CN114058081A - Preparation method and application of graphene-based heat-conducting and heat-dissipating composite material - Google Patents
Preparation method and application of graphene-based heat-conducting and heat-dissipating composite material Download PDFInfo
- Publication number
- CN114058081A CN114058081A CN202111575607.9A CN202111575607A CN114058081A CN 114058081 A CN114058081 A CN 114058081A CN 202111575607 A CN202111575607 A CN 202111575607A CN 114058081 A CN114058081 A CN 114058081A
- Authority
- CN
- China
- Prior art keywords
- heat
- graphene
- composite material
- conducting
- dissipating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a preparation method of a graphene-based heat conduction and dissipation composite material, which comprises the following steps: activating porous graphene and needle-shaped heat conduction and dissipation particles, mechanically stirring and dispersing, and then ultrasonically dispersing to obtain uniformly dispersed activation treatment liquid; adding a particle surface modifier into the activation treatment liquid, carrying out wet grinding and shearing dispersion treatment in a high-speed stirring manner to obtain mixed slurry, heating the mixed slurry in a protective environment, cooling the mixed slurry to obtain a modified graphene-based heat-conducting and heat-dissipating solution, separating and filtering the solution, and then carrying out high-temperature sintering and drying treatment to obtain the graphene-based heat-conducting and heat-dissipating composite material. According to the invention, through activation, surface modification and high-temperature sintering treatment, the needle-shaped high-thermal-conductivity material is directionally linked on the phase interface of the graphene method, so that the structural complementation and the thermal conductivity isotropy can be realized, and the thermal conductivity and heat dissipation characteristics of the composite material are greatly improved. The invention also provides application of the composite material electronic component plastic packaging material prepared by the method.
Description
Technical Field
The invention belongs to the technical field of heat conduction materials, and particularly relates to a preparation method and application of a heat conduction and heat dissipation composite material for packaging electronic components.
Background
The development of large capacity, high power, high integration and small and light weight of electronic components brings a great deal of heat accumulation problem, and the temperature rise can reduce the problems of stable performance and service life of electronic devices, thus bringing serious potential safety hazard. The traditional electronic plastic package material cannot meet the requirement of high development of electronic components.
The unique two-dimensional lamellar structure of graphene has pi-pi conjugation with each other, a compact and ordered lamellar structure is easy to realize, the ordered lamellar structure constructs a propagation path in a plane direction and is beneficial to phonon propagation in the plane direction, the in-plane thermal conductivity of the graphene can reach as high as 5300W/m.K, the graphene has great potential as a thermal interface material in the aspect of removing redundant heat generated by a high-integrated electronic device, but the interlayer structure defect of the graphene can become a heat flow scattering center, the interlayer phonon scattering problem exists, the heat dissipation capacity of the graphene is weakened due to the defect of interface structure rearrangement, the intrinsic thermal conductivity is reduced, the graphene has the characteristic of anisotropic heat conduction that the in-plane thermal conductivity is high and the out-plane thermal conductivity is low, the problems of difficult dispersion, easy agglomeration and high cost exist, and the practical application is limited to a certain extent.
Therefore, it is necessary to solve the above problems.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and firstly provides a preparation method of a graphene-based heat conduction and dissipation composite material.
The preparation method of the graphene-based heat conduction and dissipation composite material provided by the invention comprises the following steps:
s1, activating, mechanically stirring and dispersing the porous graphene and the needle-shaped heat conduction and dissipation particles, and then ultrasonically dispersing to obtain uniformly dispersed activation treatment liquid;
s2, adding a particle surface modifier into the activation treatment liquid, and carrying out wet grinding and shearing dispersion treatment in a high-speed stirring manner to obtain mixed slurry;
s3, transferring the mixed slurry to a hydrothermal kettle, heating in a protective environment, and cooling to obtain a modified graphene-based heat conduction and dissipation solution;
s4, separating and filtering the modified graphene-based heat conduction and dissipation solution, and then sintering and drying at high temperature to obtain the graphene-based heat conduction and dissipation composite material.
The invention also provides application of the graphene-based heat-conducting and heat-dissipating composite material prepared by the method in plastic package materials of electronic components.
The invention has the following technical effects:
(1) aiming at the defects of the graphene structure and the corresponding heat conduction anisotropy, the method combines the structural characteristics of cheap high heat conduction particles, and realizes the structural complementation and the heat conduction isotropy by directionally linking needle-shaped high heat conduction materials on the phase interface of the graphene method through activation, surface modification and high-temperature sintering treatment, thereby greatly improving the heat conduction and heat dissipation characteristics of the composite material.
(2) According to the invention, a porous graphene material is used for assembling a framework with a regulated form, needle-shaped fibrous or rod-shaped heat conduction particles are used as epitaxial connecting branches, a novel high-heat-conduction and heat-dissipation composite material with an interpenetrating structure is constructed, and meanwhile, surface modifier organic dispersion and high-temperature heating treatment are combined to prepare the non-ionic bonding heat conduction and heat dissipation material, no other by-product or impurity is introduced in the whole process, so that the subsequent use of the heat conduction and heat dissipation performance of the composite material is facilitated.
