CN105964522B - A kind of preparation method of graphene heat conducting film - Google Patents
A kind of preparation method of graphene heat conducting film Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of graphene heat conducting film, belongs to the technical field of grapheme material.The preparation method complex process for solving the problems, such as existing graphene heat conducting film, obtained graphene orientationization be low, heating conduction and tensile strength are low.Graphite is first immersed in mixed acid solution by this method, and intercalator stirring is then added, obtains mixed solution；Then organic reagent is added in mixed solution and is reacted, obtain the aqueous dispersions of graphene；Natural plants long fibre is added in graphene dispersing solution or polymeric long fiber carries out excusing from death processing, obtains graphite fiber alkene mixed dispersion liquid；Finally graphite fiber alkene mixed dispersion liquid is arranged in substrate, the film obtained after drying is handled 15-30 minutes at a temperature of 500-900 DEG C, obtains graphene heat conducting film.The graphene heat conducting film that the present invention is prepared has height-orientedization, and thermal coefficient is up to 1000-1500W/mK, mechanical stretch intensity 30-70MPa.
Description
Technical field
The invention belongs to the technical fields of grapheme material, and in particular to a kind of preparation method of graphene heat conducting film.
Background technique
Heat conduction and heat radiation all has great application in many fields such as current electronics, communication, illumination, aviation and defence and military
Demand.The Heat Conduction Material of mainstream is still mostly based on aluminium and copper metal or alloy in the market, and nearly more than ten years graphite guide hotting mask is wide
General application and the market share for capturing traditional material rapidly.The advantage with the following aspects of graphite guide hotting mask: thermally conductive system
The higher 300-1500w/mk of number, higher than the various alloys and simple substance copper product of aluminium；Weight ratio aluminium is light by 25% simultaneously, lighter than copper
75%；And cut out convenient for cutting, it is easy to use.
At present there are mainly two types of graphite heat conducting membrane preparation methods, one is pass through the dry method system of rolling by raw material of expanded graphite
At graphite film, simple process is at low cost, but thermal coefficient is lower, and generally in 300-500W/mK, and buckle resistance is poor；
Another method is by the way that highdensity graphite film, the graphite heat conducting that this technique obtains is made in macromolecule membrane pyrographite
Higher 1000-1500W/mK, tensile strength is larger, but complex process energy consumption is high.
In order to overcome these problems of graphite film, graphene heat conducting film comes into being.Because of the thermal coefficient highest of graphene
It can reach 5300W/mK, it is more taller than carbon nanotube, so many research institutions Devoting Major Efforts To Developing graphene heat conducting film, with expectation
Equalization point is found between cost, energy consumption, technique, performance.CN103449423A discloses one kind using graphene oxide as raw material
The method that graphene heat conducting film is prepared by techniques such as films, the technique are related to the process of inert atmosphere high temperature thermal reduction,
The problems such as energy consumption is higher, and graphite oxide reduction is not thorough.CN103805144A and CN104232027A be with polymer or
The graphene of other surfaces dressing agent modification is blended with other graphite, graphite oxide, carbon fiber, graphene etc., by stabilizer, glues
Acting in suction filtration treatment process for knot agent forms a film, and high annealing removal organic matter or reduction-oxidation graphite, complex process.
According to the description in newest document, the size of graphene film size is very aobvious on the thermally conductive influence of graphene
It writes, with the decline for reducing thermal coefficient geometry times of graphene film size, while above-mentioned several method is all with graphene film
For raw material, there can be grain boundary resistance film forming, and at this moment seriously affect the thermally conductive factor of graphene film, because material
It is thermally conductive mainly by the way that electronics is thermally conductive and phonon vibration, and mainly to pass through electronics thermally conductive for graphene.So it can be concluded that, piece is got over
The thermal conductivity of big graphene, film will be higher.But it is worth supplement, lamella will lead to greatly graphene curling, reunite,
A large amount of stomata is had after film forming influences thermally conductive, institute's orientation in need by graphene height, and reduction bubble improves stacking
Continuity.
