CN109318564B - Method for preparing graphene heat-conducting film through self-assembly ultrasonic spraying - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 112
- 238000005507 spraying Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000001338 self-assembly Methods 0.000 title claims abstract description 20
- 238000011282 treatment Methods 0.000 claims abstract description 22
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- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000005098 hot rolling Methods 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 21
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
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- 238000012986 modification Methods 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
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- 230000000694 effects Effects 0.000 abstract description 5
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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Abstract
The invention relates to a method for preparing a graphene heat-conducting film by self-assembly ultrasonic spraying. According to the weakly oxidized modified graphene, a large number of functional groups exist on the surface, and the weakly oxidized modified graphene can be completely and uniformly dispersed in an organic solvent; according to the invention, self-assembly of uniformly dispersed graphene on the heat conducting film substrate is realized in an ultrasonic spraying mode, and then through multiple ultrasonic spraying and normal-temperature drying, sintering and hot rolling treatment, gaps among graphene layers are reduced, reduction of thermal conductivity is effectively avoided, and the graphene heat conducting film with stable quality and excellent heat dissipation effect is prepared. The graphene heat-conducting film can be prepared through simple process steps, is low in cost and high in production efficiency, and is suitable for industrial production.
Description
Technical Field
The invention relates to a method for preparing a graphene heat-conducting film by self-assembly ultrasonic spraying.
Background
With the development of technology, the dissipation power of some electronic devices and related products is increased, and heat dissipation is becoming a difficult problem to be solved in the field. Although the thermal conductivity of the existing graphite heat-conducting film can reach 1500W/(m.K), the energy consumption of the preparation process is high, and the process is complex.
Graphene as a brand-new heat conduction material has a unique two-dimensional sheet layered structure, can be well adapted to any surface, and has the heat conductivity as high as 300-. Besides high thermal conductivity, graphene also has good stability at high temperature, and is suitable for being used as a high-efficiency heat dissipation material. However, defects present in the graphene molecules, edge disorder, reduce the thermal conductivity in graphene. In the prior art, the graphene heat-conducting film prepared by one-step coating molding has large interlayer gaps between graphene sheets to form thermal resistance, and the density of the graphene film is also affected, so that the overall heat conduction coefficient of the graphene heat-conducting film is reduced, the heat conductivity is reduced, and the heat dissipation effect is poor.
Disclosure of Invention
Aiming at the prior art, the invention provides a method for preparing a graphene heat-conducting film by self-assembly ultrasonic spraying, which has the advantages of low cost, simple process, high production efficiency and the like, and the prepared graphene heat-conducting film has stable performance, stable quality and excellent heat dissipation effect.
The invention adopts the following technical scheme:
a method for preparing a graphene heat-conducting film through self-assembly ultrasonic spraying comprises the following steps:
(1) carrying out weak oxidation modification on graphene to obtain modified graphene;
(2) carrying out ultrasonic dispersion on modified graphene in a solvent uniformly for 4h to obtain a graphene dispersion liquid, wherein the wt/v of the modified graphene and the solvent is 1: 100-150;
(3) uniformly dispersing a binder in deionized water, wherein the mass concentration of the binder is 2.5-4%;
(4) uniformly mixing the solution obtained in the step (3) with the graphene dispersion liquid to obtain a mixed solution;
(5) carrying out corona treatment on the heat-conducting film substrate for 1h, then carrying out ultrasonic spraying on the mixed liquid obtained in the step (4) on the surface of the heat-conducting film substrate, and then drying at normal temperature; repeating the steps of ultrasonic spraying and normal-temperature drying for 20-30 times to form a graphene heat-conducting film semi-finished product;
(6) sintering the semi-finished product of the graphene heat-conducting film to remove impurities in the film; after sintering, forming a graphene layer on the surface of the semi-finished graphene heat-conducting film;
(7) and coating heat-conducting glue on the graphene layer, coating a PE film on the heat-conducting glue, and performing hot rolling treatment to obtain the graphene heat-conducting film.
Preferably, the graphene is prepared by a full liquid physical stripping method.
Preferably, the weak oxidative modification comprises the steps of:
(a) sequentially adding graphene and potassium permanganate into concentrated sulfuric acid, and reacting at 90-100 ℃ for 3-4 h; the mass ratio of concentrated sulfuric acid, graphene and potassium permanganate is 3: 5: 1;
(b) and collecting graphene, and washing the graphene with water until the pH value is neutral to obtain the modified graphene.
Preferably, the solvent is one of absolute ethyl alcohol, ethyl acetate and acetone.