(3) The preparation method of the invention has the advantages of simplicity, less equipment investment, short process flow, low cost and easy realization of industrial production.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The graphene heat conduction mainly comes from a sp2 bonded network, the graphene sheet layers with high axial direction have high heat conduction performance, and the sheet layers are disordered in arrangement and have low normal phase heat conduction coefficient for forming a core-shell structure. At present, the graphene used as a heat conduction and dissipation material mainly comprises three main types of graphene fibers, graphene films and graphene composite materials. The unique two-dimensional lamellar structure of graphene fiber has great slenderness ratio, and folding takes place easily in the fibre, and the fold is piled up and can't be extended to orientation control can't realize, can form great space, and graphene fiber is inside to present loose pile-up's state, and density is only 1mg/cm3Generally lower than the density of conventional carbon fibers (1.8/cm)3) The thermal conductivity of the graphene fiber can reach about 1575W/m.K to the maximum, and is far lower than the intrinsic thermal conductivity (5300W/m.K) of single-layer graphene. In order to obtain a two-dimensional lamellar structure graphene film with a high orientation degree, in the prior art, a mechanical pressure mode is generally adopted to reduce holes and wrinkles in the film so as to enhance the orientation of a graphene lamellar layer along the in-plane direction and reduce phonon scattering, and the in-plane thermal conductivity of the finally obtained graphene film can reach about 3200W/m.K, but the out-of-plane normal phase thermal conductivity is only about 14.8W/m.K at the moment, and the requirements of the electronic packaging field with high power and high heat concentration cannot be met.
The graphene heat-conducting composite material is generally prepared by compounding a polymer and a high-heat-conducting graphene filler, and is used in the field of interface heat conduction and heat dissipation of various shapes. The graphene heat-conducting composite material on the market is mainly prepared by a physical blending mode with graphene as a filler. The graphene or graphene oxide filler is prepared by chemically bonding an interface between graphene and organic resin through graphene modification treatment, but the existence of a large amount of phonon scattering can still be caused to reduce the heat-conducting property of the composite material due to the existence of various lattice defects which cannot be repaired and residual functional groups of the graphene or graphene oxide filler. In an organic-inorganic mixed dispersion system, graphene sheets cannot be mutually covered or overlapped in an organic film substrate, a heat conduction network is not communicated smoothly, polymer chains around the graphene sheets seriously block the vibration and heat transfer of phonons, so that the heat conductivity of the composite material is still in a low value, most of the heat conductivity is in a range of 1.0-3.0W/m.K, and the requirements of heat conduction and heat dissipation of high-power and highly-integrated electronic products cannot be met at all.
Aiming at the defects, the invention provides a preparation method of a graphene-based heat conduction and dissipation composite material, which comprises the following steps:
s1, respectively activating, stirring and dispersing the porous graphene and the needle-shaped heat conduction and dissipation particles, and then ultrasonically dispersing to obtain uniformly dispersed activation treatment liquid.
Specifically, the sheet diameter of the porous graphene is less than 800nm, the thickness of the porous graphene is less than 200nm, and the porous graphene has a better specific surface area.
Specifically, the heat conduction and dissipation particles comprise at least one of single-walled carbon nanotubes, rodlike boron nitride, acicular aluminum oxide or radial acicular silicon carbide, and have the particle size of 10-100 nm and the length of 1-20 microns. The material has stable chemical property, high heat conductivity coefficient, good heat dispersion and better wear resistance, is matched with the porous graphene in a needle-shaped or rod-shaped form, is favorable for filling and doping pores of the porous graphene in the subsequent treatment process and linking the pores to a porous graphene normal phase interface, and fills the defects of covalent bonding modification points of the porous graphene so as to form a composite material which takes the porous graphene as a framework and is embedded and adsorbed with a high-heat-conductivity heat-dissipation material.
Furthermore, the heat conduction and dissipation particles are subjected to activation treatment, so that surface active groups of the heat conduction and dissipation particles are hydroxylated, chemical adsorption and bonding with porous graphene are facilitated, dispersion of heat conduction and dissipation particle materials is promoted, curling or agglomeration is prevented, the heat conduction and dissipation particles after forming a mixed solution can be uniformly distributed, the physical or chemical adsorption effect is uniform, and the composite material can form uniform chemical structure characteristics after subsequent heating treatment.
The activating treatment comprises the following specific steps: mixing and diluting deionized water and concentrated nitric acid to prepare a nitric acid solution with the concentration of 10% -30%, gradually putting porous graphene and heat conducting and radiating particles into the nitric acid solution in batches, mechanically stirring and dispersing at the rotating speed of 400-700 rpm for 2-4 h, and then transferring into an ultrasonic device for ultrasonic dispersion for 1-1.5 h to obtain an activation treatment solution which is uniformly mixed.
