CN109318564A - A kind of method that the spraying of self assembly ultrasound prepares graphene heat conducting film - Google Patents
A kind of method that the spraying of self assembly ultrasound prepares graphene heat conducting film Download PDFInfo
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- CN109318564A CN109318564A CN201811052057.0A CN201811052057A CN109318564A CN 109318564 A CN109318564 A CN 109318564A CN 201811052057 A CN201811052057 A CN 201811052057A CN 109318564 A CN109318564 A CN 109318564A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 101
- 238000002604 ultrasonography Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000005507 spraying Methods 0.000 title claims abstract description 31
- 238000001338 self-assembly Methods 0.000 title claims abstract description 20
- 238000007605 air drying Methods 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 238000012545 processing Methods 0.000 claims abstract description 11
- 238000005098 hot rolling Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 239000011265 semifinished product Substances 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003292 glue Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- -1 graphite Alkene Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003851 corona treatment Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 230000017525 heat dissipation Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000011800 void material Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 5
- 238000007654 immersion Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- 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
- B32B27/281—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 comprising polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
Abstract
The present invention relates to a kind of methods that the spraying of self assembly ultrasound prepares graphene heat conducting film.The weak oxide modified graphene that the present invention uses, surface there are a large amount of functional group, can substantially uniformity be scattered in organic solvent；The present invention is by way of ultrasound spraying, finely dispersed graphene is set to realize self assembly in heat conducting film substrate, then it is sprayed by multipass ultrasound and air drying, sintering and hot rolling is handled, reduce graphene bedding void, effectively avoid the reduction of pyroconductivity, the preparation graphene heat conducting film that mass is stable, heat dissipation effect is excellent.The present invention can prepare graphene heat conducting film by simple processing step, and at low cost, high production efficiency is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of methods that the spraying of self assembly ultrasound prepares graphene heat conducting film.
Background technique
With the development of science and technology, the dissipated power of some electronic devices and Related product increases, heat dissipation has become neck
The problem for needing to solve in domain.Although the pyroconductivity of existing graphite guide hotting mask can reach 1500W/ (mK), it is made
Standby process energy consumption is higher, and complex process.
Graphene has unique two-dimensional slice layer structure, can be well adapted for as a kind of completely new Heat Conduction Material
Any surface, and there is the pyroconductivity of up to 300-3500W/ (mK).Graphene is in addition to pyroconductivity with higher
Except, it is also with good stability at high temperature, it is suitable as efficient heat sink material.However, existing in graphene molecules
Defect, the randomness at edge can reduce the coefficient of heat conduction in graphene.In the prior art, using a coated and molded system
Standby graphene heat conducting film, there are biggish bedding voids for graphene film interlayer, form thermal resistance, also will affect graphene film
Density causes the decline of pyroconductivity, heat dissipation effect bad to reduce the whole coefficient of heat conduction of graphene heat conducting film.
Summary of the invention
For the prior art, the present invention provides a kind of method that the spraying of self assembly ultrasound prepares graphene heat conducting film, has
The advantages that at low cost, simple process, high production efficiency, the thermally conductive film properties of the graphene of preparation are stable, quality is stable, heat dissipation effect
It is excellent.
The present invention takes following technical scheme:
A kind of method that the spraying of self assembly ultrasound prepares graphene heat conducting film, comprising the following steps:
(1) graphene is carried out weak oxide to be modified, obtains modified graphene；
(2) by modified graphene, ultrasonic disperse is uniform in a solvent, and ultrasonic time 4h obtains graphene dispersing solution, changes
Property graphene and solvent wt/v be 1:100-150；
(3) binder is uniformly dispersed in deionized water, the mass concentration of binder is 2.5%-4%；
(4) solution that step (3) obtains is uniformly mixed with graphene dispersing solution, obtains mixed liquor；
(5) by heat conducting film substrate sided corona treatment 1h, the mixed liquor ultrasound that step (4) obtains then is sprayed into heat conducting film base
Bottom surface, then air drying；Ultrasound spraying and air drying step 20-30 times are repeated, graphene heat conducting film semi-finished product are formed；
(6) graphene heat conducting film semi-finished product are sintered, remove the impurity in membrane removal；After sintering, in graphene heat conducting film
The surface of semi-finished product forms graphene layer；
(7) the coated with thermally conductive glue on graphene layer, then PE film is covered on heat-conducting glue, after hot rolling processing, obtain
Graphene heat conducting film.
Preferably, the graphene is prepared by full liquid physics stripping method.
