CN109096743B - Graphene film in oriented arrangement, preparation method thereof and composite heat dissipation film - Google Patents
Graphene film in oriented arrangement, preparation method thereof and composite heat dissipation film Download PDFInfo
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Abstract
The invention provides a graphene film which comprises the following components in parts by weight: the graphene film is characterized by comprising 100 parts of modified graphene, 250-450 parts of solvent, 15-50 parts of film forming agent, 0.5-1.5 parts of curing agent, 0.25-15 parts of modifier and 3-10 parts of auxiliary agent, wherein the thickness of the graphene film is 10-80 mu m, and the graphene film is directionally arranged, has a large heat dissipation area, and has high thermal conductivity, high thermal radiance, good flexibility, bending resistance and impact resistance, is not easy to fall off powder and has good processability. The invention also provides a composite heat dissipation film which is sequentially provided with the ultrathin heat conduction silica gel pad and the graphene film in directional arrangement from bottom to top, can be directly contacted with a heat source, does not need double-sided adhesive tape, greatly reduces contact thermal resistance, has good heat conduction performance and mechanical performance, and can be widely applied to the heat dissipation field of electronic products.
Description
Technical Field
The invention relates to the field of heat dissipation films, in particular to a graphene film and a composite heat dissipation film.
Background
In recent years, with the increasing performance of industrial and consumer electronic products, the heat generation problem of each electronic device is more and more serious, and the heat dissipation is more and more important. The theoretical thermal conductivity of the graphene is 3000-5000W/(m.K), and the graphene can be applied to the field of heat dissipation of electronic products. However, in practical application, after the graphene sheet layer is assembled into a film, a large interlayer gap is generated, and the gap not only forms thermal resistance, but also affects the density of the graphene film, thereby reducing the overall heat transfer efficiency of the graphene heat-conducting film. Therefore, in order to obtain a graphene thin film with high thermal conductivity, it is necessary to solve the problem of the gap between graphene sheets and prepare a graphene film with high orientation arrangement.
The prior art discloses methods for preparing certain graphene films in an oriented arrangement, but certain problems exist. For example, chinese patent 201410146002.1 discloses a method for directionally preparing a graphene film with high electrical and thermal conductivity by a liquid phase method, namely, graphene oxide is prepared into a graphene oxide film by vacuum temperature control and vacuum filtration, and then the graphene oxide film is reduced by chemical vapor deposition to obtain the graphene oxide film by directional deposition, the method has complex steps and higher requirements on equipment, and the prepared graphene film is deposited on copper foil or other base materials and is difficult to transfer, the graphene film is easy to damage during transfer, meanwhile, the graphene oxide prepared by the hummer method is adopted as a precursor, and the graphene film is obtained through reduction treatment, so that complete reduction is difficult to realize, partial defects exist in the graphene, the intrinsic high heat conductivity characteristic of the graphene is difficult to fully embody, the highest heat conductivity coefficient of the obtained graphene film only reaches 800W/(m.K), and the difference between the highest heat conductivity coefficient and the theoretical heat conductivity coefficient is large. Chinese patent 201410331358.2 discloses a method for preparing nitrogen-doped oriented graphene, which comprises adding ammonia water into graphene oxide solution, performing hydrothermal reaction, reducing graphene oxide into graphene, and performing oriented vacuum-pumping treatment, wherein the graphene film obtained by the method is only a simple powder lap joint film, is easy to fall powder, has poor mechanical properties, is easy to bend and break, is difficult to process, and is difficult to directly transfer from filter paper, and in order to reduce damage to the film layer in the transfer process, the thickness of the graphene film can be increased to millimeter level, and cannot meet the requirement of lightness and thinness in the field of electronic devices.
Disclosure of Invention
Unless otherwise specified, "parts" in the present invention mean "parts by mass".
Aiming at the problems in the prior art, the invention provides a graphene film which is directionally arranged, has a large heat dissipation area, high thermal conductivity and high thermal radiance, has good flexibility, bending resistance and impact resistance, is not easy to fall off, and has good processability: the invention also provides a composite heat dissipation film which has good heat conduction performance and mechanical performance.
