CN108251076B - Carbon nanotube-graphene composite heat dissipation film, and preparation method and application thereof - Google Patents

Carbon nanotube-graphene composite heat dissipation film, and preparation method and application thereof Download PDF

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CN108251076B
CN108251076B CN201611247595.6A CN201611247595A CN108251076B CN 108251076 B CN108251076 B CN 108251076B CN 201611247595 A CN201611247595 A CN 201611247595A CN 108251076 B CN108251076 B CN 108251076B
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carbon nanotube
graphene oxide
graphene
dispersion liquid
heat dissipation
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CN108251076A (en
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姚亚刚
卢会芬
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Abstract

The invention discloses a carbon nanotube-graphene composite heat dissipation film, and a preparation method and application thereof. The preparation method comprises the following steps: uniformly mixing the graphene oxide dispersion liquid with the acidified carbon nanotube dispersion liquid to form a carbon nanotube-graphene oxide mixed dispersion liquid; carrying out vacuum filtration treatment on the carbon nanotube-graphene oxide mixed dispersion liquid to form a carbon nanotube-graphene oxide composite film; and carrying out high-temperature thermal reduction treatment on the carbon nanotube-graphene oxide composite film to form the carbon nanotube-graphene composite heat dissipation film. The carbon nanotube-graphene composite heat dissipation film has the advantages of regular structure, no powder falling, low oxygen content, good in-plane orientation, dense interlayer accumulation, high heat conductivity and the like, is simple in preparation method, easy to control conditions, low in cost and has wide application prospects in the fields of heat dissipation of microelectronic devices and the like.

Description

Carbon nanotube-graphene composite heat dissipation film, and preparation method and application thereof
Technical Field
The invention particularly relates to a carbon nanotube-graphene composite heat dissipation film, and a preparation method and application thereof, and belongs to the technical field of nano materials.
Background
In recent years, with the continuous development and progress of microelectronic technology, the integration level, packaging density and operating frequency of chips in computer/mobile phone terminal devices (e.g., tablet computers, mobile phones, etc.) are rapidly increased, so that the heat current density in the chips is rapidly increased, the temperature of the chips is too high, and the working efficiency and system stability of the chips are seriously affected. In order to ensure the reliability and the service life of electronic consumer products, a novel heat-conducting and heat-dissipating material with higher heat conductivity, lower density and higher temperature resistance is needed. The traditional heat dissipation materials are mainly metal materials (such as silver and copper), but the materials have high density, high thermal expansion coefficient and low thermal conductivity (about 400W/m K). Therefore, new high thermal conductive materials need to be developed to meet the needs of modern scientific and technological development. Researches show that the carbon material has the advantages of high thermal conductivity (for example: the in-plane thermal conductivity of single-layer graphene is 1500-5300W/m K, and the thermal conductivity of carbon nanotubes is 3000-3500W/m K), excellent mechanical properties, low density, small thermal expansion coefficient and the like, and can be used as a novel high-thermal-conductivity material.
Currently, there are two types of thermally conductive graphite films available on the market: one is a flexible graphite film, which has certain flexibility and the thermal conductivity of about 200-500W/mK; the other is a polyimide cracked graphite film, which is obtained by cracking a polyimide film at high temperature, and the thermal conductivity of the polyimide cracked graphite film can reach 1000W/mK, but the requirements on the molecular structure and the composition of the polyimide film are high, and the polyimide cracked film needs a long heating carbonization process and a graphitization process at high temperature (about 3000 ℃), so that the working procedures are complicated and harsh, and the cost is high.
The heat-conducting property of the graphene film is equivalent to that of a polyimide cracked graphite film, but the cost is relatively low. In the prior art, the graphene film can be prepared by the following two methods: one method is to prepare the graphene through direct suction filtration, and the graphene film prepared by the method is difficult to form, mainly because the aggregation is generated in the graphene dispersing process, and a stable graphene suspension cannot be obtained. The other method is to prepare a graphene oxide film by using a graphene oxide suspension, and then prepare the graphene film by reduction treatment. The graphene oxide film prepared by the method is regular, but is easy to break, powder and slag fall off when the graphene oxide film is reduced into the graphene film, the in-plane orientation is poor, and the interlayer accumulation is not dense (air-pocket is formed between the layers), so that the heat dissipation performance of the film is poor.