Preferably, the binder is one of sodium carboxymethylcellulose, sodium polyacrylate and sodium alginate.
Preferably, the heat conducting film substrate is a PI film resistant to high temperature of 300 ℃ and has a thickness of 20 μm.
Preferably, the sintering is carried out in a nitrogen atmosphere protective furnace, the sintering temperature is 250-300 ℃, and the sintering time is 6-8 h.
Preferably, the pressure of the hot rolling treatment is 5-10MPa, and the temperature of the roller is 55-70 ℃.
In the process of repeating ultrasonic spraying and normal temperature drying, the solvent is condensed and recovered, so that potential safety hazards caused by solvent waste and excessive volatilization of the indoor solvent are avoided.
The graphene heat-conducting film is obtained by the method for preparing the graphene heat-conducting film through self-assembly ultrasonic spraying.
The graphene is prepared by a full liquid state physical stripping method.
More specifically, the method for preparing graphene by full liquid aqueous phase physical stripping comprises the following steps:
(1) soaking expanded graphite with the carbon content of 99.99% and the expansion degree of 200 times by adopting ultrapure water, and carrying out wetting and soaking treatment, wherein the mass ratio of the volume of the adopted ultrapure water to the mass of the expanded graphite is 8-15mL:1g, and the time of the wetting and soaking treatment is 18-25 h;
(2) and (2) putting the expanded graphite subjected to the wetting and soaking treatment in the step (1) into a sand mill for stirring, and then putting the sand mill for treatment to obtain an expanded graphite soaking solution, wherein the specific operation of the grinding treatment is as follows: putting the expanded graphite subjected to the wetting and soaking treatment into a sand mill filled with a small amount of zirconium beads, stirring for 1.5-4h, setting the rotating speed of the sand mill to be 1000-2000rad/min, and then putting the sand mill into a colloid mill for treatment for 3-6h, wherein the power of the colloid mill is 1-2KW, and the treatment capacity is 18-25L/h;
(3) putting the expanded graphite soak solution obtained in the step (2) into a high-pressure homogenizer for high-pressure homogenization treatment, then treating with a high-shear emulsification pump, and then treating with an ultrahigh-pressure critical device to obtain a graphene dispersion solution, wherein the conditions of the high-pressure homogenization treatment are as follows: the time is 1.5-3h, the pressure is 50-100MPa, the time of emulsification treatment is 2.5-5h, and the conditions of ultrahigh pressure critical treatment are as follows: the time is 2.5-5h, and the pressure is 120-;
(4) and (4) standing and layering the graphene dispersion liquid obtained by the treatment in the step (3), and spray drying at the temperature of 180-250 ℃ to obtain the graphene.
The graphene prepared by adopting a full liquid physical stripping method has a complete lattice structure, contains a small amount of-OH and other hydrophilic groups, has good dispersion performance, and has a specific surface area of 679m2The carbon content of the graphene is 99.99 wt%, the number of layers is 3-10, the content of metal ions is less than or equal to 100ppm, and the thermal conductivity is 3800W/(m.K).
The invention has the beneficial effects that:
(1) according to the weakly oxidized modified graphene, a large number of functional groups exist on the surface, and the weakly oxidized modified graphene can be completely and uniformly dispersed in an organic solvent; according to the invention, self-assembly of uniformly dispersed graphene on a heat-conducting film substrate is realized in an ultrasonic spraying manner, and then through multiple ultrasonic spraying and normal-temperature drying, sintering and hot rolling treatments, gaps among graphene layers are reduced, reduction of thermal conductivity is effectively avoided, and the graphene heat-conducting film with stable quality and excellent heat dissipation effect is prepared;
(2) the raw materials used in the invention have low cost, and the solvent is recycled, so that the method is green, environment-friendly and environment-friendly;
(3) the invention adopts the PI film with the thickness of 20 mu m and the high temperature resistance of 300 ℃, and the PI film is calcined at the low temperature of 300 ℃ of 250 ℃, thereby saving energy, protecting environment, effectively reducing cost and having strong operability.
(4) The graphene heat-conducting film can be prepared through simple process steps, is low in cost and high in production efficiency, and is suitable for industrial production.
Drawings
Fig. 1 is an electron microscope image of the graphene thermal conductive film prepared in example 1.
Fig. 2 is an electron microscope image of a cross section of the graphene thermal conductive film prepared in example 1.
Detailed Description
The present invention will be described in detail below with reference to examples.
