CN105731435A - High-strength flexible graphene composite heat conduction film and preparation method thereof - Google Patents
High-strength flexible graphene composite heat conduction film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-strength flexible graphene composite heat conduction film and a preparation method thereof. The film is formed by physically cross-linking macroscopic multi-layer folded graphene with micro-scale folds, wherein slice layers can slip, so that the film has extremely high flexibility. The graphene slice layers are perfect in structure, and slice-layer crystalline areas of the graphene slice layers are extremely great and have less defects, so that the graphene slice layers are compact in structure after being pressed under high pressure, and have extremely high conductivity and heat conduction. Meanwhile, in the presence of polymer based composites, the graphene slice layers can be cross-linked, so that the strength of the graphene film is strengthened. The high-strength flexible graphene composite heat conduction film has strength which can be up to 100-300MP, can be resistant to repeated bending by more than 1000 times, has elongation at break of 6-16%, has electric conductivity of 6000-8600S/cm, has thermal conductivity of 1400-1800W/mk, and can be widely used for high-strength designable heat-conduction and conductive apparatuses.
Description
Technical field
The present invention relates to Novel heat-conducting material and preparation method thereof, particularly relate to a kind of super flexible high thermal conductivity graphene film and
Its preparation method.
Background technology
2010, two of Univ Manchester UK professor Andre GeiM and Konstantin Novoselov because
It is successfully separated out stable Graphene first and obtains Nobel Prize in physics, start the upsurge that Graphene is studied by the whole world.
Graphene has excellent electric property, and (under room temperature, electron mobility is up to 2 × 105cM2/ Vs), prominent heat conductivility (5000W/
(MK), extraordinary specific surface area (2630M2/ g), its Young's modulus (1100GPa) and fracture strength (125GPa).Graphene is excellent
Different electrical and thermal conductivity performance is well beyond metal, and Graphene has an advantage of corrosion-and high-temp-resistant simultaneously, and its good machinery
Performance and relatively low density more allow it possess the potentiality at thermo electric material field substituted metal.
Macroscopic view assembles the main application that the graphene film of graphene oxide or graphene nanometer sheet is nanoscale graphite alkene
Form, conventional preparation method is suction method, scrape embrane method, spin-coating method, spraying process and dip coating etc..At further high temperature
Reason, it is possible to repair the defect of Graphene, it is possible to the effective electric conductivity improving graphene film and thermal conductance, can be widely applied to
In smart mobile phone, intelligence hardware, panel computer, notebook computer contour radiating requirements accompanied electronic equipment with oneself.
But at present, the undersize of graphene oxide used own, and containing a lot of fragments so that it is in terms of heat conduction
Not obtaining enough development, heat conductivility is limited in 1400W/mK, it is impossible to meet the demand of rapid technological growth.And film
The deficiency of structure design makes its flexibility be still not clear, and limits its application in terms of flexible device.The more important thing is, graphite
Alkene heat conduction film strength is less than 80MP so that its application is greatly limited.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of high tensile flexible Graphene composite heat conduction film and
Preparation method.
It is an object of the invention to be achieved through the following technical solutions: a kind of high tensile flexible Graphene composite heat conduction film, should
High flexibility graphene film density is 1.8-2.0g/cm3, the average-size of planar orientation it is more than the macromolecule composite stone of 100 μm
Ink alkene sheet is mutually overlapped by the pi-conjugated effect of π and forms.Wherein in macromolecule composite graphite alkene sheet, macromolecule passes through the pi-conjugated work of π
With or chemical bond be compounded on graphene film.
Further, described heat conducting film comprises the graphene-structured being made up of the macromolecule composite graphite alkene sheet of 1-4 layer.
And the defect of graphene film is few, its ID/TG＜ 0.01.
The preparation method of a kind of super flexibility high thermal conductivity graphene thin film, comprises the steps of:
(1) organic polymer of the graphene oxide and 0.01-1 mass parts that 1 mass parts average-size is more than 100um is joined
Making concentration is 6～30mg/mL graphene oxide water solution, in the solution add mass fraction 0.1-5% auxiliary agent, described in help
Agent be at 2500 DEG C degradable inorganic salt or at 2500 DEG C degradable organic molecule；After ultrasonic disperse, it is poured on mould
It is dried into graphene oxide membrane on tool plate, then reduces with reducing agent；
(2) graphene film after reduction is first arrived with the ramp of 0.1-1 DEG C/min under atmosphere of inert gases
500-800 DEG C, it is incubated 0.5-2h；
(3) with the ramp to 1000-1300 DEG C of 1-3 DEG C/min under atmosphere of inert gases, it is incubated 0.5-3h；
(4) with the ramp to 2500-3000 DEG C of 5-8 DEG C/min under atmosphere of inert gases, it is incubated 0.5-4h, natural
Porous graphene thin film is i.e. can get after cooling.