A graphene film comprises the following components in parts by mass: 100 parts of modified graphene, 250-450 parts of solvent, 15-50 parts of film forming agent, 0.5-1.5 parts of curing agent, 0.25-15 parts of modifier and 3-10 parts of auxiliary agent, wherein the curing temperature of the film forming agent is 40-120 ℃, and the thickness of the graphene film is 10-80 mu m.
The graphene film is a graphene film in an oriented arrangement.
The structural formula of the modifier is shown as a formula (1),
in the formula (1), R1Is an alkyl group of C1-C3 or a hydrogen atom, R2Is a hydrogen atom or a methyl group, R3Is a straight chain alkyl radical, R4、R5、R6、R7、R8At least 3 of the groups are polar groups, the rest are hydrogen atoms, the polar groups are sulfonic groups and/or carboxyl groups, and n is an integer of 1-3.
In the formula (1), R1Is a hydrogen atom, R2Is a hydrogen atom or a methyl group, R3Is C1-C3 alkyl, R4，R5，R6，R7，R8All are sulfonic acid groups, and n is an integer of 1-3.
In the formula (1), R1Is a hydrogen atom, R2Is a hydrogen atom or a methyl group, R3Is C1-C3 alkyl, R4，R5，R6，R7，R8All are carboxyl, and n is an integer of 1-3.
In the formula (1), R1Is a hydrogen atom, R2Is methyl, R3Is methyl, R4，R5，R6，R7，R8Are all carboxyl groups, and n is 1.
In the formula (1), R1Is a hydrogen atom, R2Is a hydrogen atom, R3Is propyl, R4，R5，R6，R7，R8Are all carboxyl, and n is 3.
The modified graphene comprises graphene and carbon nano tubes, wherein the mass of each carbon nano tube accounts for 5% -50% of the total mass of the modified graphene, and the number of layers of the graphene is within 10; the modified graphene is not treated by an oxidation reduction way, the modified graphene is prepared by a mechanical force stripping method, a chemical vapor deposition method, a high-temperature cracking method, an intercalation stripping method or a liquid phase stripping method, preferably the modified graphene is prepared by the mechanical force stripping method, and the mechanical stripping method comprises one or more of a medium grinding stripping method, an ultrasonic stripping method, a water jet stripping method, a homogenizer stripping method and a jet mill stripping method.
Preferably, the carbon nanotube comprises one or more of a single-walled carbon nanotube, a double-walled carbon nanotube and a multi-walled carbon nanotube, the diameter of the carbon nanotube is 5-50 nm, the length of the carbon nanotube is 5-35 μm, and the carbon nanotube is preferably a hydroxylated or carboxylated carbon nanotube.
The modified graphene is modified by a surfactant, the surfactant contains a polar hydrophilic group, and the polar hydrophilic group comprises one or more of carboxylic acid, sulfonic acid, sulfuric acid, amino or amino and salts thereof, hydroxyl, amido and ether bonds. Preferably, the surfactant comprises one or more of polyvinylpyrrolidone, polyvinyl alcohol and sodium polystyrene sulfonate.
The solvent is one or more of deionized water, absolute ethyl alcohol, N-methyl pyrrolidone and N, N-dimethylformamide.
The film forming agent is one or two of polyvinyl alcohol emulsion, acrylic resin and polyurethane emulsion; the preferable film-forming agent is acrylic acid modified aqueous polyurethane emulsion, the solid content is 25-40%, and the viscosity is 100-500 cps; further preferably, the film forming agent contains one or both of a self-crosslinking aqueous acrylic modified polyurethane resin and an aqueous acrylic modified aliphatic polyurethane resin.
The curing agent is self-emulsifying polyisocyanate, the-NCO content is 16-48%, and the viscosity is 500-6500 cps.
