adopted mould is realized by fixing two graphite plates through high-temperature screws.
Example 3
A preparation method of a magnetic carbon fiber graphene composite film in oriented arrangement comprises the following steps:
1) and (3) magnetic loading of carbon fibers, namely adding 20 parts of carbon fibers into 1100 parts of methanol-phenol mixed liquor with the ratio of 6:5, stirring for 40 hours, performing ultrasonic treatment for 1.5 hours, performing vacuum filtration, and drying the solid at the temperature of 60 ℃ to constant weight. Adding the dried carbon fiber into a glassware, adding 500 parts of a mixed solution of nitric acid and sulfuric acid with a ratio of 5:4, stirring and refluxing for 8 hours in an oil bath at 85 ℃, diluting, performing suction filtration and washing with deionized water in a suction filtration funnel until the filtrate is neutral, and drying at 55 ℃ to constant weight. Adding the dried solid into a glass ware, respectively adding 125 parts of deionized water and the prepared ferric trichloride solution and ferrous chloride solution, and ensuring that m (Fe)3+):m(Fe2+) 2:1, m (carbon fiber): m (Fe)3O4) Soaking for 20h at 5:1, dripping 40 parts of ammonium hydroxide into oil bath at 85 ℃, standing for 1.5h, and filtering in a filter funnelAnd filtering and washing the mixture by deionized water until the filtrate is neutral, and drying the mixture in vacuum at the temperature of 55 ℃ until the weight is constant, thereby finally obtaining the magnetic carbon fiber powder.
2) The preparation method of the magnetic carbon fiber graphene oxide composite membrane comprises the steps of dispersing prepared magnetic carbon fiber powder in 550 parts of N, N-dimethylformamide, conducting ultrasonic treatment for 20 minutes, pouring the obtained magnetic carbon fiber powder into a suction filtration funnel with magnets with opposite magnetic poles fixed on two sides, standing for 20 minutes, conducting suction filtration and washing after the magnetic carbon fiber is stabilized under the action of a magnetic field, dropwise adding 90 parts of graphene oxide dispersion liquid with the concentration of 2mg/ml, continuing suction filtration until a membrane is formed, and conducting vacuum drying at 55 ℃ until the constant weight is achieved. The graphene oxide dispersion liquid is prepared by improving a Hummers method. The selected magnet is ferrite magnet.
3) And taking the composite membrane off the filter membrane, putting the composite membrane into a mold, applying a pressure of 40MPa, putting the mold into a tubular furnace, taking argon as protective gas, raising the temperature to 1300 ℃ at a heating rate of 4 ℃/min, and preserving the temperature for 2h to obtain the magnetic carbon fiber graphene composite membrane. The adopted mould is realized by fixing two graphite plates through high-temperature screws.
Carbon fiber parallelism detection is carried out on the oriented magnetic carbon fiber graphene composite film obtained in the embodiment 1-3 through a scanning electron microscope image, and the magnetic carbon fibers and the magnetic induction lines are distributed in parallel when the included angle of the magnetic carbon fibers and the magnetic induction lines is smaller than 10 degrees by taking the magnetic induction line direction as a reference. The parallelism of the magnetic carbon fiber is shown in table 1, and since the carbon fiber loaded with the magnetic particles has good paramagnetism under the action of the magnetic field, the carbon fiber loaded with the magnetic particles in examples 1 to 3 has a tendency of being distributed in parallel along the direction of the magnetic induction line under the guidance of the external magnetic field, and at the same time, the higher the parallelism, the better the paramagnetic performance of the magnetic carbon fiber.
TABLE 1 parallelism statistics
| Species of | Parallel ratio (%) |
| Example 1 | 94 |
| Example 2 | 85 |
| Example 3 | 89 |
The composite film prepared by the invention is a multilayer graphene composite film, and the commercialized multilayer high-thermal-conductivity graphite film is most represented by TGC series multilayer high-thermal-conductivity graphite films produced by carbon source science and technology limited, wherein the TGC series is mainly applied to civil high-end electronic devices, chip materials for LEDs, radiators for industrial devices, first walls of nuclear fusion reactors and the like. The composite film prepared by the invention is mainly applied to heat dissipation of high-power electronic components, LEDs and battery packs, and simultaneously reduces the volume and mass of a system, and is similar to the application of TGC series products. By comparison, TGC-1 products with similar bulk density to the invention were selected for comparison of lamella spacing, thermal conductivity, mechanical properties and heat dissipation applications.
The oriented magnetic carbon fiber graphene composite films obtained in examples 1 to 3 and the graphene of the commercially available graphite film with high thermal conductivity were subjected to X-ray diffraction detection, and the spacing between graphene sheets was calculated by bragg formula as shown in table 2.