During activation treatment, the concentration of the heat-conducting and heat-dissipating particles in a nitric acid solution is 12 mg-13 mg/L, and the mass fraction ratio of the graphene to the heat-conducting and heat-dissipating particles is 10: 2 to 3.
S2, adding a particle surface modifier into the mixed solution, and carrying out wet grinding and shearing dispersion treatment by a high-speed stirring mode to obtain mixed slurry.
In order to ensure that the heat-conducting and heat-dissipating particles are not agglomerated and can be uniformly dispersed in the mixed solution, the particle surface modifier is added into the mixed solution in the step, so that the surface tension among various constituent phases in the mixed solution can be improved, a uniform and stable dispersion system is formed, the heat-conducting and heat-dissipating particles effectively realize organic chemical linkage, simple physical adsorption hybridization is avoided, and the uniform chemical adsorption and bonding state of the porous graphene is ensured.
The particle surface modifier is any one of sodium dodecyl benzene sulfonate, polyvinylpyrrolidone, sodium polycarboxylate and sodium polyvinyl sulfonate; the mass ratio of the particle surface modifier to the heat conduction and dissipation particles is 0.15-2%.
The particle surface modifier can be slowly added into the activation treatment liquid prepared in the step S2 by using a liquid transfer gun within 20-30min under the high-speed stirring condition of the rotating speed of 400-600 rpm, then wet grinding treatment is carried out for 1-2h under the shearing and extrusion of two zirconia microspheres with different sizes, and then ultrasonic dispersion is carried out for 1-2h, so as to obtain the mixed slurry.
When wet grinding is carried out, the size and the proportion of the zirconia microspheres are as follows: 60 percent of zirconia microspheres with the particle size of 1.0-1.4 mm, 40 percent of zirconia microspheres with the particle size of 8mm, 600-800 rpm of stirring speed and 20-30min of wet milling time; the weight ratio of the powder to the zirconia balls is 1: 1. according to the invention, the dispersible and agglomerated particles are subjected to wet grinding treatment, so that the particle sizes in the mixed slurry can be basically consistent, the mixed slurry is ensured to be in a state of stable dispersion, uniform particle size and stable chemical action, and the embedding and adsorption between the porous graphene and the heat-conducting and heat-dissipating particles are facilitated.
S3, transferring the mixed slurry to a hydrothermal kettle, heating in a protective environment, and cooling to obtain the modified graphene-based heat conduction and dissipation solution.
The mixed slurry is heated in the step, so that the polycondensation reaction can be generated among the particle surface modifiers, between the heat conduction and heat dissipation particles and among the heat conduction and heat dissipation particles, and the bonding of non-co-construction bonds is realized. The heating temperature of the mixed slurry in the hydrothermal kettle is 120-160 ℃, the heating time is 2-3 hours, the mixed slurry is heated and stirred at the speed of 400-600 rpm.
S4, separating and filtering the modified heat conduction and dissipation particle solution, and then sintering and drying at high temperature to obtain the graphene-based heat conduction and dissipation composite material.
The modified heat conduction and dissipation particle solution is separated by a centrifugal machine, the speed of the centrifugal machine is 7000-10000 rpm, the pH value of the solution is adjusted to be 5-6 during separation, the solution is in an acidic state, weak adsorption is formed between particles through hydrogen bonds and hydroxyl groups, ionization balance on the surfaces of the particles is broken, and sedimentation is facilitated. And (4) drying the separated precipitate for 20-24 hours at the temperature of 60-80 ℃ in vacuum to obtain the composite material powder.
And the separated and filtered powder is put in a vacuum drying furnace for high-temperature sintering, so that the problems of organic molecules, oxygen-containing active groups and graphene surface defects among the composite particles can be repaired and graphitization can be realized, the stability of the composite material and phonon heat transfer of the composite material are improved, the defect of a graphene-based normal phase structure can be improved, and phonon scattering can be reduced. Specifically, the high-temperature sintering temperature is 1200-1500 ℃, the heating rate is 5-10 ℃/min, and the natural cooling is carried out after the heat preservation is carried out for 2-4 h.
Through tests, the normal thermal conductivity coefficient of the prepared graphene-based thermal conductive composite material can reach 105-52W/m.K, and the graphene-based thermal conductive composite material has good thermal conductivity.
The invention also provides application of the graphene-based heat-conducting composite material prepared by the preparation method as a plastic packaging material on an electronic component, and the graphene-based heat-conducting composite material can be used as a film or a coating to cover the surface of the electronic component, so that the heat dissipation effect of the electronic component can be improved.
The preparation method of the graphite powder with heat storage and heat conduction sheet is further described in detail with reference to specific embodiments.