The auxiliary agent comprises one or more of a defoaming agent, a flatting agent, a film-forming auxiliary agent and polyethylene wax; the leveling agent is a polyether polyurethane leveling agent, and preferably is a leveling agent RM-2020; the defoaming agent is an aqueous system defoaming agent, preferably TEGO Foamex 810 or BYK-019; the film-forming assistant comprises one or more of propylene glycol methyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, isopropanol and the like; the polyethylene wax is an aqueous high-density polyethylene wax emulsion, the viscosity is 50-200 cps, the solid content is 34-36%, and the pH value is 7.5-9.5.
The preparation method of the oriented graphene film comprises the following steps:
(1) preparing modified graphene: placing graphite powder, carbon nano tubes, a surfactant, a solvent and grinding beads in a ball milling device according to the mass ratio of (10-30) to 5 to (0.15-0.3) to 250 to 100, ball milling for 1-6 h at the speed of 1000-4000 r/min, discharging, centrifuging the obtained slurry for 10-30 min at the rotating speed of 1500-2500 rpm, collecting supernatant liquid, and freeze-drying the supernatant liquid to obtain modified graphene;
(2) material preparation and material mixing: sequentially weighing modified graphene, a solvent, a film forming agent, a curing agent, a modifier and an auxiliary agent according to a mass ratio of 100: 250-450: 15-50: 0.5-1.5: 0.25-15: 3-10, stirring for 5-120 min at a rotating speed of 1500-4000 rpm in a high-speed stirrer, taking out slurry, centrifuging the slurry at a rotating speed of 1000-10000 rpm for 10-30 min, and collecting the slurry with an upper layer;
(3) vacuum filtration: and (3) carrying out vacuum filtration on the slurry obtained in the step (2), and intermittently adding a hot solution to assist in filtration while carrying out filtration to obtain the graphene membrane in directional arrangement.
The graphite powder in the step (1) comprises one of crystalline flake graphite powder, expanded graphite powder, spherical graphite, micro-powder graphite and artificial graphite, and the particle size of the graphite powder is 400-8000 meshes; the ball milling equipment comprises one of a grinder, a vibration mill, a high-speed stirrer, a sand mill and a homogenizer;
the hot solution in the step (3) comprises one or more of deionized water, absolute ethyl alcohol, toluene, N-methyl pyrrolidone and N, N-dimethylformamide; the temperature of the hot solution is 40-100 ℃;
the composite heat dissipation film is respectively an ultrathin heat conduction silica gel pad and a graphene film in oriented arrangement from bottom to top, the thickness of the ultrathin heat conduction silica gel pad is 5-50 microns, the heat conductivity coefficient is 5-17W/(m.K), the thickness of the graphene film in oriented arrangement is 10-80 microns, and the heat conductivity coefficient is 1500-1780W/(m.K).
The structure of the composite heat dissipation film is shown in figure 1:
the composite heat dissipation film can be also attached with a PET (polyethylene terephthalate) protective film, and the composite heat dissipation film sequentially comprises the PET protective film, an ultrathin heat conduction silica gel pad, a graphene film in directional arrangement and the PET protective film from bottom to top. The thickness of the PET protective film is 0.012 mm-0.25 mm, the thickness of the ultrathin heat-conducting silica gel pad is 5-50 mu m, the thickness of the graphene film in oriented arrangement is 10-80 mu m, and the thickness of the PET protective film is 0.012 mm-0.125 mm.
The structure of the composite heat dissipation film is shown in FIG. 2:
the preparation method of the composite heat dissipation film comprises the following steps:
(1) preparing a paste material of the ultrathin heat-conducting silica gel pad: weighing 10-28 parts of vinyl silicone oil, 0.5-3 parts of hydrogen-containing silicone oil, 0.10-0.25 part of platinum catalyst, 0.02-0.05 part of inhibitor, 1-3 parts of titanate silane coupling agent, 50-80 parts of nano carbon balls and 100 parts of spherical alumina according to parts by mass, uniformly stirring in a planetary mixer, and then mixing with 5-15 parts of raw rubber in a mill to obtain a paste material.