The minimum interlayer spacing of graphite is shown, and compared with similar products in carbon source science and technology, the graphene sheet interlayer spacing of the embodiment 1-3 is obviously increased, which proves that the oriented carbon fibers can effectively increase the sheet interlayer spacing of graphene, the heat transfer of graphene is mainly realized through phonon transmission, but with the increase of the number of graphene sheets, phonon is obviously increased through the phenomena of scattering and leakage between layers in the transmission process to reduce the heat conductivity of the phonon, and the increase of the sheet interlayer spacing of graphene can reduce the phonon generated between the layersAnd (4) scattering.
TABLE 2 lamellar spacing comparison
The heat conductivity and mechanical properties of the directionally-arranged magnetic carbon fiber graphene composite film obtained in examples 1-3 and the similar products of carbon source science and technology were respectively detected by a laser heat conductivity meter according to the astm e1461 standard and a universal tester according to astm f152, and table 3 was obtained. It can be seen from examples 1 to 3 that, since the oriented carbon fibers separate the graphene sheets, the phonon leakage between the layers is greatly reduced compared with similar products on the market, and thus the thermal conductivity is effectively improved. Meanwhile, the carbon fiber is used as a reinforcement, so that the tensile strength of the graphene film is effectively improved.
TABLE 3 comparison of thermal conductivity with mechanical Properties
| Species of | Coefficient of thermal conductivity (W/mK) | Tensile strength |
| Example 1 | 670±35 | 36MPa |
| Example 2 | 600±30 | 37MPa |
| Example 3 | 630±30 | 35MPa |
| TGC-1 | 300-350 | 15-20MPa |
The directionally-arranged magnetic carbon fiber graphene composite film obtained in the embodiments 1 to 3 and similar products of carbon source science and technology are applied to 24W LED heat dissipation as temperature equalization materials, the temperature equalization films are made and attached to the LED lamp back plate, the infrared camera lens is aligned to the position of the LED lamp back plate, and the temperature after the heat balance of the surface of the LED lamp back plate to which the different temperature equalization films are attached is detected to obtain table 4. After the heat balance is achieved, the lower the temperature of the back plate of the LED lamp is, the better the heat dissipation effect of the temperature-equalizing film is, and because the in-plane thermal conductivity of the examples 1-3 is obviously higher than that of the carbon source technology like products, the examples 1-3 also show the better temperature-equalizing effect in the application process.
TABLE 4 surface temperature of thermal interface materials
| Species of | Surface temperature (. degree. C.) |
| Example 1 | 62 |
| Example 2 | 68 |
| Example 3 | 66 |
| TGC-1 | 73 |
The oriented magnetic carbon fiber graphene composite film can be applied to heat dissipation of high-power electronic components, LEDs and battery packs to replace metal fins such as copper and aluminum and the like which are used traditionally. Because the thermal conductivity of metal is only hundreds of W/mK, high-quality and large-volume fins are often needed to achieve the heat dissipation requirement, and the total weight of the system is increased, so that more volume is occupied. The composite film prepared by the invention has high thermal conductivity, light weight and small volume, and is attached to the surface of a heat source to be used as a temperature-equalizing material, so that the mass of a heat-radiating material and the volume occupied by the heat-radiating material required for achieving the same heat-radiating effect are both obviously reduced, and a good solution is provided for the heat radiation of a high-heat-flux-density system. Compared with TGC series multilayer high-heat-conductivity graphite films, the composite film prepared by the invention has a better heat dissipation effect in the same LED lamp heat dissipation process, so that the LED lamp can keep a lower temperature in stable use, and the composite film is very favorable for prolonging the service life of the LED lamp.
It should be noted that those skilled in the art to which the invention pertains will appreciate that alternative or obvious modifications of the embodiments described herein may be made without departing from the spirit of the invention, and such modifications are to be considered as falling within the scope of the invention.