Disclosure of Invention
The invention mainly aims to provide a carbon nanotube-graphene composite heat dissipation film, a preparation method and application thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a carbon nanotube-graphene composite heat dissipation film, which comprises the following steps:
(1) providing a graphene oxide dispersion liquid;
(2) providing an acidified carbon nanotube dispersion;
(3) uniformly mixing the graphene oxide dispersion liquid with the acidified carbon nanotube dispersion liquid to form a carbon nanotube-graphene oxide mixed dispersion liquid;
(4) carrying out (preferably vacuum filtration) treatment on the carbon nanotube-graphene oxide mixed dispersion liquid to form a carbon nanotube-graphene oxide composite film;
(5) and carrying out high-temperature thermal reduction treatment on the carbon nanotube-graphene oxide composite film to form the carbon nanotube-graphene composite heat dissipation film.
Further, the aforementioned step (1) may include: and uniformly dispersing graphene oxide in water to form the graphene oxide dispersion liquid.
Preferably, the concentration of the graphene oxide dispersion liquid is 1-5 mg/ml.
Further, the aforementioned step (2) may include: and uniformly dispersing the acidified carbon nano tubes in water to form the acidified carbon nano tube dispersion liquid.
Preferably, the concentration of the acidified carbon nanotube dispersion liquid is 1-5 mg/ml.
Further, the step (4) may include: and carrying out vacuum filtration treatment on the carbon nanotube-graphene oxide mixed dispersion liquid to form the carbon nanotube-graphene oxide composite membrane.
Further, the step (4) may further include: and after the vacuum filtration treatment is finished, separating the filter cake from the filter membrane, and drying the filter membrane to obtain the self-supporting carbon nanotube-graphene oxide composite membrane.
There are various ways of separating the filter cake from the filter membrane, which are well known in the art, such as by hand stripping.
In some embodiments, the microfiltration membrane used in the vacuum filtration treatment includes a nylon 6,6 filter having a pore size of 0.22 μm, a mixed cellulose filter having a pore size of 0.45 μm, or a nylon 6,6 filter having a pore size of 0.45 μm, and the like, and is not limited thereto.
In some preferred embodiments, the high-temperature thermal reduction treatment in the aforementioned step (5) comprises: and (2) placing the carbon nanotube-graphene oxide composite film in a vacuum environment or a protective atmosphere, heating to 150-400 ℃ at a heating rate of 1-5 ℃/min, stopping heating, keeping the temperature for 1-2 hours, continuing heating to 500-1000 ℃ at a heating rate of 5-10 ℃/min, keeping the temperature for 1-2 hours, and cooling to room temperature to obtain the carbon nanotube-graphene composite heat dissipation film.
Further, the aforementioned protective atmosphere includes any one or a combination of two or more of argon, hydrogen, and nitrogen atmospheres, and is not limited thereto.
Furthermore, the carbon nanotube-graphene composite heat dissipation film comprises 0-50 Wt% of carbon nanotubes (the content of carbon nanotubes is not 0, preferably more than 5 Wt%). The content of the carbon nanotubes in the carbon nanotube-graphene composite heat dissipation film can be adjusted by controlling the dosage ratio of the graphene oxide dispersion liquid to the acidified carbon nanotube dispersion liquid.