(2) And (3) calendering and forming: coating the paste material of the ultrathin heat-conducting silica gel pad on one surface of a graphene film, attaching PET protective films on two surfaces of the graphene film, rolling and laminating the graphene film by a rolling machine, transferring the graphene film into a vulcanizing machine, vulcanizing the graphene film at two temperature regions of 120 ℃ and 150 ℃, wherein the vulcanizing time of each temperature region is 10-20 min, completely performing thermocuring molding on the paste material of the heat-conducting silica gel pad to form the ultrathin heat-conducting silica gel pad, and finally obtaining the directly-used composite heat dissipation film.
The heat conductivity coefficient of the ultrathin heat-conducting silica gel pad paste material in the step (1) is 5-17 (W/m.K);
the particle size of the spherical alumina in the step (1) is 10-35 nm, the particle size of the nano carbon spheres is 15-30 nm, the viscosity of the vinyl silicone oil is 1500-3000 cps, the mass fraction of vinyl is 0.14%, the hydrogen content of the hydrogen-containing silicone oil is 0.16-0.36%, the inhibitor is ethynyl cyclohexanol, and the crude rubber is Dongjue 110-2S crude rubber.
The invention has the beneficial effects that:
(1) the modified graphene comprises graphene and carbon nanotubes, the carbon nanotubes play a bridging role between graphene sheets, the problems that the graphene sheets prepared by a mechanical method are uneven in size and gaps exist in mutual overlapping are solved, line-surface contact and surface-surface contact are realized, a heat conduction network is formed, and the high heat conduction characteristic of the graphene is fully exerted. In addition, the modifier is added in the process of preparing the graphene film, and the graphene film has good bending resistance, flexibility and impact resistance, higher thermal conductivity and thermal radiance, difficult powder falling and strong processability. In addition, the graphene film is in oriented arrangement, has high thermal conductivity up to 1780 (W/m.K), has excellent heat dissipation performance, and can reduce the temperature of a heat source at 100 ℃ to about 48.8 ℃.
(2) The composite heat dissipation film comprises the ultrathin heat conduction silica gel pad and the graphene film in directional arrangement, the ultrathin heat conduction silica gel pad has good heat conductivity, insulativity, compressibility and viscoelasticity, can replace the traditional double faced adhesive tape and is in direct contact with the graphene film and a heat source, the contact thermal resistance between the heat dissipation film and the heat source is greatly reduced, and the rapid heat transfer is realized.
Drawings
FIG. 1 composite thermal film (1) represents an oriented graphene film; (2) indicating ultrathin heat-conducting silica gel pad
FIG. 2 composite heat dissipating film (1) represents a PET protective film; (2) represents an oriented graphene film; (3) representing an ultrathin heat-conducting silica gel pad; (4) PET protective film
FIG. 3 SEM picture of oriented graphene film
Detailed Description
The present invention is further described with reference to the following examples, which are only preferred embodiments of the present invention, and therefore should not be construed as limiting the scope of the invention, which is defined by the claims and the description.
The test method of the oriented graphene film and the composite heat dissipation film comprises the following steps:
(1) and (3) bending resistance test: fixing two ends of the sample on an HM-8666 bending resistance tester with a force of 0.98N, starting a bending test under the conditions that the bending radius is 5mm and the bending angle is 180 degrees, and testing whether the sample can be bent more than 10000 times.
(2) Impact resistance test:
impact resistance refers to the ability of a paint film to deform rapidly without cracking or falling off when subjected to high speed gravity. A weight, having a mass of 1kg, is dropped onto the coated panel from different heights to subject the paint film to an elongation deformation without cracking and falling, the maximum height representing the impact resistance of the paint film, usually expressed in centimeters (cm).
(3) Flexibility test:
a flexibility tester is adopted to carry out testing according to the standard of GB1731 paint film flexibility testing method, namely a rigid roller with the diameter of 1mm is used as an axis, a sample is folded in half for 1 time, and whether the sample cracks or peels is observed.
(4) And (3) thickness testing: thickness is measured by a film thickness gauge, unit: mum of
(5) And (3) testing the thermal emissivity:
an SR-5000 infrared Fourier tester (Israel SR-5000) was used at an ambient temperature of 23 + -2 deg.C and a humidity of 50 + -5% R.H, according to the detection standard GJB 5023.2-2003 section 2 of the Material and coating reflectivity and emissivity test method: emissivity > was measured.