(5) graphene film is under high pressure suppressed to obtain super flexibility high thermal conductivity graphene film.
Further, described degradable inorganic salt at 2500 DEG C is selected from ammonium hydrogen carbonate, carbamide, thiourea, azo two
Methanamide；At 2500 DEG C, degradable organic molecule is selected from glycerol, polyethylene glycol 200, PEG400；Organic high score
Son mainly by hyperbranched polyglycidyl ether, hyperbranched copolymerization (ester-amine), hyperbranched polysulfones amine, hyperbranched poly Siloxysilane,
Cellulose, Carboxymethyl cellulose sodium, fibroin, sodium alginate, chitosan, gelatin, agar, urea-melamine, polyamides are sub-
Amine, polybutylene terephthalate (PBT), PTT, polyethylene, polypropylene, polybutene, phenylethylene tree
Fat, polyoxymethylene, polyamide, Merlon, polymethyl methacrylate, polyphenylene sulfide, polyphenylene oxide, Noryl,
One or more in polysulfones, polyether sulfone, polyketone, polyether-ketone, polyether-ether-ketone, polyarylate, polyethers nitrile are according to arbitrarily ratio mixing group
Become.
Further, described reducing agent comprises hydrazine hydrate, amine, ascorbic acid, hydrogen iodide；Owing to hydrazine hydrate is in reduction
Process can make membrane material expand, and preferentially uses hydrazine hydrate.
Further, described pressing process pressure is 50-200MP, and the time is 6-300h.
Further, in described step 1, the average-size graphene oxide more than 100um obtains by the following method:
(1), after the reactant liquor dilution of oxidized graphite flake Modified-Hummer method obtained, the mesh screen in 140 mesh enters
Row filters, and obtains filtration product；
(2) filtration product step 1 obtained is after frozen water is according to volume ratio 1:10 mix homogeneously, stands 2h, dropwise adds
Enter hydrogen peroxide (H2O2Mass fraction be 30%), until the color of mixed liquor no longer changes, (i.e. the potassium permanganate in mixed liquor is
Remove completely)；
(3) mixed liquor after step 2 processes is added dropwise over concentrated hydrochloric acid (concentration is 12mol/L), until cotton-shaped oxygen
Graphite disappears, then goes out graphite oxide wafer with the screen filtration of 140 mesh；
(4) graphite oxide wafer step 3 obtained is placed in shaking table, 20～80 turns/min, concussion washing so that oxidation
Graphite wafer is peeled off, and obtains the graphene oxide without fragment super large sheet, and average-size is more than 87um, and breadth coefficient is at 0.2-0.5
Between.
Further, the Modified-Hummer method in described step 1 is particularly as follows: at-10 DEG C, fill potassium permanganate
Point be dissolved in the concentrated sulphuric acid that mass fraction is 98%, add graphite, after 60 revs/min of stirring 2h, stop stirring, low temperature (-
10-20 DEG C) under react 6-48h, obtain the oxidized graphite flake reactant liquor of wide distribution；Described graphite, potassium permanganate and concentrated sulphuric acid
Mass volume ratio is: 1g:2-4g:30-40ml, and the granularity of graphite is more than 150 μm.
Further, described mesh screen is the acidproof mesh screens such as titanium alloy.
Further, in described step 1, the reactant liquor of oxidized graphite flake is diluted by diluent such as concentrated sulphuric acids, dilute
Release agent 1-10 times that volume is reactant liquor volume.