In some more specific embodiments, the method for preparing the carbon nanotube-graphene composite heat dissipation film may include the following specific steps:
(1) adding graphene oxide into deionized water at room temperature, and stirring and ultrasonically treating to obtain a graphene oxide solution dispersion liquid, wherein the concentration of the graphene oxide dispersion liquid is 1-5 mg/ml;
(2) adding the acidified carbon nano tube into deionized water at room temperature, and stirring and carrying out ultrasonic treatment to obtain uniformly dispersed acidified carbon nano tube dispersion liquid with the concentration of 1-5 mg/ml;
(3) mixing the graphene oxide dispersion liquid obtained in the step (1) and the acidified carbon nanotube dispersion liquid obtained in the step (2) according to a certain proportion, and stirring and ultrasonically treating to obtain a uniformly dispersed graphene-carbon nanotube mixed solution;
(4) carrying out vacuum filtration on the mixed solution obtained in the step (3) by adopting a microporous filter membrane, drying the obtained filter cake together with the filter membrane, and stripping the filter cake from the filter membrane to obtain a carbon nano tube-graphene oxide composite membrane;
(5) and (3) obtaining the carbon nano tube-graphene composite membrane by adopting a high-temperature thermal reduction method.
Further, the ultrasonic treatment time in the step (1) may be 1 to 3 hours.
Further, the ultrasonic treatment time in the step (2) may be 1 to 3 hours.
Further, the ultrasonic treatment power in the aforementioned step (3) may be 500w, and the time may be 0.5 h.
Further, the high-temperature thermal reduction in the aforementioned step (5) may include: the carbon nanotube-graphene oxide film is clamped between two quartz plates, placed in a tube furnace, heated to 150-400 ℃ at a heating rate of 1-5 ℃/min in a vacuum environment or in any atmosphere of argon, nitrogen and hydrogen, stopped heating, kept at the temperature for 1-2 hours, then continuously heated to 500-1000 ℃ at a heating rate of 5-10 ℃/min, processed for 1-2 hours, and cooled to room temperature, and the carbon nanotube-graphene composite heat dissipation film is obtained.
Further, the graphene oxide and the acidified carbon nanotube may be commercially available or may be self-made. For example, the method of preparing the acidified carbon nanotubes may comprise: and carrying out acidification treatment on the carbon nano tube by nitric acid and sulfuric acid to form the acidified carbon nano tube.
Further, acidic functional groups are distributed on the surface of the acidified carbon nanotube, and the acidic functional groups comprise carboxyl groups.
Preferably, the content of carboxyl in the acidified carbon nanotube is 0.73 wt% to 3.86 wt%.
Preferably, the acidified carbon nanotube has an outer diameter of 30 to 50nm and a length of 10 to 40 μm.
In a more specific embodiment, the acidified carbon nanotube has a carboxyl content of 0.73 wt%, an outer diameter of 30-50 nm and a length of 20 μm, and the acidified carbon nanotube can form a uniform and stable dispersion in water without the need of adding a surfactant.
The embodiment of the invention also provides the carbon nanotube-graphene composite heat dissipation film prepared by any one of the methods. The carbon nanotube-graphene composite heat dissipation film has the characteristics of low oxygen content, compact interlayer accumulation, good in-plane orientation, regular film, no powder falling, high thermal conductivity and the like.
Furthermore, the carbon nanotubes in the carbon nanotube-graphene composite heat dissipation film are sandwiched by the graphene sheets to form a sandwich structure, so that the overall microscopic section of the carbon nanotube-graphene composite heat dissipation film is of a concrete-like brick and tile structure stacked layer by layer, the carbon nanotubes are similar to reinforcing steel bars, and the graphene is similar to bricks. And with the increase of the content of the carbon nano tube, the inter-layer air-pocket alleviating phenomenon of the carbon nano tube-graphene composite heat dissipation film is more obvious.
The embodiment of the invention also provides application of the carbon nanotube-graphene composite heat dissipation film, such as application in preparing heat dissipation heat conduction materials, heat dissipation heat conduction devices or electronic devices.
According to the invention, the carbon nanotube-graphene oxide film is obtained by introducing the acidified carbon nanotubes between graphene layers in an ultrasonic dispersion and suction filtration film forming manner, and is thermally treated and reduced in a limited space, and due to the strong interfacial interaction force between the carbon nanotubes and the graphene, the regular structure of the graphene composite film is maintained, and the technical problems of easy breakage, poor in-plane orientation and non-dense interlayer accumulation of the reduced graphene oxide heat dissipation film prepared from the graphene oxide film are effectively solved.