(6) And (3) testing thermal conductivity:
the measurement was carried out by using a laser thermal conductivity tester (relaxation resistant LFA 467) and a differential scanning calorimeter (relaxation resistant DSC214) under the conditions of an ambient temperature of 23. + -. 2 ℃ and a humidity of 50. + -. 5% R.H, according to the standard test method for measuring thermal diffusivity by a flash method in accordance with the test standard ASTM E1461-13.
The test specimens were prepared to the required shape dimensions for the grips (discs 25.4mm in diameter measured in the transverse direction and 12.7mm in diameter measured in the longitudinal direction). The thickness of the sample was measured and recorded using a thickness gauge. Adjusting the instrument to level the sampleAnd the sample is stably placed in a corresponding sample tray to ensure that the sample is vertical and stable, and is placed in a furnace body of a laser thermal conductivity instrument. Setting detection parameters and a temperature setting program, starting detection, and measuring the thermal diffusion coefficient alpha. Measuring the density rho of the sample by using a balance and a drainage method, and measuring the specific heat capacity C of the sample by using a differential scanning calorimeterp。
Calculating formula K ═ alpha C according to thermal conductivitypρ, calculating the thermal conductivity K of the sample.
(7) And (3) testing heat dissipation performance:
the heat dissipation test is carried out by adopting a thermal management simulation tester TT-SIM, the thermal management simulation tester comprises a platform heat source, a programmable constant power control system, a data processing system, a data management system and the like, and the performance of a heat dissipation material or a heat dissipation scheme in practical application is evaluated by simulating the states of different electronic devices in practical work and accurately measuring the actual temperatures of the electronic devices under different operating powers and different heat management schemes. Namely, according to the temperature measurement of a heating source under the condition of constant power, data of the influence of the heat dissipation material on the temperature of the device is obtained, and quantitative evaluation is given to the heat dissipation performance of the material. The test procedure was as follows:
a. firstly, attaching a composite heat dissipation film on a heat source, then starting a power supply, setting parameters through a programmable constant power control system, inputting required power, testing time and the like;
b. the test button is clicked, the test is started according to the set power and time, and the data processing system monitors and records the ambient temperature T in real time0And the temperature T of the heat source, and after the temperature of the heat source is stable and the test is finished, the power supply is closed.
c. Calculating temperature rise delta T-T0The smaller the temperature rise value is, the better the heat dissipation effect of the composite heat dissipation film is.
The materials used in the examples of the invention and comparative examples are as follows:
a represents graphite powder, A-1 is crystalline flake graphite powder, the particle size is 8000 meshes; a-2 is expanded graphite powder with the grain size of 4000 meshes; a-3 is artificial graphite with the grain diameter of 400 meshes.
B represents a carbon nanotube, B-1 is a hydroxylated carbon nanotube having a tube diameter of 5nm and a length of 5 μm, and B-2 is a carboxylated carbon nanotube having a tube diameter of 50nm and a length of 35 μm.
C represents a surfactant, C-1 is polyvinylpyrrolidone, C-2 is polyvinyl alcohol, and C-3 is sodium polystyrene sulfonate.
D represents a solvent, D-1 is deionized water, and D-2 is absolute ethyl alcohol.
F represents a bead.
G represents modified graphene, G-1, G-2, G-3 and G' -1 respectively represent modified graphene prepared under different conditions.
H represents a solvent, H-1 is deionized water, and H-2 is N' N-dimethylformamide.
I represents a film-forming agent, and I-1 is acrylic acid modified waterborne polyurethane with the solid content of 25 percent, the viscosity of 100cps and the particle size of emulsion particles of 50 nm; i-2 is acrylic acid modified waterborne polyurethane with the solid content of 40 percent, the viscosity of 500cps and the particle size of emulsion particles of 10 nm; i-3 is acrylic emulsion.
J represents a curing agent, and J-1 is self-emulsifying polyisocyanate with-NCO content of 16% and viscosity of 500 cps; j-2 is a self-emulsifying polyisocyanate having an-NCO content of 48% and a viscosity of 6500 cps.