Summary of the invention
The purpose of the present invention is to solve the preparation method complex process of existing graphene heat conducting film, obtained graphite
The problem that alkene orientationization is low, heating conduction and tensile strength are low, and a kind of preparation method of graphene heat conducting film is provided.
The present invention provides a kind of preparation method of graphene heat conducting film, this method comprises:
Step 1: graphite is immersed in mixed acid solution, and intercalator stirring is then added, obtains mixed solution；
Step 2: organic reagent being added in the mixed solution that step 1 obtains and is reacted, and obtains the water dispersion of graphene
Liquid；
Step 3: be added in graphene dispersing solution obtained in step 2 natural plants long fibre or polymeric long fiber into
Row excusing from death processing, obtains graphite fiber alkene mixed dispersion liquid；
Step 4: the graphite fiber alkene mixed dispersion liquid that step 3 is obtained is arranged in substrate, the film obtained after drying
It is handled 15-30 minutes at a temperature of 500-900 DEG C, obtains graphene heat conducting film.
Preferably, in the aqueous dispersions of the graphene, graphene thickness is less than 3 nanometers, lamella size 150-600
Micron, concentration 1-20g/L.
Preferably, the natural plants long fibre is that degreasing wood-fibred, cotton fiber, filter paper comminution pulp or silk are short
It cuts.
Preferably, the polymeric long fiber is that regenerated celulose fibre is chopped, nylon is chopped, terylene, polyamide fibre, nitrile
Synthetic fibre, polyvinyl chloride fibre, polyvinyl or spandex.
Preferably, the natural plants long fibre or the long stapled additional amount of polymer are the 3- of graphene quality
40%.
Preferably, the natural plants long fibre or the long stapled length of polymer are 0.5-7 millimeters, with a thickness of 3-
30 microns.
Preferably, the excusing from death processing time of the step three is 15-60 minutes.
Preferably, the step three further includes that carbon nanotube or chopped carbon fiber are added in graphene dispersing solution.
Preferably, the concentration of the graphite fiber alkene mixed dispersion liquid is 0.3-2g/L.
Preferably, the substrate is copper foil, aluminium foil or PET film.
Beneficial effects of the present invention
The present invention provides a kind of preparation method of graphene heat conducting film, and graphite is first immersed in mixed acid solution by this method,
Then intercalator stirring is added, obtains mixed solution；Then organic reagent is added in mixed solution and is reacted, obtain graphene
Aqueous dispersions；Natural plants long fibre is added in graphene dispersing solution or polymeric long fiber carries out excusing from death processing, obtains
Graphite fiber alkene mixed dispersion liquid；Finally graphite fiber alkene mixed dispersion liquid is arranged in substrate, the film obtained after drying exists
It is handled 15-30 minutes at a temperature of 500-900 DEG C, obtains graphene heat conducting film.
Can be agglomerated into when being dispersed in water due to the water transport property of graphene it is cotton-shaped, if filter or spraying film forming meeting so that
Graphene confusing array, to influence whole thermal conductivity, and the porosity is high.The present invention utilize fiber hydrophily, and with
The suction-operated of graphene reduces the agglomerating effect between graphene, and favorable orientation when fiber film forming, fiber is made to drive graphite
Alkene orientation chemical conversion film, the graphene heat conducting film that the present invention is prepared have height-orientedization, and thermal coefficient is up to 1000-
1500W/mK, mechanical stretch intensity 30-70MPa.
Specific embodiment
The present invention provides a kind of preparation method of graphene heat conducting film, this method comprises:
Step 1: graphite is immersed in mixed acid solution, and intercalator stirring is then added, obtains mixed solution；
Step 2: organic reagent being added in the mixed solution that step 1 obtains and is reacted, and obtains the water dispersion of graphene
Liquid；
Step 3: be added in graphene dispersing solution obtained in step 2 natural plants long fibre or polymeric long fiber into
Row excusing from death processing, obtains graphite fiber alkene mixed dispersion liquid；
Step 4: the graphite fiber alkene mixed dispersion liquid that step 3 is obtained is arranged in substrate, the film obtained after drying
It is handled 15-30 minutes at a temperature of 500-900 DEG C, obtains graphene heat conducting film.