Example 1:
s1 is prepared from 20mg porous graphene (sheet diameter less than 800nm, thickness less than 200nm) and 6mg single-walled carbon nanotube (outer diameter 15nm, length 20 μm). Mixing and diluting 500mL of deionized water and 150mg of nitric acid solution with the concentration of 30%, gradually adding porous graphene and single-walled carbon nanotubes in batches under the stirring action of the rotation speed of 400rpm, mechanically stirring and dispersing for 4 hours, transferring into an ultrasonic device, and continuing to ultrasonically disperse for 1.5 hours to obtain uniformly mixed activation treatment solution;
s2, transferring 200mL of the activation treatment solution prepared in the step S1 into an abrasive tank, transferring 4mL of sodium dodecyl benzene sulfonate solution with the mass concentration of 30% into the abrasive tank by using a liquid transfer gun within 20min under the action of the stirring speed of 600rpm, continuously stirring for 2 hours, then adding 26mg of zirconium oxide grinding balls with different diameters according to the proportion of 6(M (R1mm)):4(M (R8mm)), continuously ball-milling for 30min under the action of 800rpm, and then ultrasonically dispersing for 1 hour to obtain uniformly dispersed primary graphene-based heat-conducting and heat-dissipating composite mixed slurry;
s3, transferring the mixed slurry into a hydrothermal kettle under the protection of argon (Ar) gas, heating at 160 ℃ for 2.5h while stirring at the stirring speed of 400rpm, and cooling to obtain the modified graphene-based solution.
S4, separating the modified graphene-based heat conduction and dissipation solution by using a centrifugal machine, adding a nitric acid diluent under the action of the rotation speed of 10000rpm, adjusting the pH value of the solution to 6 to obtain a precipitation layered solution, pouring out the supernatant, and then drying the obtained precipitate in an oven at 80 ℃ for 20 hours in vacuum to obtain the composite material powder. And then heating the composite material powder in a vacuum high-temperature furnace at 1500 ℃, heating up at a speed of 5 ℃/min for 4h, and naturally cooling to obtain the graphene-based high-thermal-conductivity heat-dissipation composite material.
Through detection, the heat conductivity coefficient of the graphene-based heat conduction and dissipation composite material prepared in the embodiment is as follows: the surface thermal conductivity was 2486W/mK, and the normal thermal conductivity was 105W/mK. .
Example 2:
s1 is prepared from porous graphene (sheet diameter less than 800nm and thickness less than 200nm), single-walled carbon nanotube (4 mg, outer diameter 10nm and length 8 μm), and needle-like silicon carbide (1 mg, average particle diameter 80nm and length less than 20 μm).
Mixing and diluting 100mg of deionized water and 100mg of 20% nitric acid solution, gradually adding porous graphene, single-walled carbon nanotubes and silicon carbide particles in batches under the stirring action of the rotating speed of 400rpm, mechanically stirring and dispersing for 2 hours, transferring into an ultrasonic device, and continuing to ultrasonically disperse for 1.5 hours to obtain the uniformly mixed activation treatment solution.
S2, transferring 200mL of the activation treatment solution prepared in the step S1 into an abrasive tank, transferring 3mL of polyvinylpyrrolidone solution with the mass concentration of 30% into the abrasive tank by a liquid transferring gun within 20min under the action of the stirring speed of 500rpm, and continuously stirring for 2 hours. Then adding 25mg of zirconia grinding balls with different diameters according to the proportion of 6(M (R1mm)):4(M (R8mm)), continuously carrying out ball milling for 25min under the action of 700rpm of rotating speed, and carrying out ultrasonic treatment for 1 hour to obtain uniformly dispersed primary graphene-based composite material mixed slurry.
S3, transferring the mixed slurry into a hydrothermal kettle under the protection of argon (Ar) gas, heating for 2.5h at the heating temperature of 150 ℃, stirring at the stirring speed of 450rpm while heating, and cooling to obtain the modified graphene-based heat conduction and dissipation solution at the stirring speed of 400 rpm.
S4, separating the modified graphene-based heat conduction and dissipation solution by using a centrifuge, adding a nitric acid diluent under the action of a centrifugal speed of 9000rpm, adjusting the pH value to 5.5 to obtain a precipitation layered solution, pouring out a supernatant, and vacuum-drying the obtained precipitate in an oven at 75 ℃ for 21 hours to obtain composite material powder. And then heating the composite material powder in a vacuum high-temperature furnace at 1400 ℃, at a heating rate of 6 ℃/min and for a heat preservation time of 3.5h, and naturally cooling to obtain the graphene-based high-thermal-conductivity composite material.
Through detection, the heat conductivity coefficient of the graphene-based heat conduction and dissipation composite material prepared in the embodiment is as follows: the heat conductivity coefficient in the surface direction is 2135W/m.K, and the normal heat conductivity coefficient is 86W/m.K.
Example 3:
s1 is prepared from porous graphene (sheet diameter less than 800nm and thickness less than 200nm), single-walled carbon nanotube (outer diameter 7nm and length 10 μm) 3.0mg and needle-like aluminum oxide (average particle diameter 50nm and length less than 20 μm) 2.0 mg.