Compared with the prior art, the carbon nanotube-graphene composite heat dissipation film provided by the invention has the advantages of low oxygen content, regular structure, no powder and slag falling, good in-plane orientation, dense interlayer accumulation, high thermal conductivity and the like, and the preparation method is simple, the conditions are easy to control, the energy is saved, the environment is protected, the cost is low, and the carbon nanotube-graphene composite heat dissipation film has a wide application prospect in the field of heat dissipation of microelectronic devices.
Drawings
Fig. 1a to 1b are optical photographs of a carbon nanotube-graphene oxide composite film and a carbon nanotube-graphene composite heat dissipation film according to example 1 of the present invention;
fig. 2 is an IR spectrum of the carbon nanotube-graphene oxide composite film and the carbon nanotube-graphene composite heat dissipation film prepared in example 1 of the present invention;
fig. 3 is an XRD spectrum of the carbon nanotube-graphene oxide composite film and the carbon nanotube-graphene composite heat dissipation film prepared in example 1 of the present invention;
fig. 4 a-4 b are SEM images of the carbon nanotube-graphene oxide composite film and the carbon nanotube-graphene composite heat dissipation film according to example 1 of the present invention;
fig. 4c is an SEM image of the carbon nanotube-graphene composite heat dissipation film according to comparative example 1 of the present invention.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, implementation process and principle of the present invention will be further explained with reference to the drawings and examples.
Graphene oxide and acidified carbon nanotubes in the following examples are commercially available.
Scanning Electron Microscope (SEM) model S4800, manufactured by HITACHI corporation of Japan, was used in the following examples.
The powder X-ray diffractometer (XRD) (CuK α, λ 0.15406nm) used in the following examples was D8Advance, manufactured by Bruker AXS, Germany.
Thermal diffusivity in the plane of the film (α, mm) in the following examples2Per s) was measured using an LFA447 flash thermal analyzer from Nachi Germany, with a density (p, g/cm)3) The specific heat capacity (Cp, J/Kg ℃) of the sample is set to be the theoretical heat capacity 713J/Kg ℃ of the carbon material, and the thermal conductivity (lambda, W/m K) is calculated by the following formula, wherein lambda is α multiplied by Cp.
Of course, those skilled in the art can easily conceive of substituting reagents, equipment and the like in the following embodiments with other reagents from other suitable sources and other suitable sizes and types of equipment according to the content of the present specification.
Example 1
(1) Under the condition of room temperature, adding 500mg of graphene oxide into 100mL of deionized water, stirring by a glass rod, carrying out ultrasonic treatment for 3 hours, and uniformly mixing to obtain a graphene oxide dispersion liquid with the concentration of 5 mg/mL;
(2) under the condition of room temperature, adding 100mg of acidified carbon nano tubes (wherein the carboxyl content is about 0.73 wt%, the outer diameter is 30-50 nm, and the average length is about 20 mu m) into 100mL of deionized water, and uniformly mixing through stirring by a glass rod and ultrasonic treatment for 3h to prepare acidified carbon nano tube dispersion liquid with the concentration of 1 mg/mL;
(3) uniformly mixing 17mL of graphene oxide dispersion liquid prepared in the step (1) and 15mL of acidified carbon nanotube dispersion liquid prepared in the step (2) through stirring and ultrasonic treatment (ultrasonic power is 500W, time is 0.5h), then performing vacuum filtration by using a nylon 66 microporous filter membrane with the filter pore size of 0.45um, drying the obtained filter cake and the filter membrane for 24h at 60 ℃, and stripping the filter cake from the filter membrane to obtain the carbon nanotube-graphene oxide composite membrane containing 15 wt% of carbon nanotubes;
(4) carrying out high-temperature thermal reduction on the carbon nanotube-graphene oxide composite membrane prepared in the step (3), and specifically comprising the following steps: and clamping the carbon nanotube-graphene oxide composite film between two quartz plates, placing the carbon nanotube-graphene oxide composite film in a tube furnace, heating to 300 ℃ at a heating rate of 2 ℃/min under the protection of hydrogen, preserving heat for 2 hours, then continuously heating to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 1 hour, and cooling to room temperature to obtain the carbon nanotube-graphene composite heat dissipation film.