K represents a modifier, the structural formula is shown as a formula (1),
in the formula (1), R1Is an alkyl group of C1-C3 or a hydrogen atom, R2Is a hydrogen atom or a methyl group, R3Is a straight chain alkyl radical, R4、R5、R6、R7、R8At least 3 of the groups are polar groups, the rest are hydrogen atoms, the polar groups are sulfonic groups and/or carboxyl groups, and n is an integer of 1-3.
The structural formula of K-1 is shown as a formula (1), wherein R1Is a hydrogen atom, R2、R3Are each methyl, R4，R5，R6，R7，R8Are all carboxyl groups, and n is 1.
The structural formula of K-2 is shown as a formula (1), wherein R1Is a hydrogen atom, R2Is a hydrogen atom, R3Is propyl, R4，R5，R6，R7，R8Are all carboxyl, and n is 3.
K-3 has a structural formula shown in formula (1), wherein R1Is a hydrogen atom, R2、R3Are each methyl, R4，R5，R6，R7，R8All are sulfonic acid groups, and n is 1.
L represents an auxiliary agent, L-1 comprises a leveling agent RM-2020, a non-silicon aqueous system defoaming agent BYK-019, dipropylene glycol monomethyl ether, and aqueous high-density polyethylene wax with the viscosity of 100cps and the PH of 8, and the mass ratio of the four is 1.5: 1: 7: 0.5; l-2 comprises an antifoaming agent TEGO Foamex 810, dipropylene glycol monobutyl ether and aqueous high-density polyethylene wax with the viscosity of 50cps and the PH of 7.5, and the mass ratio of the three components is 1.5: 0.5: 1.
M represents a hot solution, M-1 is deionized water with the temperature of 40 ℃, and M-2 is deionized water with the temperature of 80 ℃; m-3 is N-methyl pyrrolidone with the temperature of 100 ℃.
TABLE 1 formulation and Process parameters (unit: kg) for preparing modified graphene
TABLE 2 formulation and Process parameters (unit: kg) for preparing graphene films in oriented arrangement
Preparation of oriented graphene films
(1) Preparing modified graphene: weighing graphite powder, carbon nanotubes, a surfactant, a solvent and grinding beads according to the formula and the dosage shown in the table 1, placing the materials in ball milling equipment, carrying out ball milling for 1-6 h at the speed of 1000 r/min-4000 rpm, discharging, centrifuging the obtained slurry for 10-30 min at the rotating speed of 1500-2500 rpm, collecting supernatant, and freeze-drying the supernatant to respectively obtain the modified graphene G-1, G-2, G-3 and G' -1.
(2) Material preparation and material mixing: weighing the modified graphene, the solvent, the film forming agent, the curing agent, the modifier and the auxiliary agent according to the formula and the dosage shown in the table 2, stirring for 5-120 min in a high-speed stirrer at the rotating speed of 1500-4000 rpm, taking out the slurry, centrifuging the slurry at the rotating speed of 1000-10000 rpm for 10-30 min, and collecting the uniform slurry on the upper layer.
(3) Vacuum filtration: and (3) carrying out vacuum filtration on the slurry obtained in the step (2), and intermittently adding a hot solution to assist in filtration while carrying out filtration to obtain the graphene membrane in directional arrangement.
The preparation method of the composite heat dissipation film comprises the following steps:
(1) preparing a paste material of the ultrathin heat-conducting silica gel pad: weighing 28 parts of vinyl silicone oil with the viscosity of 3000cps, 1.2 parts of hydrogen-containing silicone oil with the hydrogen content of 0.16%, 0.10 part of platinum catalyst, 0.025 part of ethynyl cyclohexanol inhibitor, 3 parts of titanate silane coupling agent, 80 parts of nano carbon spheres with the particle size of 15nm and 100 parts of spherical alumina with the particle size of 30nm according to the mass parts, placing the mixture in a planetary mixer for uniform stirring, then mixing the mixture and 10 parts of Dongjue 110-2S raw rubber in a mill, and finally collecting the paste.