According to the present invention, first graphite is immersed in mixed acid solution, intercalator stirring is then added, obtains mixed solution；
The mixing time is preferably 6-24 hours, preferably before stirring, is first had children outside the state plan mixture, the excusing from death time
Preferably 30min；The quality (g) of the graphite: the volume (ml) of mixed acid solution is preferably 10:(200-1000).In order to increase
Add the severe degree and discharge quantity of reaction, inorganic salts preferably are added when impregnating, keep peeling effect more preferable, the inorganic salts
Additive amount is preferably graphite quality 10-50%, and the inorganic salts preferably include ammonium nitrate, potassium chlorate, potassium hyperchlorate, chloric acid
Lithium, lithium perchlorate, phosphorus pentoxide or ammonium persulfate.
According to the present invention, the graphite is preferably the expanded graphite or crystalline flake graphite being commercialized, the carbon of the graphite
Content is preferably 98% or more；The mixed acid solution is preferably made of strong absorptive concentrated acid and oxidisability concentrated acid, strong absorptive
Concentrated acid preferably includes the concentrated sulfuric acid, concentrated phosphoric acid or pyrosulfuric acid, and oxidisability concentrated acid preferably includes concentrated nitric acid, pyrosulfuric acid, acid iodide, high iodine
Acid, perchloric acid or bromic acid；The intercalator be preferably selected from one of acid iodide, periodic acid, perchloric acid, bromic acid or chlorosulfonic acid or
It is several；The volume ratio of the strong absorptive concentrated acid, oxidisability concentrated acid and intercalator is preferably (0.5-8): (1-3): 1；
According to the present invention, organic reagent is add to the above mixed solution and is stirred to react, abnormal reaction is violent, Zhi Daoke
When the mixed liquor of flowing becomes close to the gel of solid phase, reaction terminates, and above-mentioned gel is washed, and gained gel is cleaned into
Property, resulting graphene dispersing solution is preferably dispersed by being ultrasonically treated, the graphite that can will be agglomerated in cleaning process in this way
Alkene separates, and Cheng Pengsong's is cotton-shaped, and the sonication treatment time is preferably 30 minutes, and the aqueous dispersions of graphene can be obtained.
Preferably, the organic reagent is preferably the organic reagent containing reducing agent, includes more preferably hydrazine hydrate, has
The CS of machine amine, the saturated aqueous solution of reproducibility salt or S2Saturated solution；The organic amine preferably includes ethylenediamine or the third three；Also
The saturated aqueous solution of originality salt preferably includes NaS2、Na2S2O3Or Na2S2O4；The volume ratio of the nitration mixture and organic reagent is excellent
It is selected as (2-10): (1-5)；The time that is stirred to react is 2-10min.
According to the present invention, disperse in water more preferably to make to react finally obtained graphene, it preferably can be molten in nitration mixture
Organic surface active agent is added in liquid, gel can also be dissolved in polar organic solvent after the completion of reaction, then ultrasonic water again
Adjustment pH value is washed, the graphene dispersion obtained in this way is more preferable, and single layer is more, avoids certain Second Aggregation.It is described
Organic surface active agent additive amount be preferably graphite quality 5-25%, preferably include PVP, PVA, PSS, dodecyl sulphur
Sour sodium, cetyl benzenesulfonic acid sodium, triton X-100, P123, P127 or CMC；The polar organic solvent is preferably first
Base formamide (DMF), N methyl pyrrolidone (NMP) or dimethyl sulfoxide (DMSO)；The nitration mixture and polarity organic reagent
Volume ratio is (2-10): (5-10)
According to the present invention, natural plants long fibre will be added in above-mentioned graphene dispersing solution or polymeric long fiber surpasses
Raw processing, the excusing from death processing time is preferably 15-60 minutes, obtains graphite fiber alkene mixed dispersion liquid；The fiber
The concentration of graphene mixed liquor dispersion liquid is preferably 0.3-2g/L, and in the aqueous dispersions of the graphene, graphene thickness is excellent
Choosing is less than 3 nanometers, and lamella size is preferably 150-600 microns, and concentration is preferably 1-20g/L.
According to the present invention, the natural plants long fibre be preferably degreasing wood-fibred, cotton fiber, filter paper comminution pulp or
Silk is chopped；The polymeric long fiber be preferably regenerated celulose fibre be chopped, nylon be chopped, terylene, polyamide fibre, acrylic fibers,
Polyvinyl chloride fibre, polyvinyl or spandex.The natural plants long fibre or the long stapled additional amount of polymer are preferably graphene quality
3-40%.The natural plants long fibre or the long stapled length of polymer are preferably 0.5-7 millimeters, more preferably 1-5 milli
Rice, thickness is preferably 3-30 microns, more preferably 3-15 microns.
According to the present invention, in order to improve mechanical property, carbon nanotube or chopped carbon are added preferably in graphene dispersing solution
Fiber.The diameter of the carbon nanotube is preferably 20-50nm, and 50-500 microns of length, additive amount is preferably graphene quality
5%wt, the additive amount of chopped carbon fiber is the 7.5%wt of graphene quality, preferably 7 microns of chopped carbon fiber diameter, length 3
Millimeter.
According to the present invention, above-mentioned graphite fiber alkene mixed dispersion liquid is arranged in substrate, the substrate is not special
Limitation, preferably copper foil, aluminium foil or PET film, the graphite fiber alkene mixed dispersion liquid preferably pass through suction filtration or spraying
Mode is arranged in substrate, and more preferably spraying method is, it can be achieved that continuous production.
According to the present invention, after the film associated basis bottom that above-mentioned spraying or suction filtration obtain is dried together, then press polish processing is led to
It crosses machine to peel, then by above-mentioned processed film, air atmosphere is handled 15-30 minutes at a temperature of 500-900 DEG C, will be mixed
Miscellaneous fiber calcination is clean, and at this time due to using the graphene of the extremely low oxygen content of high-quality, graphene still may be used at high temperature
It keeps stablizing.Finally, burnt graphene is handled using multiple grade press polish, stomata is excluded, improves density, it is final to obtain
To pure graphene heat conducting film.
The present invention is further elaborated below with reference to embodiment, the raw material being related in embodiment is commercially available obtains
?.
Embodiment 1
10g expanded graphite (25 mesh) is added in 200mL nitration mixture (concentrated sulfuric acid and concentrated nitric acid), perchloric acid is then added,
Wherein dense H2SO4/HClO4/ dense HNO3=0.5/1/1, it stirs evenly and closes, for ultrasonic treatment after 30 minutes, magnetic agitation 6 is small
When, 100mL hydrazine hydrate solution is then slowly added dropwise into mixed liquor while agitating, stirs 2min, said mixture can body
Product sharply expands, and becomes dark thick colloid, is cleaned gained gel to neutrality with deionized water, excusing from death processing 30min is obtained
The aqueous dispersions of graphene, in the aqueous dispersions of the graphene, 2 nanometers of graphene thickness, lamella size is 300 microns,
Concentration is 10g/L；
Degreasing wood-fibred is added into above-mentioned graphene dispersing solution to be chopped, the additive amount of opposite graphene is 12.5%, fine
Mixed solution 7 microns of fiber thickness, is then diluted to 0.3/L, is ultrasonically treated 15 minutes, obtains cebollite by 3 millimeters of length of dimension
Black alkene mixed dispersion liquid；
It is by above-mentioned graphite fiber alkene mixed dispersion liquid spray treatment in copper foil substrate, the above-mentioned film sprayed to is related
Together then film transfer is got off the membrane pressure light processing of drying to substrate by 60 DEG C of vacuum dryings by machine, by above-mentioned processing
Film at a temperature of 900 DEG C air atmosphere handle 15 minutes, the calcining that is chopped of the degreasing wood-fibred of doping is clean, at this time due to making
It is the graphene of the extremely low oxygen content of high-quality, graphene can still keep stable at high temperature.Finally, by burnt graphite
Alkene is handled using multiple grade press polish, excludes stomata, is improved density, is finally obtained pure graphene heat conducting film.
The graphene heat conducting film thermal coefficient that embodiment 1 obtains is 1000W/mK, and mechanical stretch intensity is 50MPa.
Embodiment 2
10g crystalline flake graphite (200 mesh) is added in 1L nitration mixture (concentrated sulfuric acid and concentrated nitric acid), bromic acid is then added, wherein
Dense H2SO4/HBrO3/ dense HNO3=8/1/3, it stirs evenly and closes, ultrasonic treatment is after 30 minutes, and magnetic agitation 24 hours, so
500mL hydrazine hydrate solution is slowly added dropwise into mixed liquor while agitating afterwards, stirs 10min, said mixture can volume urgency
Play expansion, becomes dark thick colloid, is cleaned gained gel to neutrality with deionized water, excusing from death processing 30min obtains graphite
The aqueous dispersions of alkene, in the aqueous dispersions of the graphene, 2 nanometers of graphene thickness, lamella size is 150 microns, concentration
For 1g/L；
Degreasing cotton fiber is added into above-mentioned graphene dispersing solution to be chopped, the additive amount of opposite graphene is 10%, fiber
3 millimeters of length, 6 microns of fiber thickness, mixed solution is then diluted to 1/L, is ultrasonically treated 60 minutes, obtains graphite fiber alkene
Mixed dispersion liquid；
It is by above-mentioned graphite fiber alkene mixed dispersion liquid with filtering processing in aluminum foil substrate, the above-mentioned film sprayed to is related
Together then film transfer is got off the membrane pressure light processing of drying to substrate by 60 DEG C of vacuum dryings by machine, by above-mentioned processing
Film at a temperature of 500 DEG C air atmosphere handle 30 minutes, the calcining that is chopped of the degreasing cotton fiber of doping is clean, at this time due to making
It is the graphene of the extremely low oxygen content of high-quality, graphene can still keep stable at high temperature.Finally, by burnt graphite
Alkene is handled using multiple grade press polish, excludes stomata, is improved density, is finally obtained pure graphene heat conducting film.
The graphene heat conducting film thermal coefficient that embodiment 2 obtains is 1500W/mK, and mechanical stretch intensity is 40MPa.
Embodiment 3
10g crystalline flake graphite (100 mesh) is added in 500mL nitration mixture (concentrated sulfuric acid and concentrated nitric acid), periodic acid is then added,
Wherein dense H2SO4/HIO4/ dense HNO3=3/1/2, it stirs evenly and closes, ultrasonic treatment is after 30 minutes, and magnetic agitation 12 hours,
Then 300mL hydrazine hydrate solution is slowly added dropwise into mixed liquor while agitating, stirs 5min, said mixture can volume urgency
Play expansion, becomes dark thick colloid, is cleaned gained gel to neutrality with deionized water, excusing from death processing 30min obtains graphite
The aqueous dispersions of alkene, in the aqueous dispersions of the graphene, 2 nanometers of graphene thickness, lamella size is 600 microns, concentration
For 20g/L；
Regenerated cellulose chopped strand is added into above-mentioned graphene dispersing solution, the additive amount of opposite graphene is 10%,
2 millimeters of fibre length, 5 microns of fiber thickness, mixed solution is then diluted to 1/L, is ultrasonically treated 30 minutes, obtains cebollite
Black alkene mixed dispersion liquid；
It is by above-mentioned graphite fiber alkene mixed dispersion liquid with filtering processing in aluminum foil substrate, the above-mentioned film sprayed to is related
Together then film transfer is got off the membrane pressure light processing of drying to substrate by 60 DEG C of vacuum dryings by machine, by above-mentioned processing
Film at a temperature of 800 DEG C air atmosphere handle 20 minutes, the regenerated cellulose chopped strand of doping is calcined it is clean, at this time by
In the graphene for using the extremely low oxygen content of high-quality, graphene can still keep stable at high temperature.Finally, by burnt
Graphene is handled using multiple grade press polish, excludes stomata, is improved density, is finally obtained pure graphene heat conducting film.
The graphene heat conducting film thermal coefficient that embodiment 3 obtains is 1300W/mK, and mechanical stretch intensity is 30MPa.
Embodiment 4
10g expanded graphite (25 mesh) is added in 200mL nitration mixture (concentrated sulfuric acid and concentrated nitric acid), perchloric acid is then added,
Wherein dense H2SO4/HClO4/ dense HNO3=0.5/1/1, it stirs evenly and closes, for ultrasonic treatment after 30 minutes, magnetic agitation 6 is small
When, 100mL hydrazine hydrate solution is then slowly added dropwise into mixed liquor while agitating, stirs 2min, said mixture can body
Product sharply expands, and becomes dark thick colloid, is cleaned gained gel to neutrality with deionized water, excusing from death processing 30min is obtained
The aqueous dispersions of graphene, in the aqueous dispersions of the graphene, 2 nanometers of graphene thickness, lamella size is 300 microns,
Concentration is 10g/L；
Vinylon fibre (vinylon) is added into above-mentioned graphene dispersing solution, the addition of opposite graphene
Amount is 15%, 2 millimeters of fibre length, 5 microns of fiber thickness, mixed solution is then diluted to 1.5/L, is ultrasonically treated 20 points
Clock obtains graphite fiber alkene mixed dispersion liquid；
Above-mentioned graphite fiber alkene mixed dispersion liquid is used through suction method film setting in copper foil substrate, is arrived above-mentioned
Together then film transfer is got off the membrane pressure light processing of drying, in process by 60 DEG C of vacuum dryings by machine at film associated basis bottom
The film of processing air atmosphere at a temperature of 900 DEG C is stated to handle 15 minutes, the vinylon fibre of doping is calcined it is clean, at this time due to making
It is the graphene of the extremely low oxygen content of high-quality, graphene can still keep stable at high temperature.Finally, by burnt graphite
Alkene is handled using multiple grade press polish, excludes stomata, is improved density, is finally obtained pure graphene heat conducting film.
The graphene heat conducting film thermal coefficient that embodiment 4 obtains is 1200W/mK, and mechanical stretch intensity is 45MPa.
Embodiment 5
10g expanded graphite (25 mesh) is added in 200mL nitration mixture (concentrated sulfuric acid and concentrated nitric acid), perchloric acid is then added,
Wherein dense H2SO4/HClO4/ dense HNO3=0.5/1/1, it stirs evenly and closes, for ultrasonic treatment after 30 minutes, magnetic agitation 6 is small
When, 100mL hydrazine hydrate solution is then slowly added dropwise into mixed liquor while agitating, stirs 2min, said mixture can body
Product sharply expands, and becomes dark thick colloid, is cleaned gained gel to neutrality with deionized water, excusing from death processing 30min is obtained
The aqueous dispersions of graphene, in the aqueous dispersions of the graphene, 2 nanometers of graphene thickness, lamella size is 300 microns,
Concentration is 10g/L；
Acrylic fiber (polyacrylonitrile fibre) is added into above-mentioned graphene dispersing solution, the additive amount of opposite graphene is
9%, 3 millimeters of fibre length, 7 microns of fiber thickness, mixed solution is then diluted to 0.3/L, is ultrasonically treated 20 minutes, obtains
Graphite fiber alkene mixed dispersion liquid；
Above-mentioned graphite fiber alkene mixed dispersion liquid is used through spray treatment in copper foil substrate, the above-mentioned film arrived is related
Together then film transfer is got off the membrane pressure light processing of drying to substrate by 60 DEG C of vacuum dryings by machine, by above-mentioned processing
Film at a temperature of 800 DEG C air atmosphere handle 20 minutes, the acrylic fiber of doping is calcined it is clean, at this time due to using
The graphene of the extremely low oxygen content of high-quality, graphene can still keep stable at high temperature.Finally, burnt graphene is passed through again
Excessive grade press polish processing, excludes stomata, improves density, finally obtain pure graphene heat conducting film.
The graphene heat conducting film thermal coefficient that embodiment 5 obtains is 1400W/mK, and mechanical stretch intensity is 45MPa.
Embodiment 6
10g expanded graphite (25 mesh) is added in 200mL nitration mixture (concentrated sulfuric acid and concentrated nitric acid), perchloric acid is then added,
Wherein dense H2SO4/HClO4/ dense HNO3=0.5/1/1, it stirs evenly and closes, for ultrasonic treatment after 30 minutes, magnetic agitation 6 is small
When, 100mL hydrazine hydrate solution is then slowly added dropwise into mixed liquor while agitating, stirs 2min, said mixture can body
Product sharply expands, and becomes dark thick colloid, is cleaned gained gel to neutrality with deionized water, excusing from death processing 30min is obtained
The aqueous dispersions of graphene, in the aqueous dispersions of the graphene, 2 nanometers of graphene thickness, lamella size is 300 microns,
Concentration is 10g/L；
It is more with respect to graphene amount that acrylic fiber (polyacrylonitrile fibre) and 5%wt are added into above-mentioned graphene dispersing solution
Wall carbon nano tube, acrylic fiber with respect to graphene additive amount be 9%, 3 millimeters of fibre length, 7 microns of fiber thickness, carbon Guan Zhi
Mixed solution 200 microns of length, is then diluted to 0.3/L, is ultrasonically treated 20 minutes, it is mixed to obtain graphite fiber alkene by diameter 30nm
Close dispersion liquid；
Above-mentioned graphite fiber alkene mixed dispersion liquid is used through spray treatment in copper foil substrate, the above-mentioned film arrived is related
Together then film transfer is got off the membrane pressure light processing of drying to substrate by 60 DEG C of vacuum dryings by machine, by above-mentioned processing
Film at a temperature of 800 DEG C air atmosphere handle 20 minutes, the acrylic fiber of doping is calcined it is clean, at this time due to using
The graphene of the extremely low oxygen content of high-quality, graphene can still keep stable at high temperature.Finally, burnt graphene is passed through again
Excessive grade press polish processing, excludes stomata, improves density, finally obtain pure graphene heat conducting film.
The graphene heat conducting film thermal coefficient that embodiment 6 obtains is 1500W/mK, and mechanical stretch intensity is 60MPa.
Embodiment 7
10g expanded graphite (25 mesh) is added in 200mL nitration mixture (concentrated sulfuric acid and concentrated nitric acid), perchloric acid is then added,
Wherein dense H2SO4/HClO4/ dense HNO3=0.5/1/1, it stirs evenly and closes, for ultrasonic treatment after 30 minutes, magnetic agitation 6 is small
When, 100mL hydrazine hydrate solution is then slowly added dropwise into mixed liquor while agitating, stirs 2min, said mixture can body
Product sharply expands, and becomes dark thick colloid, is cleaned gained gel to neutrality with deionized water, excusing from death processing 30min is obtained
The aqueous dispersions of graphene, in the aqueous dispersions of the graphene, 2 nanometers of graphene thickness, lamella size is 300 microns,
Concentration is 10g/L；
Acrylic fiber (polyacrylonitrile fibre) and 7.5%wt are added into above-mentioned graphene dispersing solution with respect to graphene amount
Carbon fiber is chopped, and carbon fiber is chopped 7 microns of diameter, and 3 millimeters of length, acrylic fiber is 9% with respect to the additive amount of graphene, acrylic fibers
3 millimeters of fibre length, 7 microns of acrylic fiber thickness, mixed solution, is then diluted to by carbon pipe diameter 30nm by 200 microns of length
0.3/L is ultrasonically treated 20 minutes, obtains graphite fiber alkene mixed dispersion liquid；
Above-mentioned graphite fiber alkene mixed dispersion liquid is used through spray treatment in copper foil substrate, the above-mentioned film arrived is related
Together then film transfer is got off the membrane pressure light processing of drying to substrate by 60 DEG C of vacuum dryings by machine, by above-mentioned processing
Film at a temperature of 800 DEG C air atmosphere handle 20 minutes, the acrylic fiber of doping is calcined it is clean, at this time due to using
The graphene of the extremely low oxygen content of high-quality, graphene can still keep stable at high temperature.Finally, burnt graphene is passed through again
Excessive grade press polish processing, excludes stomata, improves density, finally obtain pure graphene heat conducting film.
The graphene heat conducting film thermal coefficient that embodiment 7 obtains is 1500W/mK, and mechanical stretch intensity is 70MPa.
Claims (8)
1. a kind of preparation method of graphene heat conducting film, which is characterized in that this method comprises:
Step 1: graphite is immersed in mixed acid solution, and intercalator stirring is then added, obtains mixed solution；
Step 2: organic reagent being added in the mixed solution that step 1 obtains and is reacted, and obtains the aqueous dispersions of graphene；Institute
The organic reagent stated includes the CS of hydrazine hydrate, organic amine, the saturated aqueous solution of reproducibility salt or S2Saturated solution；
Step 3: natural plants long fibre is added in graphene dispersing solution obtained in step 2 or polymeric long fiber is surpassed
Sonication obtains graphite fiber alkene mixed dispersion liquid；The natural plants long fibre or the long stapled length of polymer are
0.5-7 millimeters, with a thickness of 3-30 microns；
Step 4: the graphite fiber alkene mixed dispersion liquid that step 3 is obtained is arranged in substrate, and the film obtained after drying exists
500-900oIt is handled 15-30 minutes at a temperature of C, obtains graphene heat conducting film；
In the aqueous dispersions of the graphene, graphene thickness is less than 3 nanometers, and 150-600 microns of lamella size, concentration 1-
20g/L。
2. a kind of preparation method of graphene heat conducting film according to claim 1, which is characterized in that the natural plants
Long fibre is that degreasing wood-fibred, cotton fiber, filter paper comminution pulp or silk are chopped.
3. a kind of preparation method of graphene heat conducting film according to claim 1, which is characterized in that the polymeric long
Fiber is that regenerated celulose fibre is chopped, nylon is chopped, terylene, polyamide fibre, acrylic fibers, polyvinyl chloride fibre, polyvinyl or spandex.
4. a kind of preparation method of graphene heat conducting film according to claim 1, which is characterized in that the natural plants
Long fibre or the long stapled additional amount of polymer are the 3-40% of graphene quality.
5. a kind of preparation method of graphene heat conducting film according to claim 1, which is characterized in that the step three
Sonication treatment time is 15-60 minutes.
6. a kind of preparation method of graphene heat conducting film according to claim 1, which is characterized in that the step three is also
It is included in graphene dispersing solution and carbon nanotube or chopped carbon fiber is added.
7. a kind of preparation method of graphene heat conducting film according to claim 1, which is characterized in that the graphite fiber
The concentration of alkene mixed dispersion liquid is 0.3-2g/L.
8. a kind of preparation method of graphene heat conducting film according to claim 1, which is characterized in that the substrate is copper
Foil, aluminium foil or PET film.
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| CN105802589A (en) * | 2016-05-09 | 2016-07-27 | 中国石油大学(北京) | High-strength heat-conducting film and preparation method thereof |
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| CN107500279B (en) * | 2017-08-04 | 2020-04-07 | 湖南国盛石墨科技有限公司 | Method for preparing graphene in batches and production system thereof |
| CN107416813A (en) * | 2017-10-03 | 2017-12-01 | 王干 | A kind of simple and easy method for preparing high-quality graphene |
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| CN111978931A (en) * | 2020-08-27 | 2020-11-24 | 清华大学深圳国际研究生院 | Graphene composite slurry, graphite heat dissipation film structure and preparation method thereof |
| CN112038654B (en) * | 2020-08-27 | 2021-10-19 | 清华大学深圳国际研究生院 | Preparation method of bipolar plate and bipolar plate |
| CN115745608B (en) * | 2022-11-29 | 2023-12-22 | 科泽新材料股份有限公司 | Method for preparing graphene heat conduction film by doping carbon nano tube |
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