Referring to fig. 1a to 1b, which are optical photographs of the carbon nanotube-graphene composite heat dissipation film prepared in this embodiment, it can be seen that the carbon nanotube-graphene oxide composite film after high-temperature thermal reduction is changed from black to gray with metallic luster, and the integrity is maintained, and the surface is smooth and has a certain flexibility.
Referring to fig. 2, IR spectra of the carbon nanotube-graphene oxide composite film (line a) and the carbon nanotube-graphene composite heat dissipation film (line b) prepared in example 1 show that the wavelength is 3650cm after the thermal reduction at high temperature-1(O-H)、1087cm-1(C-O)、1400cm-1(C-O-H) and 1790cm-1The peak of the oxygen-containing functional group (C ═ O) disappeared, and the peak corresponding to C ═ C was 1600cm-1Still present, indicating that the high temperature thermal reduction treatment is effective in removing oxygen-containing functional groups from the feedstock and even in repairing the SP2The C ═ C bonds of the hybrid graphite sheets.
Referring to fig. 3, XRD patterns of the carbon nanotube-graphene oxide composite film (line a) and the carbon nanotube-graphene composite heat dissipation film (line b) prepared in example 1 show that after high-temperature thermal reduction, a diffraction peak appears at 2 θ ═ 10.6 °, and a diffraction peak appears at 2 θ ═ 26.2 ° after high-temperature thermal reduction treatment, which indicates that the interlayer spacing of the composite heat dissipation film after thermal reduction is decreased and develops into a structure similar to graphite.
Referring to fig. 4 a-4 b, which are SEM images of the carbon nanotube-graphene oxide composite film and the carbon nanotube-graphene composite heat dissipation film prepared in this example 1, there is no obvious "air pocket" between the carbon nanotube-graphene composite heat dissipation film layers after the high-temperature thermal reduction treatment, and the composite heat dissipation film has good in-plane orientation and is densely stacked.
Through tests, the thermal conductivity of the carbon nanotube-graphene composite film prepared in the embodiment 1 of the invention is 1388W/m K.
Example 2
(1) Under the condition of room temperature, adding 500mg of graphene oxide into 250mL of deionized water, stirring by a glass rod, carrying out ultrasonic treatment for 1h, and uniformly mixing to obtain a graphene oxide dispersion liquid with the concentration of 2 mg/mL;
(2) under the condition of room temperature, adding 100mg of acidified carbon nano tubes (wherein the carboxyl content is about 3.86 wt%, the outer diameter is 10-20 nm, and the average length is about 10-30 mu m) into 50mL of deionized water, stirring by a glass rod, carrying out ultrasonic treatment for 1h, and uniformly mixing to prepare acidified carbon nano tube dispersion liquid with the concentration of 2 mg/mL;
(3) uniformly mixing 47.5mL of graphene oxide dispersion liquid prepared in the step (1) and 2.5mL of acidified carbon nanotube dispersion liquid prepared in the step (2) through stirring and ultrasonic treatment (ultrasonic power is 500W, time is 0.5h), then performing vacuum filtration by using a nylon 66 microporous filter membrane with the filter pore diameter of 0.22um, drying the obtained filter cake and the filter membrane for 24h at 60 ℃, and stripping the filter cake from the filter membrane to obtain the carbon nanotube-graphene oxide composite membrane containing 5 wt% of carbon nanotubes;
(4) carrying out high-temperature thermal reduction on the carbon nanotube-graphene oxide composite membrane prepared in the step (3), and specifically comprising the following steps: and clamping the carbon nanotube-graphene oxide composite film between two quartz plates, placing the quartz plates in a tube furnace, heating to 150 ℃ at a heating rate of 1 ℃/min under the protection of argon, preserving heat for 1h, then continuously heating to 500 ℃ at a heating rate of 8 ℃/min, preserving heat for 1h, and cooling to room temperature to obtain the carbon nanotube-graphene composite heat dissipation film containing 5 wt% of carbon nanotubes.