(2) Laminating ultra-thin heat conduction silica gel pad in the graphite fin: coating the paste materials prepared in the steps on one surface of the graphene film in the oriented arrangement prepared in the examples 1-5 and the comparative examples 1-1, 1-2, 1-3, 1-4 and 1-5 respectively, attaching a PET protective film on two surfaces of the graphene film, calendering and laminating the graphene film by a calender, then vulcanizing the graphene film in a vulcanizing machine with two temperature regions of 120 ℃ and 150 ℃, and vulcanizing each temperature region for 20min respectively to realize complete thermosetting molding of the heat-conducting silica gel pad, thereby obtaining the composite heat dissipation film consisting of the PET protective film, the graphene film in the oriented arrangement, the ultrathin heat-conducting silica gel pad and the PET protective film. At this time, the thickness of the ultra-thin heat-conducting silica gel pad is 10 μm, the compressibility is 40%, and the thermal conductivity is 7W/m.K
TABLE 3 Properties of graphene films aligned
Table 4 test of heat dissipation effect of composite heat dissipation film
As can be seen from fig. 3, the graphene film is sheet-shaped, is closely arranged in parallel orientation, and has a large specific surface area. As can be seen from Table 3, the graphene film with the oriented arrangement has the thickness of 10-80 μm, excellent bending resistance, impact resistance and flexibility, and higher thermal emissivity and thermal conductivity; as can be seen from table 4, the composite heat dissipation film is prepared by attaching the graphene film in the oriented arrangement to the ultrathin heat conductive silica gel pad, and has excellent heat dissipation performance. As can be seen from comparison between examples 1 to 3 and comparative examples 1-1, 2-1 and 3-1, after the modifier represented by formula (1) is added in the preparation process of the graphene film, the properties of the graphene film, such as bending resistance, impact resistance, flexibility, thermal emissivity and thermal conductivity, are obviously improved; under the condition of not adding a modifier, the obtained graphene film has poor mechanical properties, low thermal conductivity and thermal emissivity and poor heat dissipation performance.
In the formula (1), R1Is an alkyl group of C1-C3 or a hydrogen atom, R2Is a hydrogen atom or a methyl group, R3Is a straight chain alkyl radical, R4、R5、R6、R7、R8At least 3 of the groups are polar groups, the rest are hydrogen atoms, the polar groups are sulfonic groups and/or carboxyl groups, and n is an integer of 1-3.
Specifically, the following description is provided: the ultrathin heat-conducting silica gel pad has the thickness of 5-50 mu m, the compression rate of 30-80 percent and the heat conductivity of 5-17W/m.K, and can also realize the purpose of the invention; the ultrathin heat-conducting silica gel pad can be purchased from the market, and the models such as Fujipoly Fuji Sarcon XR-E, XR-HE and the like all meet the use requirements.
Claims (10)
1. The graphene film is characterized by comprising the following components in parts by mass: 100 parts of modified graphene, 250-450 parts of solvent, 15-50 parts of film forming agent, 0.5-1.5 parts of curing agent, 0.25-15 parts of modifier and 3-10 parts of other auxiliary agents, wherein the thickness of the graphene film is 10-80 microns;
the structural formula of the modifier is shown as a formula (1),
in the formula (1), R1Is an alkyl group of C1-C3 or a hydrogen atom, R2Is a hydrogen atom or a methyl group, R3Is a straight chain alkyl radical, R4、R5、R6、R7、R8At least 3 of the groups are polar groups, the rest are hydrogen atoms, the polar groups are sulfonic groups and/or carboxyl groups, and n is an integer of 1-3;
the preparation method of the modified graphene comprises the following steps: placing graphite powder, carbon nano tubes, a surfactant, a solvent and grinding beads in a ball milling device according to the mass ratio of (10-30) to 5 to (0.15-0.3) to 250 to 100, ball milling for 1-6 h at the speed of 1000-4000 r/min, discharging, centrifuging the obtained slurry for 10-30 min at the rotating speed of 1500-2500 rpm, collecting supernatant liquid, and freeze-drying the supernatant liquid to obtain modified graphene powder;
the graphene film is a graphene film in an oriented arrangement.