Preferably, the weak oxide it is modified the following steps are included:
(a) graphene, potassium permanganate are sequentially added in the concentrated sulfuric acid, react 3-4h at 90-100 DEG C of temperature；The concentrated sulfuric acid, stone
The mass ratio that black alkene, potassium permanganate are added is 3:5:1；
(b) it collects graphene and is washed to pH value to be neutral to get to modified graphene.
Preferably, the solvent is one of dehydrated alcohol, ethyl acetate, acetone.
Preferably, the binder is one of sodium carboxymethylcellulose, Sodium Polyacrylate, sodium alginate.
Preferably, the heat conducting film substrate is the PI film of resistance to 300 DEG C of high temperature, with a thickness of 20 μm.
Preferably, the sintering carries out in nitrogen atmosphere protection stove, and the temperature of sintering is 250-300 DEG C, time 6-
8h。
Preferably, the pressure of the heat rolling processing is 5-10MPa, is 55-70 DEG C to roller bearing temperature.
During repeating ultrasound spraying and air drying, condensing recovery solvent avoids waste of solvent and indoor solvent
It volatilizees excessive bring security risk.
The graphene heat conducting film that the method that above-mentioned self assembly ultrasound spraying prepares graphene heat conducting film obtains.
Graphene of the invention is prepared by full liquid physics stripping method.
More specifically, the method that full liquid water phase physics removing prepares graphene, comprising the following steps:
(1) using ultrapure water to impregnate carbon content is 99.99%, and dilation is 200 times of expanded graphite, carries out wetting immersion
Processing, for 8-15mL:1g, the time for soaking immersion treatment is 18- for the volume of the ultrapure water used and the mass ratio of expanded graphite
25h；
(2) expanded graphite after wetting immersion treatment in step (1) is put into sand mill stirring, placed at colloid mill
Reason, obtains expanded graphite soak, wherein the concrete operations of milled processed are as follows: puts the expanded graphite after wetting immersion treatment
Entering stir process 1.5-4h in the sand mill equipped with a small amount of zirconium pearl, the revolving speed of sand mill is set as 1000-2000rad/min, then
It is put into milling treatment of colloid 3-6h, the power of colloid mill is 1-2KW, treating capacity 18-25L/h；
(3) the expanded graphite soak in step (2) is put into high pressure homogenizer and carries out high-pressure homogeneous processing, then with height
The processing of emulsification pretreatment pump, then handled with super-pressure critical assembly, obtain graphene dispersing solution, wherein the item of high-pressure homogeneous processing
Part are as follows: time 1.5-3h, pressure 50-100MPa, the time of emulsification treatment are 2.5-5h, the condition of the critical processing of super-pressure
Are as follows: time 2.5-5h, pressure 120-180MPa；
(4) step (3) are handled to obtained graphene dispersing solution stratification, are done by spraying at being 180-250 DEG C in temperature
It is dry to get arrive graphene.
The graphene lattice structure being prepared using full liquid physics stripping method is complete, simultaneously containing a small amount of-OH etc.
Hydrophilic radical has preferable dispersion performance, specific surface area 679m2/ g, graphene carbon content are 99.99wt%, the number of plies
It is 3-10 layers, metal ion content≤100ppm, thermal coefficient is 3800W/ (mK).
Beneficial effects of the present invention:
(1) the weak oxide modified graphene that the present invention uses, there are a large amount of functional groups on surface, can substantially uniformity dispersion
In organic solvent；The present invention realizes finely dispersed graphene in heat conducting film substrate certainly by way of ultrasound spraying
Then assembling is sprayed by multipass ultrasound and air drying, sintering and hot rolling is handled, reduced graphene bedding void, have
Effect avoids the reduction of pyroconductivity, the preparation graphene heat conducting film that mass is stable, heat dissipation effect is excellent；
(2) low raw-material cost used in the present invention, solvent passes through recycling and reusing, environmentally protective, environmentally friendly；
(3) present invention uses resistance to 300 DEG C of high temperature, with a thickness of 20 μm of PI films, the low temperature calcination at 250-300 DEG C, energy conservation
Environmental protection effectively reduces cost, strong operability.
(4) present invention can prepare graphene heat conducting film by simple processing step, and at low cost, high production efficiency is fitted
For industrial production.
Detailed description of the invention
Fig. 1 is the electron microscope of graphene heat conducting film prepared by embodiment 1.
Fig. 2 is the electron microscope of the section of graphene heat conducting film prepared by embodiment 1.