Example 1
A method for preparing a graphene heat-conducting film through self-assembly ultrasonic spraying comprises the following steps:
(1) preparing graphene by a full-liquid physical stripping method, sequentially adding 5g of graphene and 1g of potassium permanganate into 3g of concentrated sulfuric acid, reacting at 90 ℃ for 4 hours, collecting the graphene, and washing the graphene with water until the pH value is neutral to obtain modified graphene;
(2) ultrasonically dispersing 5g of modified graphene in 500mL of absolute ethyl alcohol uniformly for 4h to obtain a graphene dispersion liquid;
(3) uniformly dispersing 1.2g of sodium carboxymethylcellulose in 30mL of deionized water;
(4) uniformly mixing the solution obtained in the step (3) with the graphene dispersion liquid to obtain a mixed solution;
(5) carrying out corona treatment on the PI film resistant to the high temperature of 300 ℃ for 1h, then ultrasonically spraying the mixed solution obtained in the step (4) on the surface of the PI film resistant to the high temperature of 300 ℃, and then drying at normal temperature; repeating the steps of ultrasonic spraying and normal-temperature drying for 20 times to form a graphene heat-conducting film semi-finished product; condensing and recovering absolute ethyl alcohol in the process of repeating ultrasonic spraying and normal-temperature drying;
(6) sintering the semi-finished product of the graphene heat-conducting film in a nitrogen atmosphere protective furnace at the sintering temperature of 300 ℃ for 6 hours, and removing impurities in the film; after sintering, forming a graphene layer on the surface of the semi-finished graphene heat-conducting film;
(7) and coating a layer of heat-conducting glue with the thickness of 5 microns on the graphene layer, coating a layer of PE film with the thickness of 25 microns on the heat-conducting glue, and performing hot rolling treatment at the pressure of 5MPa and the temperature of a rolling shaft of 65 ℃ to obtain the graphene heat-conducting film.
Example 2
A method for preparing a graphene heat-conducting film through self-assembly ultrasonic spraying comprises the following steps:
(1) preparing graphene by a full-liquid physical stripping method, sequentially adding 5g of graphene and 1g of potassium permanganate into 3g of concentrated sulfuric acid, reacting at 100 ℃ for 3 hours, collecting the graphene, and washing the graphene with water until the pH value is neutral to obtain modified graphene;
(2) ultrasonically dispersing 3g of modified graphene in 400mL of ethyl acetate uniformly for 4h to obtain a graphene dispersion liquid;
(3) 1.5g of sodium polyacrylate is uniformly dispersed in 40mL of deionized water;
(4) uniformly mixing the solution obtained in the step (3) with the graphene dispersion liquid to obtain a mixed solution;
(5) carrying out corona treatment on the PI film resistant to the high temperature of 300 ℃ for 1h, then ultrasonically spraying the mixed solution obtained in the step (4) on the surface of the PI film resistant to the high temperature of 300 ℃, and then drying at normal temperature; repeating the steps of ultrasonic spraying and normal-temperature drying for 25 times to form a graphene heat-conducting film semi-finished product; condensing and recovering ethyl acetate in the process of repeating ultrasonic spraying and normal-temperature drying;
(6) sintering the semi-finished product of the graphene heat-conducting film in a nitrogen atmosphere protective furnace at the sintering temperature of 250 ℃ for 7 hours, and removing impurities in the film; after sintering, forming a graphene layer on the surface of the semi-finished graphene heat-conducting film;
(7) and coating a layer of heat-conducting glue with the thickness of 5 microns on the graphene layer, coating a layer of PE film with the thickness of 25 microns on the heat-conducting glue, and performing hot rolling treatment at the pressure of 10MPa and the temperature of 68 ℃ on a rolling shaft to obtain the graphene heat-conducting film.
Example 3
A method for preparing a graphene heat-conducting film through self-assembly ultrasonic spraying comprises the following steps:
(1) preparing graphene by a full-liquid physical stripping method, sequentially adding 5g of graphene and 1g of potassium permanganate into 3g of concentrated sulfuric acid, reacting at 90 ℃ for 3 hours, collecting the graphene, and washing the graphene with water until the pH value is neutral to obtain modified graphene;
(2) ultrasonically dispersing 2.5g of modified graphene in 375mL of acetone uniformly for 4h to obtain graphene dispersion liquid;
(3) uniformly dispersing 0.95g of sodium alginate in 35mL of deionized water;
(4) uniformly mixing the solution obtained in the step (3) with the graphene dispersion liquid to obtain a mixed solution;
(5) carrying out corona treatment on the PI film resistant to the high temperature of 300 ℃ for 1h, then ultrasonically spraying the mixed solution obtained in the step (4) on the surface of the PI film resistant to the high temperature of 300 ℃, and then drying at normal temperature; repeating the steps of ultrasonic spraying and normal-temperature drying 28 times to form a graphene heat-conducting film semi-finished product; and condensing and recovering the acetone in the process of repeating the ultrasonic spraying and the normal-temperature drying.