Through testing, the thermal conductivity of the carbon nanotube-graphene composite film prepared in the embodiment 2 of the invention is 190W/m K.
Example 3
(1) Under the condition of room temperature, adding 500mg of graphene oxide into 250mL of deionized water, stirring by a glass rod, carrying out ultrasonic treatment for 2 hours, and uniformly mixing to obtain a graphene oxide dispersion liquid with the concentration of 2 mg/mL;
(2) under the condition of room temperature, adding 100mg of acidified carbon nano tubes (wherein the carboxyl content is about 2.0 wt%, the outer diameter is 30-50 nm, and the average length is about 20 mu m) into 100mL of deionized water, and uniformly mixing through stirring by a glass rod and ultrasonic treatment for 2h to prepare acidified carbon nano tube dispersion liquid with the concentration of 1 mg/mL;
(3) uniformly mixing 25mL of graphene oxide dispersion liquid prepared in the step (1) and 50mL of acidified carbon nanotube dispersion liquid prepared in the step (2) through stirring and ultrasonic treatment (ultrasonic power is 500W, time is 0.5h), then performing vacuum filtration by using a nylon 66 microporous filter membrane with the filter pore size of 0.45um, drying the obtained filter cake and the filter membrane for 24h at 60 ℃, and stripping the filter cake from the filter membrane to obtain the carbon nanotube-graphene oxide composite membrane containing 50 wt% of carbon nanotubes;
(4) carrying out high-temperature thermal reduction on the carbon nanotube-graphene oxide composite membrane prepared in the step (3), and specifically comprising the following steps: and clamping the carbon nanotube-graphene oxide composite film between two quartz plates, placing the quartz plates in a tube furnace, heating to 400 ℃ at a heating rate of 5 ℃/min under a vacuum condition, preserving heat for 1h, then continuously heating to 1000 ℃ at a heating rate of 10 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain the carbon nanotube-graphene composite heat dissipation film containing 50 wt% of carbon nanotubes.
Through tests, the thermal conductivity of the carbon nanotube-graphene composite film prepared in the embodiment of the invention is 780W/m K.
Example 4
(1) Under the condition of room temperature, adding 500mg of graphene oxide into 500mL of deionized water, stirring by a glass rod, carrying out ultrasonic treatment for 2 hours, and uniformly mixing to obtain a graphene oxide dispersion liquid with the concentration of 1 mg/mL;
(2) under the condition of room temperature, adding 100mg of acidified carbon nano tubes (wherein the carboxyl content is about 0.73 wt%, the outer diameter is 30-50 nm, and the average length is about 20 mu m) into 50mL of deionized water, and uniformly mixing the materials through stirring by a glass rod and ultrasonic treatment for 1h to prepare acidified carbon nano tube dispersion liquid with the concentration of 2 mg/mL;
(3) uniformly mixing 75mL of graphene oxide dispersion liquid prepared in the step (1) and 2.5mL of acidified carbon nanotube dispersion liquid prepared in the step (2) through stirring and ultrasonic treatment (ultrasonic power is 500W, time is 0.5h), then performing vacuum filtration by using a nylon 66 microporous filter membrane with the filter pore diameter of 0.45um, drying the obtained filter cake and the filter membrane for 24h at 60 ℃, and stripping the filter cake from the filter membrane to obtain the carbon nanotube-graphene oxide composite membrane containing 25 wt% of carbon nanotubes;
(4) carrying out high-temperature thermal reduction on the carbon nanotube-graphene oxide composite membrane prepared in the step (3), and specifically comprising the following steps: and clamping the carbon nanotube-graphene oxide composite film between two quartz plates, placing the quartz plates in a tube furnace, heating to 400 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, preserving heat for 1h, then continuously heating to 800 ℃ at a heating rate of 6 ℃/min, preserving heat for 1h, and cooling to room temperature to obtain the carbon nanotube-graphene composite heat dissipation film containing 25 wt% of carbon nanotubes.