Mixing and diluting 120mg of deionized water and 80mg of 15% nitric acid solution, gradually adding porous graphene, single-walled carbon nanotubes and aluminum oxide particles in batches under the stirring action of the rotating speed of 600rpm, mechanically stirring and dispersing for 4 hours, transferring into an ultrasonic device, continuing ultrasonic dispersion for 1 hour, and then obtaining uniformly mixed activation treatment solution;
s2, sodium polycarboxylate (5040) is selected as a surface modifier of particles such as graphene; 200mL of the activation treatment solution prepared in the step S1 was transferred to an abrasive tank, and 3mL of a 30% by mass sodium polycarboxylate solution was transferred to the abrasive tank by a pipette gun at a stirring speed of 500rpm and added thereto for 1.5 hours with continuous stirring within 20 minutes. Then adding 24mg of zirconia grinding balls with different diameters according to the proportion of 6(M (R1mm)):4(M (R8mm)), continuously carrying out ball milling for 25min at the rotating speed of 700rpm, and then carrying out ultrasonic dispersion for 1 hour to obtain uniformly dispersed primary graphene-based composite material mixed slurry;
s3, transferring the mixed slurry into a hydrothermal kettle under the protection of argon (Ar) gas, heating for 2h at the temperature of 140 ℃, stirring while heating at the stirring speed of 550rpm, and cooling to obtain the modified graphene-based heat conduction and dissipation solution.
S4, separating the organic modified graphene-based mixed solution by a centrifuge, adding a nitric acid diluent to adjust the pH value to 5.8 under the action of the rotation speed of 8000rpm to obtain a precipitation layered solution, pouring out the supernatant, and then drying the obtained precipitate in an oven at 70 ℃ for 22 hours in vacuum to obtain the composite powder. And then heating the composite powder in a vacuum high-temperature furnace at 1300 ℃, at a heating speed of 8 ℃/min and for 3h, and naturally cooling to obtain the graphene-based high-thermal-conductivity composite material.
Through detection, the heat conductivity coefficient of the graphene-based heat conduction and dissipation composite material prepared in the embodiment is as follows: the surface thermal conductivity was 1773W/m.K, and the normal thermal conductivity was 74W/m.K.
Example 4:
s1 is prepared by selecting three powders of 20mg porous graphene (sheet diameter less than 800nm, thickness less than 200nm), 2.5mg single-walled carbon nanotube (outer diameter 12nm, length 15 μm) and 1.5mg boron nitride (average particle diameter 50nm, length less than 10 μm).
Mixing and diluting 150mg of deionized water and 50mg of 25% nitric acid solution, gradually adding porous graphene, single-walled carbon nanotubes and boron nitride particles in batches under the stirring action of the rotating speed of 700rpm, mechanically stirring and dispersing for 3 hours, transferring into an ultrasonic device, and continuing to ultrasonically disperse for 1 hour to obtain an activation treatment solution which is uniformly mixed;
s2 sodium Polyvinylsulfonate (PSS) is selected as a surface modifier of particles such as graphene; 200mL of the activation treatment solution prepared in the step S1 was transferred to a grinding tank, and 3mL of a 30% sodium polyvinylsulfonate solution was transferred to the grinding tank by a pipetting gun at a stirring speed of 400rpm within 20min, and the mixture was stirred continuously for 1.0 hour. Then adding 24mg of zirconia grinding balls with different diameters according to the proportion of 6(M (R1mm)):4(M (R8mm)), continuously carrying out ball milling for 20min at the rotating speed of 600rpm, and then carrying out ultrasonic dispersion for 1 hour to obtain uniformly dispersed primary graphene-based composite material mixed slurry;
s3, transferring the mixed slurry into a hydrothermal kettle under the protection of argon (Ar) gas, heating at 120 ℃ for 3h while stirring at the stirring speed of 550rpm, and cooling to obtain the modified graphene-based heat conduction and dissipation solution.
S4, separating the organic modified graphene-based mixed solution by a centrifuge, adding a nitric acid diluent to adjust the pH value to 6 under the action of the rotation speed of 7000rpm of the centrifuge speed, obtaining a precipitation layered solution, pouring out the supernatant, and then drying the obtained precipitate in an oven at 60 ℃ for 20 hours in vacuum to obtain the composite powder. And then heating the composite powder in a vacuum high-temperature furnace at 1200 ℃, at a heating rate of 10 ℃/min for 2h, and naturally cooling to obtain the graphene-based high-thermal-conductivity composite material.
Through detection, the heat conductivity coefficient of the graphene-based heat conduction and dissipation composite material prepared in the embodiment is as follows: the face thermal conductivity is about 1926W/m.K, and the normal thermal conductivity is about 52W/m.K.
The above-described embodiments of the present invention are merely exemplary and not intended to limit the present invention, and those skilled in the art may make various modifications, substitutions and improvements without departing from the spirit of the present invention.