The beneficial effects of the present invention is: by the present invention in that and use super large sheet graphene oxide film forming, and allow it at high temperature
Under the mode of lower annealing, perfect reparation Graphene defect, and edge defect is preferably minimized, formed and be perfectly conjugated greatly knot
Structure, its conjugation size has even extended to the Graphene of full wafer, it is ensured that Graphene thermal conducting path unimpeded；Further by three
Walk independent temperature-rise period so that the functional group of graphenic surface gradually disengages, the auxiliary agent (drilling being mixed between graphene film
Agent) slowly to decompose, both of which discharges the most step by step, meanwhile, and graphitizing process stepwise development, form the micro-gas of Graphene
Capsule；Use condition of high voltage to be compressed by micro-air bag further, form fold so that the deformation of graphene film is remembered, compose
Give the flexibility of its superelevation.The macromolecule being compound on Graphene, under conditions of nitrogen is protected, progressively sloughs functional group, along with stone
The ink graphitization of alkene and graphitization develops, form crosslinking with the form of conjugated structure or chemical bond between the layers, greatly increase
See by force graphene film intensity.
And in the forming process of micro-air bag, the most stable functional group of graphenic surface comes off the most therewith, adds under high temperature
Gas expansion, thereby produces the graphene-structured being made up of 1-4 layer graphene sheet；Being successfully introduced into of the few Rotating fields of Graphene,
It is greatly improved the electrical and thermal conductivity performance of material.Super-high heat-conductive heat conductivity and flexible combination so that this heat conducting film is at high frequency
Flexible electronic device aspect has the widest application potential.
Accompanying drawing explanation
Fig. 1 is the graphite oxide crystal (left) before filtering, the graphite oxide crystal (right) after filtration.
Fig. 2 is the graphene oxide (left) before filtering, the graphene oxide (right) after filtration.
Fig. 3 is to react the graphene oxide obtained under 50 degree.
Fig. 4 is to react the graphene oxide distribution of sizes (left) obtained under 50 degree, and 20 degree are reacted the graphite oxide obtained down
Alkene distribution of sizes (right).
Fig. 5 is graphene film sectional view.
Fig. 6 is graphene membrane surface and inner scanning electron microscopic picture.
Fig. 7 is elongation at break and the relation schematic diagram of intensity of graphene film.
Detailed description of the invention
By the present invention in that and use super large sheet graphene oxide film forming, wherein the average-size of planar orientation is more than 100 μm
Graphene film is important role during constituting graphene film of the present invention, and the present invention washes it at graphite oxide crystal
Before, the way using mesh screen to separate, chip separation is gone out.And using 10 times to be diluted with the frozen water of upper volume so that it is brilliant
Sheet will not be destroyed because of the heat of solution of sulphuric acid.Use shaking table concussion washing further so that graphene oxide lamella is in stripping
From when avoid the broken of mechanical force.Further, the present invention prepares graphene film also by cryogenic conditions, at low temperature
Under, potassium permanganate oxidation is more weak, and the speed that its selfdecomposition produces oxygen is slow, and therefore gas is to graphite oxide crystal
Fragmentation is the most weak so that the graphene oxide of big lamella is preserved.And course of reaction and cleaning process do not have
Violent stirring and ultrasonic procedure, therefore lamella there is no broken.The most what time, we have obtained the nothing of super large sheet
The graphene oxide of fragment, average-size is more than 87um, and breadth coefficient is between 0.2-0.5, and shive content is less than 1%.And stone
The defect of ink alkene sheet is few, its ID/TG＜ 0.01.
Below in conjunction with the accompanying drawings and embodiment the invention will be further described.The present embodiment be served only for the present invention is done into
The explanation of one step, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according in foregoing invention
Hold and make some nonessential change and adjustment, belong to protection scope of the present invention.
Embodiment 1: without the preparation of the graphene oxide of fragment super large sheet
Embodiment 1-1
(1) at-10 DEG C, potassium permanganate is slowly added in the concentrated sulphuric acid of quickly agitation, after fully dissolving, adds
Graphite, 60 revs/min are slowly stirred after 2h and stop stirring, 20 DEG C, react 6h respectively at 50 DEG C, respectively obtain the oxygen of wide distribution
Graphite crystal；As it is shown in figure 1, all there is more fragment in the graphite oxide wafer obtained at a temperature of two kinds, this makes it
Corresponding graphene oxide has a lot of fragments (Fig. 2) equally.
(2) (extension rate can be any multiple to reactant liquor diluting concentrated sulfuric acid step 1 obtained, and the present embodiment is dilute
Release about 10 times), and with the titanium alloy mesh screen of 150um aperture (140 mesh) graphite oxide crystal filtered out (reactant liquor returns
Receive), and be poured slowly in the frozen water relative to 10 times of volumes of filtration product of quickly stirring, stand 2h, be slowly added to H2O2, with
Remove potassium permanganate unnecessary in reaction, add appropriate hydrochloric acid until cotton-shaped graphite oxide disappears, then use titanium alloy mesh screen
(140 mesh) filters out graphite oxide wafer；Shaking table slowly shakes washing, obtains the graphene oxide without fragment super large sheet (average
A size of 87um, breadth coefficient is 0.5).Graphite, potassium permanganate with concentrated sulphuric acid mass volume ratio is: 1g:2g:40ml, graphite
Granularity is 200um.