Through tests, the thermal conductivity of the carbon nanotube-graphene composite film prepared in the embodiment of the invention is 1100W/m K.
Comparative example 1
(1) Under the condition of room temperature, adding 500mg of graphene oxide into 250mL of deionized water, stirring by a glass rod, carrying out ultrasonic treatment for 2 hours, and uniformly mixing to obtain a graphene oxide dispersion liquid with the concentration of 2 mg/mL;
(2) under the condition of room temperature, 100mg of acidified carbon nano tubes (same as the embodiment 1) are added into 50mL of deionized water, and are stirred by a glass rod and subjected to ultrasonic treatment for 2 hours to be uniformly mixed, so that acidified carbon nano tube dispersion liquid with the concentration of 2mg/mL is prepared;
(3) carrying out ultrasonic treatment (with ultrasonic power of 500W and time of 0.5h) on 100mL of graphene oxide dispersion liquid prepared in the step (1), then carrying out vacuum filtration by using a nylon 66 microporous filter membrane with the filter pore diameter of 0.45um, drying the obtained filter cake and the filter membrane for 24h at 60 ℃, and then stripping the filter cake from the filter membrane to obtain the carbon nanotube-graphene oxide composite membrane containing 0 wt% of carbon nanotubes;
(4) carrying out high-temperature thermal reduction on the carbon nanotube-graphene oxide composite membrane prepared in the step (3), and specifically comprising the following steps: and clamping the carbon nanotube-graphene oxide composite film between two quartz plates, placing the quartz plates in a tube furnace, heating to 300 ℃ at a heating rate of 2 ℃/min under the protection of hydrogen, preserving heat for 1h, then continuously heating to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 1h, and cooling to room temperature to obtain the carbon nanotube-graphene composite heat dissipation film containing 0 wt% of carbon nanotubes.
The thermal conductivity of the carbon nanotube-graphene composite film prepared in the comparative example was tested to be 742W/m K.
Fig. 4c is an SEM image of the carbon nanotube-graphene composite heat dissipation film prepared in the comparative example, and it can be seen that there is an obvious "air pocket" phenomenon between the carbon nanotube-graphene composite heat dissipation film layers after the high-temperature thermal reduction treatment, the in-plane orientation is poor, and the stacking is loose.
Comparative example 2
(1) Under the condition of room temperature, adding 500mg of graphene oxide into 250mL of deionized water, stirring by a glass rod, carrying out ultrasonic treatment for 2 hours, and uniformly mixing to obtain a graphene oxide dispersion liquid with the concentration of 2 mg/mL;
(2) under the condition of room temperature, adding 100mg of commercially available ordinary carbon nano tubes and 100mg of polystyrene dispersion aid into 50mL of deionized water, stirring by a glass rod, carrying out ultrasonic treatment for 2 hours, and uniformly mixing to prepare a carbon nano tube dispersion liquid with the concentration of 2 mg/m;
(3) carrying out ultrasonic treatment (ultrasonic power is 500W, time is 0.5h) on 42.5mL of graphene oxide dispersion liquid prepared in the step (1) and 15mL of acidified carbon nanotube dispersion liquid prepared in the step (2), then carrying out vacuum filtration by adopting a nylon 66 microporous filter membrane with the filter pore size of 0.22um, drying the obtained filter cake and the filter membrane for 24h at 60 ℃, and stripping the filter cake from the filter membrane to obtain the carbon nanotube-graphene oxide composite membrane containing 15 wt% of carbon nanotubes;
(4) carrying out high-temperature thermal reduction on the carbon nanotube-graphene oxide composite membrane prepared in the step (3), and specifically comprising the following steps: and clamping the carbon nanotube-graphene oxide composite film between two quartz plates, placing the quartz plates in a tube furnace, heating to 300 ℃ at a heating rate of 2 ℃/min under the protection of hydrogen, preserving heat for 2h, then continuously heating to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 1h, and cooling to room temperature to obtain the carbon nanotube-graphene composite heat dissipation film containing 15 wt% of carbon nanotubes.