Claims (10)
1. A preparation method of a graphene-based heat conduction and dissipation composite material is characterized by comprising the following steps:
s1, activating, mechanically stirring and dispersing the porous graphene and the needle-shaped heat conduction and dissipation particles, and then ultrasonically dispersing to obtain uniformly dispersed activation treatment liquid;
s2, adding a particle surface modifier into the activation treatment liquid, and carrying out wet grinding and shearing dispersion treatment in a high-speed stirring manner to obtain mixed slurry;
s3, transferring the mixed slurry to a hydrothermal kettle, heating in a protective environment, and cooling to obtain a modified graphene-based heat conduction and dissipation solution;
s4, separating and filtering the modified graphene-based heat conduction and dissipation solution, and then sintering and drying at high temperature to obtain the graphene-based heat conduction and dissipation composite material.
2. The method for preparing the graphene-based heat-conducting and heat-dissipating composite material according to claim 1, wherein in the step S1, the porous graphene has a sheet diameter of less than 800nm and a thickness of less than 200 nm.
3. The preparation method of the graphene-based heat-conducting and heat-dissipating composite material of claim 1, wherein in the step S1, the heat-conducting and heat-dissipating particles comprise at least one of single-walled carbon nanotubes, rod-shaped boron nitride, needle-shaped aluminum oxide, or radial needle-shaped silicon carbide, and have a particle size of 10 to 100nm and a length of 1 to 20 μm.
4. The method for preparing the graphene-based heat-conducting and heat-dissipating composite material according to claim 1 or 3, wherein in the step of S1, the step of activating treatment is: putting the porous graphene and the heat conducting and radiating particles into a nitric acid solution with the concentration of 15% -30% in batches, mechanically stirring at a high speed of 400-700 rpm for 2-4 h, and then ultrasonically dispersing for 1-1.5 h; the concentration of the heat-conducting and heat-dissipating particles in the nitric acid solution is 12 mg-13 mg/L, and the mass fraction ratio of the graphene to the heat-conducting and heat-dissipating particles is 10: 2 to 3.
5. The method for preparing the graphene-based heat-conducting and heat-dissipating composite material according to claim 1, wherein in the step S2, the particle surface modifier is any one of sodium dodecylbenzene sulfonate, polyvinylpyrrolidone, sodium polycarboxylate and sodium polyvinyl sulfonate; the mass ratio of the particle surface modifier to the heat conduction and dissipation particles is 0.15-2%.
6. The preparation method of the graphene-based heat-conducting and heat-dissipating composite material according to claim 1 or 5, wherein in the step S2, the particle surface modifier is slowly added into the activation treatment solution under a high-speed stirring condition at a rotation speed of 400-600 rpm, then wet grinding treatment is performed for 20-30min under shearing and extrusion of two zirconia microspheres with different sizes, and then ultrasonic dispersion is performed for 1-2h to obtain the mixed slurry.
7. The preparation method of the graphene-based heat-conducting and heat-dissipating composite material according to claim 1, wherein in the step S3, the mixed slurry is heated in a hydrothermal kettle at a temperature of 120 to 160 ℃ for 2 to 3 hours at a stirring speed of 400 to 600 rpm.
8. The preparation method of the graphene-based heat-conducting and heat-dissipating composite material according to claim 1, wherein in the step S4, the modified heat-conducting and heat-dissipating particle solution is separated by a centrifuge, the centrifuge is operated at 7000-10000 rpm, the pH of the solution is adjusted to 5-6 during separation, and the separated precipitate is vacuum-dried at 60-80 ℃ for 20-24 hours.
9. The preparation method of the graphene-based heat-conducting and heat-dissipating composite material according to claim 1 or 8, wherein in the step S4, the separated and filtered powder is placed in a vacuum drying furnace for high-temperature sintering, the sintering temperature is 1200-1500 ℃, the temperature rise rate is 5-10 ℃/min, and the heat preservation time is 2-4 hours.