As it is shown on figure 3, isolated graphite oxide wafer washs, after separating, the oxidation stone obtained after the lower reaction of high temperature 50 degree
Ink alkene has a lot of fragments equally；From fig. 4, it can be seen that large stretch of graphene oxide size after (20 DEG C) Reaction Separation under low temperature
Being distributed more uniform concentration, shive content is few.
Embodiment 1-2
At-10 DEG C, potassium permanganate is slowly added in the concentrated sulphuric acid of quickly agitation, after fully dissolving, adds stone
Ink, 60 revs/min are slowly stirred stopping stirring after 2h, react 48h, obtain reactant liquor under low temperature (0 DEG C)；Reactant liquor is divided
It is not diluted with the dilute sulfuric acid that the concentrated sulphuric acid of mass fraction more than 98%, mass fraction are 10%, then with 150um aperture
Graphite oxide crystal is filtered out (reactant liquor recovery) by titanium alloy mesh screen, and is poured slowly into producing relative to filtering of quickly stirring
In the frozen water of 10 times of volumes of thing, stand 2h, be slowly added to H2O2, to remove potassium permanganate unnecessary in reaction, add appropriate salt
Acid is until cotton-shaped graphite oxide disappears, then leaches graphite oxide wafer with titanium alloy reticulated is sieved；Shaking table slowly shakes washing, obtains
Product.Graphite, potassium permanganate with concentrated sulphuric acid mass volume ratio is: 1:4g:30ml；The granularity of graphite is 500um.
Using diluting concentrated sulfuric acid, (average-size is 98um to the graphene oxide of the sheet of super large without fragment that reaction obtains, distribution
Coefficient is 0.4), and dilute with dilute sulfuric acid, containing a large amount of fragments in the product obtained, distribution of sizes coefficient is more than 100%.This is
Due in dilute sulfuric acid dilution, highly exothermic, destroy graphite oxide crystal.
Embodiment 1-3
At-10 DEG C, potassium permanganate is slowly added in the concentrated sulphuric acid of quickly agitation, after fully dissolving, adds stone
Ink, 60 revs/min are slowly stirred stopping stirring after 2h, react 28h under low temperature (20 DEG C), obtain the graphite oxide crystalline substance of wide distribution
Body；By reactant liquor diluting concentrated sulfuric acid and with the titanium alloy mesh screen in 150um aperture, graphite oxide crystal is filtered out (reactant liquor
Reclaim), and be poured slowly into respectively quickly stirring relative to 5 times of volumes of filtration product, 8 times of volumes, 10 times of volumes frozen water in,
Stand 2h, be slowly added to H2O2, to remove potassium permanganate unnecessary in reaction, add appropriate hydrochloric acid until cotton-shaped graphite oxide
Disappear, then leach graphite oxide wafer with titanium alloy reticulated is sieved；Shaking table slowly shakes washing, obtains product；Graphite, Gao Meng
Acid potassium with concentrated sulphuric acid mass volume ratio is: 1:5g:34ml, the granularity of graphite is 2mm.
Experimental result shows, the frozen water of 5 times of volumes and 8 times of volumes all can not the graphene film obtaining size uniformity,
Graphene oxide without fragment super large sheet (average-size is 92um, breadth coefficient 0.2) just can be obtained under 10 times of volumes.Thus
Understanding, the amount of frozen water is too low, the heat of mixing will be made to concentrate release, destroy crystal structure.
Embodiment 2: the graphene oxide of the sheet of super large without fragment that employing embodiment 1 prepares prepares super flexible high heat conduction
Graphene film.