Specific embodiment
Below by embodiment, the present invention will be described in detail.
Embodiment 1
A kind of method that the spraying of self assembly ultrasound prepares graphene heat conducting film, comprising the following steps:
(1) graphene is prepared by full liquid physics stripping method, 5g graphene, 1g is then sequentially added in the 3g concentrated sulfuric acid
Potassium permanganate, reacts 4h at 90 DEG C of temperature, collects graphene and is washed to pH value to be neutral to get to modified graphite
Alkene；
(2) by 5g modified graphene, ultrasonic disperse is uniform in 500mL dehydrated alcohol, and ultrasonic time 4h obtains graphite
Alkene dispersion liquid；
(3) 1.2g sodium carboxymethylcellulose is uniformly dispersed in 30mL deionized water；
(4) solution that step (3) obtains is uniformly mixed with graphene dispersing solution, obtains mixed liquor；
(5) the PI film of resistance to 300 DEG C of high temperature is subjected to sided corona treatment 1h, the mixed liquor ultrasound for then obtaining step (4) is sprayed
It is coated onto the PI film surface of resistance to 300 DEG C of high temperature, then air drying；Ultrasound spraying and air drying step 20 time are repeated, stone is formed
Black alkene heat conducting film semi-finished product；During repeating ultrasound spraying and air drying, condensing recovery dehydrated alcohol；
(6) graphene heat conducting film semi-finished product being sintered in nitrogen atmosphere protection stove, the temperature of sintering is 300 DEG C,
Time is 6h, removes the impurity in membrane removal；After sintering, the surface of graphene heat conducting film semi-finished product forms graphene layer；
(7) heat-conducting glue that a layer thickness is 5 μm is coated on graphene layer, then covering a layer thickness on heat-conducting glue is 25
μm PE film, then carry out pressure be 5MPa, to roller bearing temperature be 65 DEG C hot rolling handle, obtain graphene heat conducting film.
Embodiment 2
A kind of method that the spraying of self assembly ultrasound prepares graphene heat conducting film, comprising the following steps:
(1) graphene is prepared by full liquid physics stripping method, 5g graphene, 1g is then sequentially added in the 3g concentrated sulfuric acid
Potassium permanganate, reacts 3h at 100 DEG C of temperature, collects graphene and is washed to pH value to be neutral to get to modified graphite
Alkene；
(2) by 3g modified graphene, ultrasonic disperse is uniform in 400mL ethyl acetate, and ultrasonic time 4h obtains graphite
Alkene dispersion liquid；
(3) 1.5g Sodium Polyacrylate is uniformly dispersed in 40mL deionized water；
(4) solution that step (3) obtains is uniformly mixed with graphene dispersing solution, obtains mixed liquor；
(5) the PI film of resistance to 300 DEG C of high temperature is subjected to sided corona treatment 1h, the mixed liquor ultrasound for then obtaining step (4) is sprayed
It is coated onto the PI film surface of resistance to 300 DEG C of high temperature, then air drying；Ultrasound spraying and air drying step 25 time are repeated, stone is formed
Black alkene heat conducting film semi-finished product；During repeating ultrasound spraying and air drying, condensing recovery ethyl acetate；
(6) graphene heat conducting film semi-finished product being sintered in nitrogen atmosphere protection stove, the temperature of sintering is 250 DEG C,
Time is 7h, removes the impurity in membrane removal；After sintering, the surface of graphene heat conducting film semi-finished product forms graphene layer；
(7) heat-conducting glue that a layer thickness is 5 μm is coated on graphene layer, then covering a layer thickness on heat-conducting glue is 25
μm PE film, then carry out pressure be 10MPa, to roller bearing temperature be 68 DEG C hot rolling handle, obtain graphene heat conducting film.
Embodiment 3
A kind of method that the spraying of self assembly ultrasound prepares graphene heat conducting film, comprising the following steps:
(1) graphene is prepared by full liquid physics stripping method, 5g graphene, 1g is then sequentially added in the 3g concentrated sulfuric acid
Potassium permanganate, reacts 3h at 90 DEG C of temperature, collects graphene and is washed to pH value to be neutral to get to modified graphite
Alkene；
(2) by 2.5g modified graphene, ultrasonic disperse is uniform in 375mL acetone, and ultrasonic time 4h obtains graphene
Dispersion liquid；
(3) 0.95g sodium alginate is uniformly dispersed in 35mL deionized water；
(4) solution that step (3) obtains is uniformly mixed with graphene dispersing solution, obtains mixed liquor；
(5) the PI film of resistance to 300 DEG C of high temperature is subjected to sided corona treatment 1h, the mixed liquor ultrasound for then obtaining step (4) is sprayed
It is coated onto the PI film surface of resistance to 300 DEG C of high temperature, then air drying；Ultrasound spraying and air drying step 28 time are repeated, stone is formed
Black alkene heat conducting film semi-finished product；During repeating ultrasound spraying and air drying, condensing recovery acetone.