10. The product prepared by the preparation method of the graphene-based heat-conducting and heat-dissipating composite material as claimed in any one of claims 1 to 9, which is used as a packaging material for electronic components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111575607.9A CN114058081B (en) | 2021-12-21 | 2021-12-21 | Preparation method and application of graphene-based heat-conducting and heat-dissipating composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111575607.9A CN114058081B (en) | 2021-12-21 | 2021-12-21 | Preparation method and application of graphene-based heat-conducting and heat-dissipating composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114058081A true CN114058081A (en) | 2022-02-18 |
| CN114058081B CN114058081B (en) | 2023-04-07 |
Family
ID=80230125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111575607.9A Active CN114058081B (en) | 2021-12-21 | 2021-12-21 | Preparation method and application of graphene-based heat-conducting and heat-dissipating composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114058081B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115092916A (en) * | 2022-06-23 | 2022-09-23 | 湖南大学 | Graphene-based thermal interface material with sandwich structure and preparation method thereof |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146024A (en) * | 2013-03-19 | 2013-06-12 | 苏州格瑞丰纳米科技有限公司 | Porous graphene/polymer composite structure and preparation method and application thereof |
| CN103384007A (en) * | 2013-07-23 | 2013-11-06 | 深圳清华大学研究院 | Carbon nano tube/graphene composite negative pole material, preparation method thereof and lithium battery |
| CN103725263A (en) * | 2013-12-17 | 2014-04-16 | 张家港康得新光电材料有限公司 | Film made from graphene-carbon nanotube composite material and preparation method of film |
| CN106433131A (en) * | 2015-08-05 | 2017-02-22 | 中国科学院宁波材料技术与工程研究所 | Graphene heat conduction silica gel and preparation method thereof |
| US20180034055A1 (en) * | 2016-07-28 | 2018-02-01 | University-Industry Foundation, Yonsei University | Composite including porous graphene and carbon nanotube material |
| CN108711611A (en) * | 2018-04-04 | 2018-10-26 | 广东工业大学 | A kind of metal nanoparticle/graphene of three-dimensional high-density is composite porous and its preparation method and application |
| CN109054292A (en) * | 2018-06-15 | 2018-12-21 | 安徽赤诚塑胶科技有限公司 | A kind of preparation method of thermally conductive porous graphene-epoxy resin composite material |
| CN109095926A (en) * | 2018-08-01 | 2018-12-28 | 中国科学院上海硅酸盐研究所 | A kind of high-volume fractional graphene enhancing carborundum based material and preparation method thereof |
| CN109988360A (en) * | 2019-04-09 | 2019-07-09 | 上海超碳石墨烯产业技术有限公司 | A kind of graphene heat-conducting polymer material and preparation method thereof |
| WO2019246104A1 (en) * | 2018-06-19 | 2019-12-26 | Sabic Global Technologies B.V. | Graphene-based porous carbon materials for lithium-sulfur cathode |
| CN110734055A (en) * | 2019-11-27 | 2020-01-31 | 北京航空航天大学 | three-dimensional porous graphene skeleton-single-walled carbon nanotube flexible composite material and preparation method thereof |
| CN110886089A (en) * | 2019-11-19 | 2020-03-17 | 杭州超探新材料有限公司 | Preparation method of graphene and carbon nanotube in-situ growth co-modified toughened carbon fiber |
| CN112812341A (en) * | 2021-02-09 | 2021-05-18 | 桂林电子科技大学 | High-thermal-conductivity composite particle/polyimide film with four-needle-shaped structure and preparation method thereof |
| US20210234167A1 (en) * | 2020-01-27 | 2021-07-29 | Global Graphene Group, Inc. | Porous graphene/carbon composite balls for an alkali metal battery anode |
| CN113372107A (en) * | 2021-07-08 | 2021-09-10 | 铜陵四拓智能装备科技有限公司 | Preparation process of low-thermal-expansion composite material |
-
2021
- 2021-12-21 CN CN202111575607.9A patent/CN114058081B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146024A (en) * | 2013-03-19 | 2013-06-12 | 苏州格瑞丰纳米科技有限公司 | Porous graphene/polymer composite structure and preparation method and application thereof |
| CN103384007A (en) * | 2013-07-23 | 2013-11-06 | 深圳清华大学研究院 | Carbon nano tube/graphene composite negative pole material, preparation method thereof and lithium battery |
| CN103725263A (en) * | 2013-12-17 | 2014-04-16 | 张家港康得新光电材料有限公司 | Film made from graphene-carbon nanotube composite material and preparation method of film |
| CN106433131A (en) * | 2015-08-05 | 2017-02-22 | 中国科学院宁波材料技术与工程研究所 | Graphene heat conduction silica gel and preparation method thereof |
| US20180034055A1 (en) * | 2016-07-28 | 2018-02-01 | University-Industry Foundation, Yonsei University | Composite including porous graphene and carbon nanotube material |
| CN108711611A (en) * | 2018-04-04 | 2018-10-26 | 广东工业大学 | A kind of metal nanoparticle/graphene of three-dimensional high-density is composite porous and its preparation method and application |
| CN109054292A (en) * | 2018-06-15 | 2018-12-21 | 安徽赤诚塑胶科技有限公司 | A kind of preparation method of thermally conductive porous graphene-epoxy resin composite material |
| WO2019246104A1 (en) * | 2018-06-19 | 2019-12-26 | Sabic Global Technologies B.V. | Graphene-based porous carbon materials for lithium-sulfur cathode |