The fibroin of 1 mass parts average-size is more than 100um graphene oxide and 1 mass parts is configured to concentration and is
30mg/mL graphene oxide water solution, adds mass fraction 5% carbamide in the solution, is poured on Die and mould plate after ultrasonic disperse
On be dried into graphene oxide membrane, then reduce with hydrogen iodide reducing agent；Graphene film after reduction is at noble gas
The most progressively heat up 500 DEG C under atmosphere, be incubated 0.5h；Under atmosphere of inert gases, progressively it is warmed up to 1000 DEG C, is incubated 0.5h；Lazy
Property atmosphere under be progressively warmed up to 3000 DEG C, be incubated 0.5h, i.e. can get porous graphene thin film after Temperature fall.By graphite
Alkene thin film under high pressure suppresses to obtain super flexibility high thermal conductivity graphene film.
At described 500 DEG C, heating rate is 1 DEG C/min, and at 1000 DEG C, heating rate is 3 DEG C/min, less than 3000 DEG C,
Heating rate is 8 DEG C/min.
Described pressing process pressure is 200MP, and the time is 300h.
The film density obtained is 1.8g/cm3, it being resistant to repeatedly bend more than 900 times, elongation at break is 14%, and intensity is
210MP, conductivity is 6000S/cm, and thermal conductivity is 1400W/mK.
Fig. 5 is the section front view of graphene film compacting.From figure, graphene film layer assembly is cross-linked with each other, and this is high
Intensity lays the foundation.
Fig. 6 is graphene membrane surface scanning electron microscopic picture.There is figure it can be seen that there is a lot of folds its surface and inside,
This flexibility being graphene film is laid a good foundation.
Fig. 7 is elongation at break and the intensity of graphene film.From figure, the fracture of the graphene film that we prepare is stretched
Long rate has reached 14%, and intensity is up to 210MP；And the elongation at break of the graphene film containing 20% fragment only has about 6%,
Intensity is less than 100MP.After doubling repeatedly, conductivity variations is little, illustrates that it is flexible very well, and after repeatedly rolling, its property
Can recover as before again, this explanation, the Graphene macroscopic view that the graphene film that we prepare is real assembles.
Comparative example 1: such as embodiment 1 step, the quantitative change of fibroin is become 2 mass parts, then the film density obtained is 1.6g/
cm3, it being resistant to repeatedly bend more than 100 times, elongation at break is 6%, and intensity is 60MP, and conductivity is 2500S/cm, thermal conductivity
For 600W/mK.
Comparative example 2: such as embodiment 1 step, per minute is heated to 3000 by direct for the graphene oxide membrane after reduction 100 degree
Degree, then the film density obtained is 1.63g/cm3, it being resistant to repeatedly bend more than 400 times, elongation at break is 5%, and intensity is
90MP, conductivity is 4000S/cm, and thermal conductivity is 700W/mK.
Comparative example 3: shown in example 1 performed as described above, change the raw material of graphene oxide used by it, left 20% with shive content
Right graphene oxide.The density of then prepared film is 1.63g/cm3, repeatedly bending 240 caudacorias and damage, elongation at break is
6%, intensity is 84MP, and conductivity is 2400S/cm, and thermal conductivity is 800W/mK.
Embodiment 3: the graphene oxide of the sheet of super large without fragment that employing embodiment 1 prepares prepares super flexible high heat conduction
Graphene film.
1 mass parts average-size is more than graphene oxide and the 0.01 mass parts hyperbranched polyglycidyl ether of 100um
The concentration that is configured to be 6mg/mL graphene oxide water solution, in the solution add mass fraction 0.1 ammonium hydrogen carbonate, through ultrasonic
It is poured on after dispersion on Die and mould plate and is dried into graphene oxide membrane, then reduce with hydrazine hydrate reduction agent；Graphite after reduction
Alkene thin film the most progressively heats up 700 DEG C under atmosphere of inert gases, is incubated 2h；1100 progressively it are warmed up under atmosphere of inert gases
DEG C, it is incubated 3h；Under atmosphere of inert gases, progressively it is warmed up to 3000 DEG C, is incubated 4h, after Temperature fall, i.e. can get porous graphite
Alkene thin film.Graphene film is under high pressure suppressed to obtain super flexibility high thermal conductivity graphene film.
At described 700 DEG C, heating rate is 0.2 DEG C/min, and at 1100 DEG C, heating rate is 1 DEG C/min, 3000 DEG C with
Under, heating rate is 5 DEG C/min.
Described pressing process pressure is 200MP, and the time is 100h.
The film density obtained is 2.0g/cm3, it being resistant to repeatedly bend more than 1000 times, elongation at break is 16%, and intensity is
100MP, conductivity is 8600S/cm, and thermal conductivity is 1800W/mK.