(6) graphene heat conducting film semi-finished product being sintered in nitrogen atmosphere protection stove, the temperature of sintering is 250 DEG C,
Time is 7.5h, removes the impurity in membrane removal；After sintering, the surface of graphene heat conducting film semi-finished product forms graphene layer；
(7) heat-conducting glue that a layer thickness is 5 μm is coated on graphene layer, then covering a layer thickness on heat-conducting glue is 25
μm PE film, then carry out pressure be 9MPa, to roller bearing temperature be 70 DEG C hot rolling handle, obtain graphene heat conducting film.
By test, the thickness for the graphene heat conducting film that embodiment obtains is only 9.5-10.5 μm, and horizontal pyroconductivity can
Up to 1300W/ (mK), vertical heat conduction rate is 25W/ (mK), and showing graphene heat conducting film has excellent heat dissipation effect,
Meet application request.
Claims (9)
1. a kind of method that the spraying of self assembly ultrasound prepares graphene heat conducting film, which comprises the following steps:
(1) graphene is carried out weak oxide to be modified, obtains modified graphene；
(2) by modified graphene, ultrasonic disperse is uniform in a solvent, ultrasonic time 4h, obtains graphene dispersing solution, modified stone
The wt/v of black alkene and solvent is 1:100-150；
(3) binder is uniformly dispersed in deionized water, the mass concentration of binder is 2.5%-4%；
(4) solution that step (3) obtains is uniformly mixed with graphene dispersing solution, obtains mixed liquor；
(5) by heat conducting film substrate sided corona treatment 1h, the mixed liquor ultrasound that step (4) obtains then is sprayed into heat conducting film substrate table
Face, then air drying；Ultrasound spraying and air drying step 20-30 times are repeated, graphene heat conducting film semi-finished product are formed；
(6) graphene heat conducting film semi-finished product are sintered, remove the impurity in membrane removal；In graphene heat conducting film semi-finished product after sintering
Surface formed graphene layer；
(7) the coated with thermally conductive glue on graphene layer, then PE film is covered on heat-conducting glue, after hot rolling processing, obtain graphite
Alkene heat conducting film.
2. the method that self assembly ultrasound spraying according to claim 1 prepares graphene heat conducting film, which is characterized in that described
Graphene prepared by full liquid physics stripping method.
3. the method that self assembly ultrasound spraying according to claim 1 prepares graphene heat conducting film, which is characterized in that described
Weak oxide it is modified the following steps are included:
(a) graphene, potassium permanganate are sequentially added in the concentrated sulfuric acid, react 3-4h at 90-100 DEG C of temperature；The concentrated sulfuric acid, graphite
The mass ratio that alkene, potassium permanganate are added is 3:5:1；
(b) it collects graphene and is washed to pH value to be neutral to get to modified graphene.
4. the method that self assembly ultrasound spraying according to claim 1 prepares graphene heat conducting film, which is characterized in that described
Solvent be one of dehydrated alcohol, ethyl acetate, acetone.
5. the method that self assembly ultrasound spraying according to claim 1 prepares graphene heat conducting film, which is characterized in that described
Binder be one of sodium carboxymethylcellulose, Sodium Polyacrylate, sodium alginate.
6. the method that self assembly ultrasound spraying according to claim 1 prepares graphene heat conducting film, which is characterized in that described
Heat conducting film substrate be resistance to 300 DEG C of high temperature PI film, with a thickness of 20 μm.
7. the method that self assembly ultrasound spraying according to claim 1 prepares graphene heat conducting film, which is characterized in that described
Sintering carries out in nitrogen atmosphere protection stove, and the temperature of sintering is 250-300 DEG C, time 6-8h.
8. the method that self assembly ultrasound spraying according to claim 1 prepares graphene heat conducting film, which is characterized in that described
The pressure of heat rolling processing is 5-10MPa, is 55-70 DEG C to roller bearing temperature.
9. the graphene that the method that the described in any item self assembly ultrasound sprayings of claim 1-8 prepare graphene heat conducting film obtains
Heat conducting film.
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