(6) Sintering the semi-finished product of the graphene heat-conducting film in a nitrogen atmosphere protective furnace at the sintering temperature of 250 ℃ for 7.5 hours, and removing impurities in the film; after sintering, forming a graphene layer on the surface of the semi-finished graphene heat-conducting film;
(7) and coating a layer of heat-conducting glue with the thickness of 5 microns on the graphene layer, coating a layer of PE film with the thickness of 25 microns on the heat-conducting glue, and performing hot rolling treatment at the pressure of 9MPa and the temperature of a rolling shaft of 70 ℃ to obtain the graphene heat-conducting film.
Through tests, the thickness of the graphene heat-conducting film obtained in the embodiment is only 9.5-10.5 micrometers, the horizontal thermal conductivity can reach 1300W/(m.K), and the vertical thermal conductivity is 25W/(m.K), so that the graphene heat-conducting film has an excellent heat dissipation effect and meets the requirements of practical application.
Claims (8)
1. A method for preparing a graphene heat-conducting film through self-assembly ultrasonic spraying is characterized by comprising the following steps:
(1) carrying out weak oxidation modification on graphene to obtain modified graphene; the graphene is prepared by a full liquid state physical stripping method;
(2) carrying out ultrasonic dispersion on modified graphene in a solvent uniformly for 4h to obtain a graphene dispersion liquid, wherein the wt/v of the modified graphene and the solvent is 1: 100-150;
(3) uniformly dispersing a binder in deionized water, wherein the mass concentration of the binder is 2.5-4%;
(4) uniformly mixing the solution obtained in the step (3) with the graphene dispersion liquid to obtain a mixed solution;
(5) carrying out corona treatment on the heat-conducting film substrate for 1h, then carrying out ultrasonic spraying on the mixed liquid obtained in the step (4) on the surface of the heat-conducting film substrate, and then drying at normal temperature; repeating the steps of ultrasonic spraying and normal-temperature drying for 20-30 times to form a graphene heat-conducting film semi-finished product;
(6) sintering the semi-finished product of the graphene heat-conducting film in a nitrogen atmosphere protective furnace to remove impurities in the film; forming a graphene layer on the surface of the semi-finished graphene heat-conducting film after sintering;
(7) and coating heat-conducting glue on the graphene layer, coating a PE film on the heat-conducting glue, and performing hot rolling treatment to obtain the graphene heat-conducting film.
2. The method for preparing the graphene thermal conductive film by self-assembly ultrasonic spraying according to claim 1, wherein the weak oxidation modification comprises the following steps:
(a) sequentially adding graphene and potassium permanganate into concentrated sulfuric acid, and reacting at 90-100 ℃ for 3-4 h; the mass ratio of concentrated sulfuric acid, graphene and potassium permanganate is 3: 5: 1;
(b) and collecting graphene, and washing the graphene with water until the pH value is neutral to obtain the modified graphene.
3. The method for preparing the graphene thermal conductive film by self-assembly ultrasonic spraying according to claim 1, wherein the solvent is one of absolute ethyl alcohol, ethyl acetate and acetone.
4. The method for preparing the graphene thermal conductive film through self-assembly ultrasonic spraying according to claim 1, wherein the binder is one of sodium carboxymethylcellulose, sodium polyacrylate and sodium alginate.
5. The method for preparing the graphene thermal conductive film by self-assembly ultrasonic spraying according to claim 1, wherein the substrate of the thermal conductive film is a PI film resistant to a high temperature of 300 ℃ and has a thickness of 20 μm.
6. The method for preparing the graphene thermal conductive film by self-assembly ultrasonic spraying as claimed in claim 1, wherein the sintering temperature is 250-300 ℃ and the sintering time is 6-8 h.
7. The method for preparing the graphene heat-conducting film through self-assembly ultrasonic spraying according to claim 1, wherein the pressure of the hot rolling treatment is 5-10MPa, and the temperature of a roller is 55-70 ℃.
8. The graphene thermal conductive film obtained by the method for preparing the graphene thermal conductive film by self-assembly ultrasonic spraying according to any one of claims 1 to 7.
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