The thermal conductivity of the carbon nanotube-graphene composite film prepared in the comparative example was tested to be 24.2W/m K.
In conclusion, the carbon nanotube-graphene composite heat dissipation film prepared by the invention has the advantages of low oxygen content, regular structure, no powder and slag falling, good in-plane orientation, dense interlayer accumulation, high thermal conductivity and the like.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (12)

1. A preparation method of a carbon nanotube-graphene composite heat dissipation film is characterized by comprising the following steps:
(1) providing a graphene oxide dispersion liquid;
(2) providing an acidified carbon nanotube dispersion, wherein the acidified carbon nanotube contains 0.73 wt% to 3.86 wt% of carboxyl groups;
(3) uniformly mixing the graphene oxide dispersion liquid with the acidified carbon nanotube dispersion liquid to form a carbon nanotube-graphene oxide mixed dispersion liquid;
(4) filtering the carbon nanotube-graphene oxide mixed dispersion liquid to form a carbon nanotube-graphene oxide composite membrane;
(5) performing high-temperature thermal reduction treatment on the carbon nanotube-graphene oxide composite film to form the carbon nanotube-graphene composite heat dissipation film;
wherein the high-temperature thermal reduction treatment comprises: and (2) placing the carbon nanotube-graphene oxide composite membrane in a vacuum environment or a protective atmosphere, heating to 150-400 ℃ at a heating rate of 1-5 ℃/min, stopping heating, keeping the temperature for 1-2 hours, then continuously heating to 500-1000 ℃ at a heating rate of 5-10 ℃/min, keeping the temperature for 1-2 hours, and cooling to room temperature.
2. The method according to claim 1, wherein the step (1) comprises: uniformly dispersing graphene oxide in water to form the graphene oxide dispersion liquid, wherein the concentration of the graphene oxide dispersion liquid is 1-5 mg/ml.
3. The method according to claim 1, wherein the step (2) comprises: and uniformly dispersing the acidified carbon nano tubes in water to form the acidified carbon nano tube dispersion liquid.
4. The method according to claim 1, wherein the acidified carbon nanotube dispersion has a concentration of 1 to 5 mg/ml.
5. The method of claim 1, wherein the acidified carbon nanotubes have an outer diameter of 10 to 50nm and a length of 10 to 40 μm.
6. The method according to claim 1, wherein the step (4) comprises: and carrying out vacuum filtration treatment on the carbon nanotube-graphene oxide mixed dispersion liquid to form the carbon nanotube-graphene oxide composite membrane.
7. The method of claim 6, wherein step (4) further comprises: and after the vacuum filtration treatment is finished, separating the filter cake from the filter membrane, and drying the filter cake to obtain the self-supporting carbon nanotube-graphene oxide composite membrane.
8. The production method according to claim 6 or 7, characterized in that: the microporous filter membrane adopted in the vacuum filtration treatment comprises a nylon 6,6 filter membrane with the filter pore diameter of 0.22 mu m, a mixed cellulose filter membrane with the filter pore diameter of 0.45 mu m or a nylon 6,6 filter membrane with the filter pore diameter of 0.45 mu m.
9. The method of claim 1, wherein: the protective atmosphere comprises any one or the combination of more than two of argon, hydrogen and nitrogen atmospheres.
10. The method of claim 1, wherein: the content of the carbon nanotubes in the carbon nanotube-graphene composite heat dissipation film is greater than 0 and less than or equal to 50 wt%.
11. The method of manufacturing according to claim 10, wherein: the carbon nanotube content in the carbon nanotube-graphene composite heat dissipation film is 5 wt% -50 wt%.
12. The carbon nanotube-graphene composite heat spreading film prepared by the method of any one of claims 1-11.
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