| CN109095926A (en) * | 2018-08-01 | 2018-12-28 | 中国科学院上海硅酸盐研究所 | A kind of high-volume fractional graphene enhancing carborundum based material and preparation method thereof |
| CN109988360A (en) * | 2019-04-09 | 2019-07-09 | 上海超碳石墨烯产业技术有限公司 | A kind of graphene heat-conducting polymer material and preparation method thereof |
| CN110886089A (en) * | 2019-11-19 | 2020-03-17 | 杭州超探新材料有限公司 | Preparation method of graphene and carbon nanotube in-situ growth co-modified toughened carbon fiber |
| CN110734055A (en) * | 2019-11-27 | 2020-01-31 | 北京航空航天大学 | three-dimensional porous graphene skeleton-single-walled carbon nanotube flexible composite material and preparation method thereof |
| US20210234167A1 (en) * | 2020-01-27 | 2021-07-29 | Global Graphene Group, Inc. | Porous graphene/carbon composite balls for an alkali metal battery anode |
| CN112812341A (en) * | 2021-02-09 | 2021-05-18 | 桂林电子科技大学 | High-thermal-conductivity composite particle/polyimide film with four-needle-shaped structure and preparation method thereof |
| CN113372107A (en) * | 2021-07-08 | 2021-09-10 | 铜陵四拓智能装备科技有限公司 | Preparation process of low-thermal-expansion composite material |
Non-Patent Citations (1)
| Title |
|---|
| 柴雅琼;李章朋;莫尊理;杨志刚;王金清;: "多孔石墨烯的制备及应用" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115092916A (en) * | 2022-06-23 | 2022-09-23 | 湖南大学 | Graphene-based thermal interface material with sandwich structure and preparation method thereof |
| CN115092916B (en) * | 2022-06-23 | 2023-08-15 | 湖南大学 | Graphene-based thermal interface material with sandwich structure and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114058081B (en) | 2023-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | Preparation of boron nitride nanosheet/nanofibrillated cellulose nanocomposites with ultrahigh thermal conductivity via engineering interfacial thermal resistance | |
| Ma et al. | Strategies for enhancing thermal conductivity of polymer-based thermal interface materials: A review | |
| Ouyang et al. | Recent progress of thermal conductive ploymer composites: Al2O3 fillers, properties and applications | |
| Su et al. | Anisotropic thermally conductive flexible polymer composites filled with hexagonal born nitride (h-BN) platelets and ammine carbon nanotubes (CNT-NH2): Effects of the filler distribution and orientation | |
| Guo et al. | High thermal conductive poly (vinylidene fluoride)-based composites with well-dispersed carbon nanotubes/graphene three-dimensional network structure via reduced interfacial thermal resistance | |
| CN111154126B (en) | Preparation method of nano-diamond modified boron nitride high-flexibility high-thermal conductivity composite film | |
| CN106636992B (en) | A kind of CNTs and CNFs collaborations enhancing Cu-base composites and preparation method | |
| Zhao et al. | A combination of aramid nanofiber and silver nanoparticle decorated boron nitride for the preparation of a composite film with superior thermally conductive performance | |
| Wang et al. | Ionic liquid‐modified graphene/poly (vinyl alcohol) composite with enhanced properties | |
| Li et al. | Improving thermal conductivity of poly (vinyl alcohol) composites by using functionalized nanodiamond | |
| CN114058081B (en) | Preparation method and application of graphene-based heat-conducting and heat-dissipating composite material | |
| Yoon et al. | Review on three-dimensional ceramic filler networking composites for thermal conductive applications | |
| WO2021164225A1 (en) | Chemical and physical treatment method for filler with high thermal conductivity | |
| Wu et al. | Green preparation of high-yield and large-size hydrophilic boron nitride nanosheets by tannic acid-assisted aqueous ball milling for thermal management | |
| CN108659457A (en) | A kind of boron nitride cladding sulfonated graphene-epoxy resin composite material and preparation method thereof | |
| CN115584038A (en) | Flexible aramid nanofiber/MXene high-thermal-conductivity flame-retardant composite film and preparation method and application thereof | |
| Gong et al. | Highly flexible cellulose nanofiber/single-crystal nanodiamond flake heat spreader films for heat dissipation | |
| Hu et al. | Flexible and thermal conductive poly (vinylidene fluoride) composites with silver decorated hexagonal boron nitride/silicon carbide hybrid filler | |
| Yu et al. | Boron nitride nanosheets: Large-scale exfoliation in NaOH-LiCl solution and their highly thermoconductive insulating nanocomposite paper with PI via electrospinning-electrospraying | |
| Liu et al. | Synthesis of novel nanocomposites reinforced with 3D graphene/highly-dispersible nanodiamonds nano-hybrids | |
| CN109370493B (en) | Thermal interface material and preparation method thereof | |
| Wang et al. | Improving thermal conductivity of ethylene-vinyl acetate composites by covalent bond-connected carbon nanotubes@ boron nitride hybrids | |
| Zhang et al. | A green and facile method to fabricate multifunctional and highly thermally conductive boron nitride‐based polymer composites | |
| Wang et al. | Facile fabrication of three-dimensional thermal conductive composites with synergistic effect of multidimensional fillers | |
| CN105295098B (en) | A kind of graphene oxide, CNT multi-arm determine the preparation method of configuration heat filling |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |