CN108658615A - A kind of graphene-based laminated film of high heat conduction and preparation method thereof - Google Patents

A kind of graphene-based laminated film of high heat conduction and preparation method thereof Download PDF

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CN108658615A
CN108658615A CN201810612571.9A CN201810612571A CN108658615A CN 108658615 A CN108658615 A CN 108658615A CN 201810612571 A CN201810612571 A CN 201810612571A CN 108658615 A CN108658615 A CN 108658615A
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graphene
laminated film
graphite
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graphene oxide
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CN108658615B (en
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李静
陈旭阳
李阳
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South China University of Technology SCUT
Zhuhai Institute of Modern Industrial Innovation of South China University of Technology
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South China University of Technology SCUT
Zhuhai Institute of Modern Industrial Innovation of South China University of Technology
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Abstract

The invention discloses graphene-based laminated films of a kind of high heat conduction and preparation method thereof.In terms of the mass percent of solid material, the raw material group of the graphene-based laminated film becomes：40 70% graphene oxide, 30 60% stabilizer, 1 3% surfactant and 1 10% reinforcing agent；When preparation, graphene oxide dispersion, stabilizer, surfactant and enhancing agent dispersing liquid are mixed into ultrasound and are uniformly mixing to obtain graphite oxide alkenyl composite dispersion liquid, graphene oxide based coextruded film is obtained using solution film formation, finally obtains graphene-based laminated film by secondary hot pressing reducing process.The graphene-based laminated film thickness of the present invention is for 10 50 microns and controllable, and room temperature is 800 1600W m towards thermal coefficient‑1k‑1, tensile strength can reach 10 30MPa, and 180 ° of bendings are without breakage.

Description

A kind of graphene-based laminated film of high heat conduction and preparation method thereof
Technical field
The present invention relates to heat-conductive composite materials, and in particular to a kind of lightweight, flexibility and high thermal conductivity it is graphene-based multiple Condensation material and preparation method thereof is used for high-power, high heat flux density electronics industry and smart machine dissipation from electronic devices field.
Background technology
As electronic equipment size increasingly minimizes, component power density is continuously improved, and people are to quick high heat conduction elder generation Concern into material has obtained surprising growth.Although traditional metal materials flexibility is good, density is big, thermal conductivity is low, Cannot meet the needs of people.Therefore, nonmetallic materials at people research hotspot.Although high quality graphite and Buddha's warrior attendant The thermal coefficient of stone film can reach 2000W m-1k-1, but harsh working condition and high production cost limit the big of them Sizable application.In addition, the shortcomings of unprocessed graphite block is due to its low heat conductivity, frangible and easy picking and cannot be directly used to electricity Sub- industry.
Graphene, a kind of novel two-dimensional material have that thermal conductivity is good, mechanical performance is excellent, and acid and alkali-resistance etc. is a variety of excellent Performance.The thermal conductivity of suspension single-layer graphene at room temperature is up to 5300W m-1k-1, considerably beyond graphite and diamond, it is It is currently known the highest material of thermal coefficient.Direct apply of graphene mostly enhances the performance of substrate as additive, Such as thermal conductivity, electric conductivity and mechanical performance, this can not give full play to the due excellent properties of graphene.As graphene The graphene film of one of macroscopic material is widely paid close attention to by high thermal conductivity coefficient, conductivity and mechanical performance.And it is current The preparation method of graphene-based membrane material is typically first to be formed a film with graphene oxide (or graphene nanometer sheet), using high temperature (2000-3000 DEG C) thermal anneal process and high mechanical pressure (200-300MPa) compacting, obtain high thermal conductivity coefficient (>800W m-1k-1) and certain mechanical performance thin-film material.There are apparent drawbacks for this technique, if energy consumption is big, with energy-saving and emission-reduction trend It is not consistent；Operating condition is harsh, and superhigh temperature and super-pressure realize that difficulty is big；Production cost is high, and product economy benefit is low etc..Cause This, prepares high thermal conductivity coefficient and the graphene-based thin-film material of good mechanical properties under the conditions of a kind of low-temp low-pressure of research and development Production technology becomes a kind of development trend.
Invention content
For overcome the deficiencies in the prior art, it is 800-1600W m that the present invention provides a kind of room temperatures towards thermal coefficient- 1k-1, tensile strength is up to 10-30MPa, 180 ° of unabroken graphene-based laminated films of high heat conduction of bending and preparation method thereof, With preparation process temperature low-pressure is low, easy to operate and energy consumption is small, a series of advantages such as at low cost.
The object of the invention is achieved through the following technical solutions：
A kind of graphene-based laminated film of high heat conduction, it is characterised in that：In terms of the mass percent of solid material, the stone The raw material group of mertenyl laminated film becomes：It lives on the surface of the graphene oxide of 40-70%, the stabilizer of 30-60%, 1-3% The reinforcing agent of property agent and 1-10%；The mass ratio of solid material and liquid dispersant is 1-10:1000；
The graphene oxide is added with graphene oxide dispersion；
The stabilizer is one or more mixing in nano-cellulose, xylitol, glucose and sorbierite；
The surfactant is the mixing of one or both of dodecyl benzene sulfonic acid and Dodecyl Glucoside；
The reinforcing agent is added with carbon nanotube and/or carbon fiber dispersion liquid；
The graphene-based laminated film thickness is for 10-50 microns and controllable, and room temperature is 800-1600W towards thermal coefficient m-1k-1, tensile strength 10-30MPa, 180 ° of bendings are without breakage.
To further realize the object of the invention, it is preferable that the graphene oxide dispersion aoxidizes stone using water as solvent A concentration of 1.0-8.0mg ml of black alkene dispersion liquid-1, stablize storage and 6 months or more generated without precipitation；The carbon nanotube and/or Carbon fiber dispersion liquid is using absolute ethyl alcohol as solvent, a concentration of 0.5-1.5mg ml-1。
Preferably, the graphene oxide dispersion is prepared by the Hummers methods improved, is included the following steps：
1) it pre-oxidizes：Graphite powder, potassium peroxydisulfate and phosphorus pentoxide are scattered in the concentrated sulfuric acid, 75-85 DEG C of condensation of water-bath Back flow reaction 5-8 hours, is cooled to room temperature plus deionized water dilution, vacuum filtration are washed with deionized water and ethyl alcohol to neutrality, It is dry, obtain pre-oxidation graphite；
2) it reoxidizes：The pre-oxidation graphite and the concentrated sulfuric acid are blended under ice-water bath and stirring condition and are slowly added to Gao Meng Sour potassium ensures that mixture temperature is no more than 20 DEG C, then heats to 30-40 DEG C and reacts 1-4 hours, adds deionized water to dilute, room Hydrogen peroxide is added dropwise to remove remaining potassium permanganate in temperature stirring after 1-2 hours, obtain the graphite oxide suspension of glassy yellow.
3) washing dispersion：After the graphite oxide suspension stratification, supernatant is outwelled, is precipitated to graphite oxide Dilute hydrochloric acid is added dropwise in object；Stratification adds dilute hydrochloric acid, repeated washing, to last time oxygen into sediment after outwelling supernatant again Deionized water is added in graphite sediment, centrifugal treating outwells centrifuged supernatant, is added in being precipitated to remaining graphite oxide Deionized water, ultrasonic disperse 2-4 hours, is then charged into bag filter, is positioned in deionized water a couple of days of dialysing, until dialysis It is 6.5-7.0 that deionized water, which can't detect sulfate ion and pH value, obtains graphene oxide dispersion.
Preferably, the mass ratio of the graphite powder, potassium peroxydisulfate and phosphorus pentoxide is 1:0.5-0.7:0.5-0.7； The mass ratio ranging from 1 of the pre-oxidation graphite, the concentrated sulfuric acid and potassium permanganate:55-73:3-5.
Preferably, the concentrated sulfuric acid molar concentration is 15-18mol L-1, the dilute hydrochloric acid molar concentration is 2.5- 3.0mol L-1。
Preferably, the temperature of the drying is 100-110 DEG C；The number of the repeated washing is 4-6 times；Described The rotating speed of centrifugal treating is 4000-6000rpm, and the time is 15-30 minutes.
Preferably, the carbon nanotube is that outer diameter is led less than 10 nanometers, the height of 5-15 microns of length, purity more than 97% Hot multi-walled carbon nanotube；The carbon fiber is that carbon content is more than 95%, mesh number 300-200, maximum length is 50-74 microns Carbon fiber powder.
The preparation method of the graphene-based laminated film of the high heat conduction：By graphene oxide dispersion, stabilizer, surface Activating agent and enhancing agent dispersing liquid mix ultrasound and are uniformly mixing to obtain graphite oxide alkenyl composite dispersion liquid, utilize solution film forming Method obtains graphene oxide based coextruded film, finally obtains graphene-based laminated film by secondary hot pressing reducing process；It is described Secondary hot pressing reducing process be made of following two steps：
1) graphene oxide based coextruded film is positioned in high temperature resistant graphite jig, applies 1-3MPa pressure, in inertia In atmosphere, it is warming up to 250-300 DEG C, heat preservation is gradually cooling to room temperature after 30-60 minutes, the graphite oxide alkenyl just restored Laminated film；
2) the graphene oxide based coextruded film just restored is applied to the pressure of 10-12MPa, in an inert atmosphere, heating To 700-800 DEG C, 60-120 minutes postcoolings of heat preservation obtain graphene-based laminated film to room temperature.
Preferably, described in step 1) and step 2) it is high temperature process furnances in inert atmosphere in an inert atmosphere In；The inert gas includes argon gas or nitrogen.
Preferably, the solution film formation is vacuum filtration method, coating method or evaporation solwution method.
The present invention prepares graphene oxide dispersion by improveing Hummers methods, adds a certain amount of stabilizer, surface is lived Property agent and enhancing agent dispersing liquid and being stirred by ultrasonic be uniformly mixed, obtain graphite oxide alkenyl composite dispersion liquid, vacuum recycled to take out Filter method, coating method or evaporation solwution method etc. obtain graphene oxide based coextruded film, finally pass through secondary hot pressing also at membrane means Former technique receives graphene-based laminated film, and thickness is for 10-50 microns and controllable, and room temperature is 800-1600W towards thermal coefficient m-1k-1, tensile strength 10-30MPa, 180 ° are bent without breakage, and it is special to possess good heat transfer property, mechanical performance and lightweight Property, there is prodigious actual application value.
Compared with the existing technology, the invention has the advantages that and advantageous effect：
(1) present invention Hummers methods used improved prepare graphene oxide dispersion without using harmful nitrate (such as sodium nitrate)；First passing through " pre-oxidation " can make " reoxidizing " process under compared with low reaction temperatures (30-40 DEG C) by graphite Powder is fully oxidized；The graphene oxide dispersion of preparation can stablize storage 6 months or more without precipitation, subsequently to prepare graphene Based coextruded film provides sufficient raw material guarantee.
(2) the graphene-based laminated film thickness prepared by the present invention is for 10-50 microns and controllable, at room temperature towards heat conduction Coefficient is in 800-1600W m-1k-1, tensile strength 10-30MPa, 180 ° of bendings are without breakage, without apparent picking, with good Heat transfer property, mechanical performance and light weight characteristics.
(3) the secondary hot pressing reducing process that the present invention uses, can be first in low temperature (250-300 DEG C) low pressure (1-3MPa) item Most of oxygen-containing group in graphene oxide based coextruded film is removed under part, then in lower temperature (700-800 DEG C) compared with low pressure Surfacing is obtained while removing portion of residual oxygen-containing group under power (10-12MPa) and has the high-termal conductivity, excellent of metallic luster Different mechanicalness and graphene-based laminated film compared with low-density.Compared with the existing technology in high temperature (2000-3000 DEG C) high pressure Commercial graphite film or graphene film are prepared under (200-300MPa) pressure has high energy-saving effect and milder production The distinguishing features such as condition.
(4) present invention employs stabilizer and reinforcing agent is added in graphene oxide dispersion, heat can be effectively realized The air gap in the reparation and filled composite film of graphene nano chip architecture in reduction process is pressed, there is more complete lamella knot Structure forms more smoothly passage of heat, improves the heat conductivility and mechanical performance of film.
Specific implementation mode
With reference to embodiment, the invention will be further described, but the present embodiment should not be understood as protecting the present invention The limitation of range, those skilled in the art make some nonessential changes and adjustment according to the present invention, belong to the present invention Protection domain.
The thermal coefficient of prepared film sample is calculated by formula λ=α ρ Cp, and wherein λ is the heat conduction of sample Coefficient (W m-1k-1), α is the thermal diffusion coefficient (mm of sample2s-1), ρ is density (the g cm of sample-3), Cp is the specific heat of sample Hold (J g-1K-1)；Further, the measurement towards thermal diffusion coefficient of sample is shone using the laser with quick, accurate feature Method, instrument are flicker method thermal conductivity factor instrument (NETZSCH LFA 447NanoFlas), and test temperature is room temperature；Sample Density is calculated by the quality and volume of sample；The specific heat capacity of sample by dynamic streaming differential scanning calorimeter (DSC, NETZSCH DSC 204F1) measure obtain, 25 DEG C of test temperature.Specific test process ginseng of the film sample towards thermal coefficient Examine document (Kong, Qing-Qiang, Liu Z, Gao, Jian-Guo, et al.Hierarchical Graphene-Carbon Fiber Composite Paper as a Flexible Lateral Heat Spreader[J].Advanced Functional Materials,2014,24(27):4222-4228；The preparation of the graphene-based films of Song Ningjing and mechanics and University of thermal property research [D] the Chinese Academy of Sciences, 2016).
Tensile strength refers to the drag for the maximum uniform plastic deformation that material can be born, to the mechanical property of judgement material Energy.The tensile strength of sample analyzes (TA DMA Q800) using dynamic thermomechanical, prestressing force 0.01N, tensile speed 0.05% min-1。
Film sample, is directly carried out 180 ° of bendings by bend test under no supporting condition, and radius of curvature minimum can reach 3.5 millimeters, no any damaged appearance.
Embodiment 1
A kind of graphene-based laminated film of high heat conduction and preparation method thereof, comprises the following specific steps that：
(1) graphene oxide dispersion is prepared by the Hummers methods of improvement
Pre-oxidation：0.7 gram of potassium peroxydisulfate and 0.7 gram of phosphorus pentoxide are evenly spread into 6 milliliters of 18mol L-1Dense sulphur In acid, 1 gram of graphite powder is added, is rocked uniformly, condensing reflux reacts 6 hours in 80 DEG C of water-baths, is diluted after being cooled to room temperature Into 150 ml deionized waters, vacuum filtration is rinsed with deionized water and ethyl alcohol for several times to neutrality, by solid in 105 DEG C of dryings 4 hours, obtain pre-oxidation graphite；
It reoxidizes：By 1 gram of pre-oxidation graphite and 40 milliliters of 18mol L-1The concentrated sulfuric acid be blended in ice-water bath and stirring condition Under be slowly added to 5 grams of potassium permanganate, ensure that mixture temperature is no more than 20 DEG C, then heat to 35 DEG C or so and react 2 hours, instead It is slowly added to 200 milliliters of deionization dilutions (solution temperature is kept to be not higher than 50 DEG C) after answering, is added dropwise after being stirred at room temperature 2 hours 8 milliliters of hydrogen peroxide obtain the graphene oxide suspension that glassy yellow is presented in solution to remove remaining potassium permanganate；
Washing dispersion：The graphene oxide suspension stratification that will be obtained, carefully outwells supernatant, is dripped into sediment Add 150 milliliters of 3mol L-1Dilute hydrochloric acid, then stratification outwell supernatant and be added 150 milliliters of 3mol L-1Dilute hydrochloric acid, weight It is 6 times multiple, 100 ml deionized waters are added into last time graphite oxide sediment, 20 points are centrifuged under the conditions of 6000rpm Clock outwells centrifuged supernatant, and 200 ml deionized waters are added in being precipitated to remaining graphite oxide, ultrasonic disperse 3 hours, so Be fitted into bag filter afterwards, be positioned in deionized water and dialyse 7 days, until the deionized water of dialysis can't detect sulfate ion and PH value is 7.0, obtains graphene oxide dispersion.
(2) 10 milligrams of carbon nanotubes are scattered in 10 milliliters of absolute ethyl alcohols, ultrasound 2 hours obtains a concentration of 1.0mg ml-1Carbon nano tube dispersion liquid；10 milligrams of carbon fibers are scattered in 10 milliliters of absolute ethyl alcohols, ultrasound 2 hours obtains a concentration of 1.0mg ml-1Carbon fiber dispersion liquid；By 6 milliliters of a concentration of 4.2mg ml-1Graphene oxide dispersion and 15 milligrams of grapes Sugar, 0.5 milligram of dodecyl benzene sulfonic acid, 1.5 milliliters of a concentration of 1.0mg ml-1Carbon nano tube dispersion liquid and 1 milliliter it is a concentration of 1.0mg ml-1Carbon fiber dispersion liquid mixing, ultrasound after twenty minutes stir 5 minutes, obtain uniformly mixed graphite oxide alkenyl Composite dispersion liquid；
(3) vacuum filtration method is used, by uniformly mixed graphite oxide alkenyl composite dispersion liquid in 50 millimeters of diameter and hole Vacuum filter 4 hours on the cellulose mixture filter membrane (Tianjin is risen, water system filter membrane) of 45 microns of diameter then removes filter membrane and is put in 50 DEG C very It is 2 hours dry in empty drying box, it tears cellulose mixture filter membrane and obtains graphene oxide based coextruded film；
(4) among graphene oxide based coextruded film being positioned over graphite jig, apply 3MPa pressure, protected in argon gas atmosphere 300 DEG C are warming up in the high temperature process furnances of shield, heat preservation is gradually cooled to room temperature after sixty minutes, the graphene oxide just restored Based coextruded film；
(5) the graphene oxide based coextruded film just restored is applied into 12MPa pressure, is put into the high-temperature tubular of argon atmosphere In stove, it is warming up to 800 DEG C and keeps the temperature 120 minutes postcoolings to room temperature, obtain graphene-based laminated film.
By above-mentioned steps, graphene-based laminated film thickness is 12 microns, is 1580W m towards thermal conductivity-1k-1, resist Tensile strength is 20MPa, and 180 ° of bendings are without breakage.
Embodiment 2：
(1) graphene oxide dispersion is prepared by the Hummers methods of improvement
Pre-oxidation：0.5 gram of potassium peroxydisulfate and 0.6 gram of phosphorus pentoxide are evenly spread into 5 milliliters of 18mol L-1Dense sulphur In acid, 1 gram of graphite powder is added, is rocked uniformly, condensing reflux reacts 5 hours in 83 DEG C of water-baths, is diluted after being cooled to room temperature Into 120 ml deionized waters, vacuum filtration is rinsed with deionized water and ethyl alcohol for several times to neutrality, by solid in 100 DEG C of dryings 5 hours, obtain pre-oxidation graphite；
It reoxidizes：By 1 gram of pre-oxidation graphite and 30 milliliters of 18mol L-1The concentrated sulfuric acid be blended in ice-water bath and stirring condition Under be slowly added to 3 grams of potassium permanganate, ensure that mixture temperature is no more than 20 DEG C, then heat to 38 DEG C or so and react 3 hours, instead It is slowly added to 180 milliliters of deionization dilutions (solution temperature is kept to be not higher than 50 DEG C) after answering, is dripped after being stirred at room temperature 1.5 hours Add 6 milliliters of hydrogen peroxide to remove remaining potassium permanganate, obtains the graphene oxide suspension that glassy yellow is presented in solution；
Washing dispersion：The graphene oxide suspension stratification that will be obtained, carefully outwells supernatant, is dripped into sediment Add 180 milliliters of 2.6mol L-1Dilute hydrochloric acid, then stratification outwell supernatant and be added 180 milliliters of 2.6mol L-1Dilute salt Acid is repeated 5 times, and 120 ml deionized waters are added into last time graphite oxide sediment, are centrifuged under the conditions of 5000rpm 25 minutes, centrifuged supernatant is outwelled, 220 ml deionized waters are added in being precipitated to remaining graphite oxide, ultrasonic disperse 2.5 is small When, it is then charged into bag filter, is positioned in deionized water and dialyses 7 days, until the deionized water of dialysis can't detect sulfate radical Ion and pH value are 6.7, obtain graphene oxide dispersion.
(2) 10 milligrams of carbon nanotubes are scattered in 10 milliliters of absolute ethyl alcohols, ultrasound 2 hours obtains a concentration of 1.0mg ml-1Carbon nano tube dispersion liquid；5 milligrams of carbon fibers are scattered in 5 milliliters of absolute ethyl alcohols, ultrasound 2 hours obtains a concentration of 1.0mg ml-1Carbon fiber dispersion liquid；By 10 milliliters of a concentration of 4.0mg ml-1Graphene oxide dispersion and 25 milligrams of wood Sugar alcohol, 1 milligram of Dodecyl Glucoside, 2 milliliters of a concentration of 1.0mg ml-1Carbon nano tube dispersion liquid and 0.5 milliliter it is a concentration of 1.0mg ml-1Carbon fiber dispersion liquid mixing, ultrasound 15 minutes after stir 5 minutes, obtain uniformly mixed graphite oxide alkenyl Composite dispersion liquid；
(3) vacuum filtration method is used, by uniformly mixed graphite oxide alkenyl composite dispersion liquid in 50 millimeters of diameter and hole Vacuum filter 6 hours on the cellulose mixture filter membrane (Tianjin is risen, water system filter membrane) of 45 microns of diameter then removes filter membrane and is put in 50 DEG C very It is 2 hours dry in empty drying box, it tears cellulose mixture filter membrane and obtains graphene oxide based coextruded film；
(4) among graphene oxide based coextruded film being positioned over graphite jig, apply 2MPa pressure, protected in argon gas atmosphere 280 DEG C are warming up in the high temperature process furnances of shield, heat preservation is gradually cooled to room temperature after forty minutes, the graphene oxide just restored Based coextruded film；
(5) the graphene oxide based coextruded film just restored is applied into 10MPa pressure, is put into the high-temperature tubular of argon atmosphere In stove, it is warming up to 750 DEG C and keeps the temperature 100 minutes postcoolings to room temperature, obtain graphene-based laminated film.
By above-mentioned steps, graphene-based laminated film thickness is 20 microns, is 1300W m towards thermal conductivity-1k-1, resist Tensile strength is 12MPa, and 180 ° of bendings are without breakage.
Embodiment 3：
(1) graphene oxide dispersion is prepared by the Hummers methods of improvement
Pre-oxidation：0.7 gram of potassium peroxydisulfate and 0.5 gram of phosphorus pentoxide are evenly spread into 6 milliliters of 18mol L-1Dense sulphur In acid, 1 gram of graphite powder is added, is rocked uniformly, condensing reflux reacts 7 hours in 78 DEG C of water-baths, is diluted after being cooled to room temperature Into 130 ml deionized waters, vacuum filtration with deionized water ethyl alcohol and rinses for several times to neutrality, by solid in 110 DEG C of dryings 4 hours, obtain pre-oxidation graphite；
It reoxidizes：By 1 gram of pre-oxidation graphite and 35 milliliters of 16mol L-1The concentrated sulfuric acid be blended in ice-water bath and stirring condition Under be slowly added to 4 grams of potassium permanganate, ensure that mixture temperature is no more than 20 DEG C, then heat to 40 DEG C and react 2.5 hours, reaction After be slowly added to 160 milliliters of deionizations dilution (solution temperature is kept to be not higher than 50 DEG C), be added dropwise after being stirred at room temperature 1.5 hours 7 milliliters of hydrogen peroxide obtain the graphene oxide suspension that glassy yellow is presented in solution to remove remaining potassium permanganate；
Washing dispersion：The graphene oxide suspension stratification that will be obtained, carefully outwells supernatant, is dripped into sediment Add 140 milliliters of 2.8mol L-1Dilute hydrochloric acid, then stratification outwell supernatant and be added 140 milliliters of 2.8mol L-1Dilute salt Acid is repeated 5 times, and 140 ml deionized waters are added into last time graphite oxide sediment, are centrifuged under the conditions of 5500rpm 15 minutes, centrifuged supernatant is outwelled, 200 ml deionized waters are added in being precipitated to remaining graphite oxide, ultrasonic disperse 3 is small When, it is then charged into bag filter, is positioned in deionized water and dialyses 7 days, until the deionized water of dialysis can't detect sulfate radical Ion and pH value are 6.5, obtain graphene oxide dispersion.
(2) 10 milligrams of carbon fibers are scattered in 10 milliliters of absolute ethyl alcohols, ultrasound 2 hours obtains a concentration of 1.0mg ml-1 Carbon fiber dispersion liquid；By 40 milliliters of a concentration of 3.0mg ml-1Graphene oxide dispersion and 60 milligrams of nano-celluloses, 2 Milligram Dodecyl Glucoside, 2 milligrams of dodecyl benzene sulfonic acid, 5 milliliters of a concentration of 1.0mg ml-1Carbon fiber dispersion liquid mixing, Ultrasound stirs 5 minutes after 25 minutes, obtains uniformly mixed graphite oxide alkenyl composite dispersion liquid；
(3) using evaporation solwution method, uniformly mixed graphite oxide alkenyl composite dispersion liquid is poured into 50 millimeters of circles of diameter In shape flat-bottomed glass dish, it is put in 55 DEG C of air blast electrically heated drying cabinets and evaporates solvent 6 hours, film is carefully torn from glass dish Under, obtain graphene oxide based coextruded film.
(4) among graphene oxide based coextruded film being positioned over graphite jig, apply 1MPa pressure, protected in argon gas atmosphere 250 DEG C are warming up in the high temperature process furnances of shield, heat preservation is gradually cooled to room temperature after 30 minutes, the graphene oxide just restored Based coextruded film；
(5) the graphene oxide based coextruded film just restored is applied into 12MPa pressure, is put into the high-temperature tubular of argon atmosphere In stove, it is warming up to 700 DEG C and keeps the temperature 90 minutes postcoolings to room temperature, obtain graphene-based laminated film.
By above-mentioned steps, graphene-based laminated film thickness is 42 microns, is 900W m towards thermal conductivity-1k-1, tension Intensity is 25MPa, and 180 ° of bendings are without breakage.
Embodiment 4：
(1) graphene oxide dispersion is prepared by the Hummers methods of improvement
Pre-oxidation：0.6 gram of potassium peroxydisulfate and 0.6 gram of phosphorus pentoxide are evenly spread into 5 milliliters of 18mol L-1Dense sulphur In acid, 1 gram of graphite powder is added, is rocked uniformly, condensing reflux reacts 5.5 hours in 85 DEG C of water-baths, is cooled to room temperature rear dilute It releases into 160 ml deionized waters, is filtered by vacuum, rinsed for several times to neutrality with deionized water and ethyl alcohol, solid is done at 108 DEG C Dry 3.5 hours, obtain pre-oxidation graphite；
It reoxidizes：By 1 gram of pre-oxidation graphite and 38 milliliters of 18mol L-1The concentrated sulfuric acid be blended in ice-water bath and stirring condition Under be slowly added to 3.5 grams of potassium permanganate, ensure that mixture temperature is no more than 20 DEG C, then heat to 36 DEG C and react 3.5 hours, instead It is slowly added to 170 milliliters of deionization dilutions (solution temperature is kept to be not higher than 50 DEG C) after answering, is added dropwise after being stirred at room temperature 2 hours 7 milliliters of hydrogen peroxide obtain the graphene oxide suspension that glassy yellow is presented in solution to remove remaining potassium permanganate；
Washing dispersion：The graphene oxide suspension stratification that will be obtained, carefully outwells supernatant, is dripped into sediment Add 180 milliliters of 3mol L-1Dilute hydrochloric acid, then stratification outwell supernatant and be added 180 milliliters of 3mol L-1Dilute hydrochloric acid, weight It is 4 times multiple, 120 ml deionized waters are added into last time graphite oxide sediment, 20 points are centrifuged under the conditions of 4500rpm Clock outwells centrifuged supernatant, and 180 ml deionized waters are added in being precipitated to remaining graphite oxide, ultrasonic disperse 2.5 hours, It is then charged into bag filter, is positioned in deionized water and dialyses 7 days, until the deionized water of dialysis can't detect sulfate ion And pH value is 6.8, obtains graphene oxide dispersion.
(2) 10 milligrams of carbon fibers are scattered in 10 milliliters of absolute ethyl alcohols, ultrasound 2 hours obtains a concentration of 1.0mg ml-1 Carbon fiber dispersion liquid；By 10 milliliters of a concentration of 5.0mg ml-1Graphene oxide dispersion and 10 milligrams of glucose, 50 milligrams Sorbierite, 1.5 milligrams of dodecyl benzene sulfonic acid, 1.2 milliliters of a concentration of 1.0mg ml-1Carbon fiber dispersion liquid mixing, ultrasound 25 It is stirred 5 minutes after minute, obtains uniformly mixed graphite oxide alkenyl composite dispersion liquid；
(3) coating method is used, it is using coating device that uniformly mixed graphite oxide alkenyl composite dispersion liquid is uniform several times It is coated onto on glass substrate, is put in drying 2 hours in 55 DEG C of drying boxes, film is carefully torn from glass substrate, is aoxidized Graphene-based laminated film；
(4) among graphene oxide based coextruded film being positioned over graphite jig, apply 3MPa pressure, protected in argon gas atmosphere 280 DEG C are warming up in the high temperature process furnances of shield, heat preservation is gradually cooled to room temperature after forty minutes, the graphene oxide just restored Based coextruded film；
(5) the graphene oxide based coextruded film just restored is applied into 11MPa pressure, is put into the high-temperature tubular of argon atmosphere In stove, it is warming up to 750 DEG C and heat preservation is cooled to room temperature after sixty minutes, obtain graphene-based laminated film.
By above-mentioned steps, graphene-based laminated film thickness is 26 microns, is 1100W m towards thermal conductivity-1k-1, resist Tensile strength is 16MPa, and 180 ° of bendings are without breakage.
High temperature (2000-3000 DEG C) high pressure (200-300MPa) pressure is mostly used when existing graphene film and compound film preparation Power, operating condition is harsh, and energy consumption is big, and production cost is high.The preparation process of the present invention has low temperature, low pressure, energy consumption smaller The characteristics of.Low temperature is that thermal reduction temperature used is 700-800 DEG C, is compared with 2000-3000 DEG C of prior art processes temperature Apparent temperature is lower, and the lower required energy expenditure of temperature is just less, has the smaller advantage of energy consumption；Low pressure is institute It is 1-3MPa and 10-12MPa with pressure, operation pressure 200-300MPa is also lower with significant pressure compared with prior art Advantage, required mechanical energy are as a result just more energy saving with regard to smaller；The present invention is due to smaller with low temperature, low pressure, energy consumption Advantage, on the one hand working condition can be made milder production is upper, used equipment harsh conditions require less, operation Safety and reliability higher, operation is also simpler, conveniently, and production cost substantially reduces；On the other hand, low energy consumption more accords with Close energy-saving and emission-reduction, friendly environment society construction demand, the discharge capacitys such as more greenhouse gases can be reduced so that environmental protection at Originally it is significantly reduced.
Existing graphene film thermal coefficient is generally in 1000W m-1k-1Hereinafter, graphene-based multiple prepared by the present invention It is for 10-50 microns and controllable to close film thickness, room temperature is towards thermal coefficient in 800-1600W m-1k-1, tensile strength can reach To 10-30MPa, 180 ° of bendings have good heat transfer property, mechanical performance and light weight characteristics, graphene of the present invention without breakage Excellent combination property, thermal coefficient are not less than the graphene film of the prior art to based coextruded film compared with prior art, and also slightly Advantage, it is often more important that the present invention is more energy efficient under mild process conditions, the flexible light high thermal conductivity of more inexpensive preparation Graphene composite film；It has wide range of applications, in high-power, high heat flux density electronics industry and smart machine dissipation from electronic devices Field has great application prospect.

Claims (10)

1. a kind of graphene-based laminated film of high heat conduction, it is characterised in that：In terms of the mass percent of solid material, the graphite The raw material group of alkenyl laminated film becomes：The graphene oxide of 40-70%, the stabilizer of 30-60%, the surface-active of 1-3% The reinforcing agent of agent and 1-10%；The mass ratio of solid material and liquid dispersant is 1-10:1000；
The graphene oxide is added with graphene oxide dispersion；
The stabilizer is one or more mixing in nano-cellulose, xylitol, glucose and sorbierite；
The surfactant is the mixing of one or both of dodecyl benzene sulfonic acid and Dodecyl Glucoside；
The reinforcing agent is added with carbon nanotube and/or carbon fiber dispersion liquid；
The graphene-based laminated film thickness is for 10-50 microns and controllable, and room temperature is 800-1600W m towards thermal coefficient- 1k-1, tensile strength 10-30MPa, 180 ° of bendings are without breakage.
2. the graphene-based laminated film of high heat conduction according to claim 1, it is characterised in that：The graphene oxide point Dispersion liquid is using water as solvent, a concentration of 1.0-8.0mg ml of graphene oxide dispersion-1, stablize storage 6 months or more without precipitation It generates；The carbon nanotube and/or carbon fiber dispersion liquid are using absolute ethyl alcohol as solvent, a concentration of 0.5-1.5mg ml-1。
3. the graphene-based laminated film of high heat conduction according to claim 1, it is characterised in that：The graphene oxide dispersion Liquid is prepared by the Hummers methods improved, is included the following steps：
1) it pre-oxidizes：Graphite powder, potassium peroxydisulfate and phosphorus pentoxide are scattered in the concentrated sulfuric acid, 75-85 DEG C of condensing reflux of water-bath Reaction 5-8 hours, is cooled to room temperature plus deionized water dilution, vacuum filtration are washed with deionized water and ethyl alcohol to neutrality, does It is dry, obtain pre-oxidation graphite；
2) it reoxidizes：The pre-oxidation graphite and the concentrated sulfuric acid are blended under ice-water bath and stirring condition and are slowly added to permanganic acid Potassium ensures that mixture temperature is no more than 20 DEG C, then heats to 30-40 DEG C and reacts 1-4 hours, adds deionized water to dilute, room temperature Hydrogen peroxide is added dropwise to remove remaining potassium permanganate in stirring after 1-2 hours, obtain the graphite oxide suspension of glassy yellow.
3) washing dispersion：After the graphite oxide suspension stratification, supernatant is outwelled, into graphite oxide sediment Dilute hydrochloric acid is added dropwise；Stratification adds dilute hydrochloric acid, repeated washing to aoxidize stone to last time after outwelling supernatant into sediment again Deionized water is added in black sediment, centrifugal treating outwells centrifuged supernatant, to remaining graphite oxide precipitate in be added go from Sub- water, ultrasonic disperse 2-4 hours, is then charged into bag filter, is positioned in deionized water a couple of days of dialysing, until dialysis go from It is 6.5-7.0 that sub- water, which can't detect sulfate ion and pH value, obtains graphene oxide dispersion.
4. the graphene-based laminated film of high heat conduction according to claim 3, it is characterised in that：The graphite powder, over cure The mass ratio of sour potassium and phosphorus pentoxide is 1:0.5-0.7:0.5-0.7；Pre-oxidation graphite, the concentrated sulfuric acid and the potassium permanganate Mass ratio ranging from 1:55-73:3-5.
5. the graphene-based laminated film of high heat conduction according to claim 3, it is characterised in that：The concentrated sulfuric acid mole is dense Degree is 15-18mol L-1, the dilute hydrochloric acid molar concentration is 2.5-3.0mol L-1。
6. the graphene-based laminated film of high heat conduction according to claim 3, it is characterised in that：The temperature of the drying is 100-110℃；The number of the repeated washing is 4-6 times；The rotating speed of the centrifugal treating is 4000-6000rpm, time It is 15-30 minutes.
7. the graphene-based laminated film of high heat conduction according to claim 1, it is characterised in that：The carbon nanotube is outer Diameter is less than 10 nanometers, the high heat conduction multi-walled carbon nanotube of 5-15 microns of length, purity more than 97%；The carbon fiber contains for carbon Amount is more than 95%, mesh number 300-200, the carbon fiber powder that maximum length is 50-74 microns.
8. the preparation method of the graphene-based laminated film of claim 1-7 any one of them high heat conductions, it is characterised in that：By oxygen Graphite alkene dispersion liquid, stabilizer, surfactant and enhancing agent dispersing liquid mix ultrasound and are uniformly mixing to obtain graphite oxide Alkenyl composite dispersion liquid obtains graphene oxide based coextruded film using solution film formation, finally passes through secondary hot pressing and restores work Skill obtains graphene-based laminated film；The secondary hot pressing reducing process is made of following two steps：
1) graphene oxide based coextruded film is positioned in high temperature resistant graphite jig, applies 1-3MPa pressure, in inert atmosphere In, it is warming up to 250-300 DEG C, heat preservation is gradually cooling to room temperature after 30-60 minutes, and the graphite oxide alkenyl just restored is compound Film；
2) pressure that the graphene oxide based coextruded film just restored is applied to 10-12MPa is warming up in an inert atmosphere 700-800 DEG C, 60-120 minutes postcoolings of heat preservation obtain graphene-based laminated film to room temperature.
9. the preparation method of the graphene-based laminated film of high heat conduction according to claim 8, it is characterised in that：Step 1) and Described in step 2) is in the high temperature process furnances of inert atmosphere in an inert atmosphere；The inert gas includes argon Gas or nitrogen.
10. the preparation method of the graphene-based laminated film of high heat conduction according to claim 8, it is characterised in that：Described Solution film formation is vacuum filtration method, coating method or evaporation solwution method.
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