2. The graphene film according to claim 1, wherein in the formula (1), R is1Is a hydrogen atom, R2Is a hydrogen atom or a methyl group, R3Is C1-C3 alkyl, R4、R5、R6、R7、R8All are sulfonic acid groups, and n is an integer of 1-3.
3. The graphene film according to claim 1, wherein in the formula (1), R is1Is a hydrogen atom, R2Is a hydrogen atom or a methyl group, R3Is C1-C3 alkyl, R4、R5、R6、R7、R8All are carboxyl, and n is an integer of 1-3.
4. The graphene film according to claim 3, wherein R in the formula (1)1Is a hydrogen atom, R2Is methyl, R3Is methyl, R4、R5、R6、R7、R8Are all carboxyl groups, and n is 1.
5. The graphene film according to claim 3, wherein R in the formula (1)1Is a hydrogen atom, R2Is a hydrogen atom, R3Is propyl, R4、R5、R6、R7、R8Are all carboxyl, and n is 3.
6. The graphene membrane according to claim 1, wherein the modified graphene contains a polar hydrophilic group, and the polar hydrophilic group comprises one or more of a carboxyl group, a sulfonic group, a sulfuric group, an amino group, an amine group, a hydroxyl group, an amide group, and an ether bond.
7. The graphene film of claim 1, wherein the film-forming agent is one or both of a polyvinyl alcohol emulsion, an acrylic resin, and a polyurethane emulsion.
8. The method for preparing the graphene film according to any one of claims 1 to 7, comprising the steps of:
(1) preparing modified graphene: placing graphite powder, carbon nano tubes, a surfactant, a solvent and grinding beads in a ball milling device according to the mass ratio of (10-30) to 5 to (0.15-0.3) to 250 to 100, ball milling for 1-6 h at the speed of 1000-4000 r/min, discharging, centrifuging the obtained slurry for 10-30 min at the rotating speed of 1500-2500 rpm, collecting supernatant liquid, and freeze-drying the supernatant liquid to obtain modified graphene powder;
(2) material preparation and material mixing: sequentially weighing modified graphene, a solvent, a film forming agent, a curing agent, a modifier and other auxiliaries according to the mass ratio of 100: 250-450: 15-50: 0.5-1.5: 0.25-15: 3-10, stirring for 5-120 min at the rotating speed of 1500-4000 rpm in a high-speed stirrer, taking out slurry, centrifuging the slurry at the rotating speed of 1000-10000 rpm for 10-30 min, and collecting the upper-layer uniform slurry;
(3) vacuum filtration: and (3) carrying out vacuum filtration on the slurry obtained in the step (2), and intermittently adding a hot solution for assisting in filtration while carrying out filtration to obtain the graphene film in the oriented arrangement, wherein the temperature range of the hot solution is 40-100 ℃.
9. The composite heat dissipation film is characterized by being respectively an ultrathin heat conduction silica gel pad and a graphene film which is arranged in an oriented mode from bottom to top; the graphene film is the graphene film according to any one of claims 1 to 7 or the graphene film prepared by the preparation method according to claim 8.
10. The composite heat dissipation film of claim 9, wherein the composite heat dissipation film comprises, from bottom to top, a PET protection film, an ultra-thin heat conductive silicone pad, a graphene film in an oriented arrangement, and a PET protection film.
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| CN111171552A (en) * | 2020-02-20 | 2020-05-19 | 上海超碳石墨烯产业技术有限公司 | Graphene flexible conductive composite film and preparation method thereof |
| CN113387702A (en) * | 2021-06-23 | 2021-09-14 | 浙江原邦材料科技有限公司 | High-thermal-conductivity graphene composite heat dissipation film and preparation method thereof |
| CN113717702B (en) * | 2021-08-31 | 2023-09-29 | 中钢天源股份有限公司 | Graphene composite heat sink and preparation method thereof |
| CN115231560A (en) * | 2022-06-28 | 2022-10-25 | 烯玺科技(上海)有限公司 | Preparation method of graphene continuous film heat-conducting fin |
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