Claims (10)
1. A preparation method of a magnetic carbon fiber graphene composite film in oriented arrangement is characterized by comprising the following steps:
1) magnetic loading of carbon fibers: adding the carbon fiber into a dispersing agent, stirring, performing ultrasonic treatment, performing vacuum filtration, and drying; stirring and refluxing the dried solid and the first mixed solution in an oil bath at the temperature of 80-90 ℃, diluting, performing suction filtration in deionized water, washing with water until the filtrate is neutral, and drying; mixing the dried solid with the second mixed solution, soaking, dropwise adding an alkaline solution into an oil bath at 80-90 ℃ until a large amount of precipitate is generated, standing, performing suction filtration and water washing by using deionized water until the filtrate is neutral, and drying to obtain magnetic carbon fiber powder; the first mentionedThe mixed solution is obtained by mixing nitric acid and sulfuric acid according to the mass ratio of 1:1-3: 2; the second mixed solution is ferric chloride solution and ferrous chloride solution, wherein Fe3+With Fe2+The mass ratio of (A) to (B) is 2:1-3: 1;
2) preparing a magnetic carbon fiber graphene oxide composite membrane: ultrasonically dispersing magnetic carbon fiber powder in a solvent, pouring the ultrasonic dispersion into a suction filtration funnel with magnets with opposite magnetic poles fixed on two sides for standing, after the magnetic carbon fiber is stabilized under the action of a magnetic field, carrying out suction filtration and washing, dropwise adding a graphene oxide dispersion liquid with the concentration of 2-6mg/ml, continuously carrying out suction filtration until a film is formed, and drying;
3) thermal reduction of the composite membrane: taking the composite membrane off the filter membrane, putting the composite membrane into a mold, pressurizing, putting the mold into a tubular furnace, adding protective gas, heating to 1000-1500 ℃, and preserving heat to obtain a magnetic carbon fiber graphene composite membrane;
the thickness of the obtained oriented magnetic carbon fiber graphene composite film is 50-220 mu m, the heat conductivity coefficient is 600-800W/mK, and the tensile strength in the direction parallel to the carbon fibers is 35-37 MPa.
2. The method for preparing the directionally-arranged magnetic carbon fiber graphene composite membrane according to claim 1, wherein in the step 1), the dispersing agent is at least one of acetone, methanol and phenol; the alkaline solution is at least one of ammonium hydroxide, sodium hydroxide and potassium hydroxide;
in the step 2), the magnet is a ferrite magnet, a samarium-cobalt alloy magnet or a rubidium-cesium alloy magnet; the graphene oxide dispersion liquid is prepared by improving a Hummers method.
3. The method for preparing the directionally-arranged magnetic carbon fiber graphene composite membrane according to claim 1, wherein in the step 1), the carbon fibers and the generated Fe are controlled3O4The mass ratio of (A) to (B) is 2:1-5: 1.
4. The preparation method of the oriented magnetic carbon fiber graphene composite membrane according to claim 1, wherein in the step 1), the carbon fibers are 10-40 parts by weight, and the dispersing agent is 1000-1200 parts by weight.
5. The method for preparing the directionally-arranged magnetic carbon fiber graphene composite membrane according to claim 1, wherein in the step 1), all drying is performed at a temperature of 50-70 ℃ to a constant weight; in the step 1), adding a dispersing agent into the carbon fiber and stirring for 36-48 h; the ultrasonic treatment time is 1-2 h; the standing time is 1-2 h; the stirring reflux time is 6-8h, and the soaking time is 12-24 h.
6. The method for preparing the directionally-arranged magnetic carbon fiber graphene composite membrane according to claim 1, wherein in the step 2), the mass ratio of the magnetic carbon fibers to the graphene oxide is 1:3-1: 20; the solvent is N-methyl pyrrolidone or N, N-dimethylformamide; the ultrasonic dispersion time is 10-20 minutes; the standing time is 10-20 minutes, and the drying is carried out under the condition of vacuum drying at the temperature of 50-60 ℃ to constant weight.
7. The method for preparing the directionally-arranged magnetic carbon fiber graphene composite membrane according to claim 1, wherein in the step 3), the pressure for pressurizing is 10-50 MPa; the protective gas is argon or nitrogen; the temperature is increased to 1000-1500 ℃ from room temperature at the temperature increasing rate of 3-5 ℃/min; the heat preservation time is 2-3 h.
8. An oriented magnetic carbon fiber graphene composite film, which is characterized by being prepared by the preparation method of any one of claims 1 to 7, wherein the thickness of the oriented magnetic carbon fiber graphene composite film is 50-220 μm, the thermal conductivity is 600-800W/mK, and the tensile strength of the oriented magnetic carbon fiber graphene composite film in the direction parallel to carbon fibers is 35-37 MPa.
9. The oriented magnetic carbon fiber and graphene composite membrane according to claim 8, wherein the composite membrane is composed of magnetic carbon fibers and graphene, and comprises, by mass, 10% -40% of the magnetic carbon fibers and 60% -90% of the graphene; the diameter of the composite membrane is 40-80 mm; the magnetic carbon fibers are distributed in the graphene sheet layers in parallel under the action of an external magnetic field, and the parallelism rate reaches 85% -95%.
10. Use of the aligned magnetic carbon fiber graphene composite film according to claim 8 or 9 in LED heat dissipation.
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