Embodiment 4: the graphene oxide of the sheet of super large without fragment that employing embodiment 1 prepares prepares super flexible high heat conduction
Graphene film.
More than the graphene oxide of 100um and 0.1 mass parts polyphenylene sulfide, 1 mass parts average-size is configured to concentration is
16mg/mL graphene oxide water solution, adds mass fraction 1% glycerol in the solution, is poured on Die and mould plate after ultrasonic disperse
On be dried into graphene oxide membrane, then reduce with Vitamin C bolt；Graphene film after reduction is according to table 1 table 3 institute
The heat treatment mode shown carries out heat treatment, i.e. can get porous graphene thin film after Temperature fall.By graphene film at high pressure
Under suppress to obtain super flexibility high thermal conductivity graphene film.Described pressing process pressure is 50MP, and the time is 6h.
Table 1: first step Elevated Temperature Conditions
Table 2: second step Elevated Temperature Conditions
Table 3: the three step Elevated Temperature Conditions
From table 1～table 3 it can be seen that the performance of this material determines in terms of mainly having three, one material internal graphite oxide
Alkene chip architecture repairs coming off and the reparation of carbon conjugated structure under high temperature of situation, i.e. functional group.Its two, material internal three-dimensional takes
To the seriality of structure, the i.e. connectivity of internal sheets Rotating fields.Its three, micro-air bag formed guarantee material flexibility and
The existence of graphene film Rotating fields.Three acts on increasing the performance of graphene film jointly.
As it can be seen from table 1 compare A1, B1, C1, D1, E1, the temperature of A1 is too low, is not enough to remove major part degradable
Functional group, cause gas in second step pyroprocess the most quickly to produce, at high temperature tearing sheet Rotating fields；E1 temperature mistake
Height, produces gas too fast, can tear material internal structure in a large number, both can make deterioration in material properties.Have only B1, C1,
At a temperature of D1, functional group can slowly and thoroughly remove, to ensure material property.Relatively C1, F1, G1, H1, F1 heating rate mistake
Low, gas release is the slowest, it is impossible to makes material internal form through hole, is unfavorable for micro-air bag in ensuing temperature-rise period
Formation；H1 temperature-rise period is too fast, and gas release is too fast, tears material internal structure, is unfavorable for forming transmission channel.Have CG only
Just can both ensure the formation of micro-air bag under heating rate, can guarantee that again the complete of passage.Relatively C1, I1, J1, K1, L1, M1,
I1 temperature retention time is too short, it is impossible to ensure the degraded of major part functional group；M1 insulating process is long, can absorb Jiao inside stove
Oil, is unfavorable for the lifting of performance.C1, J1, K1, L1 just avoid both.
From Table 2, it can be seen that compare A2, B2, C2, D2, E2, too low being not enough to of A2 heating rate forms small space
Structure so that film can not form micro-air bag, has a strong impact on capability of electromagnetic shielding.E2 programming rate is too high, can tear graphene layer
Between structure so that graphene film link property be deteriorated, heat conduction capability of electromagnetic shielding is all deteriorated.Have the programming rate of B2, C2, D2 only
Under, just capable not only can ensure micro-airbag structure but also ensure the seriality within graphene film.Relatively C2, I2, J2, K2, L2,
M2, I2 temperature retention time is too short, and stable functional group can not fully come off；M2 overlong time, the easy tar adsorption of graphene film, no
It is beneficial to the lifting of film properties；And under the conditions of C2, J2, K2, M2, both can ensure that fully coming off of stabilising functional group, it is avoided that again Jiao
The puzzlement of oil.
From table 3 it is observed that compare A3, B3, C3, D3, E, A3 heating rate is too low, the mistake that stabilising functional group comes off
Slowly, it is not enough to support the formation of micro-air bag during forming micro-air bag；E3 temperature-rise period is too fast, and gas release and high temperature are swollen
Swollen too fast, it is easily destroyed the formation of micro-air bag.Only in the case of B3, C3, D3, the formation that micro-air bag could be stable, Graphene
On structure could repair slowly.Relatively C3, F3, G3, H3, I3, F3 outlet temperature is too low, and graphene-structured is repaired the completeest
It is kind, so various performance is the most very poor；I3 outlet temperature is too high, and Graphene can be vaporized；Could both at a temperature of C3, G3, H3
Ensure the reparation of graphene-structured, will not be vaporized again.Relatively C3, J3, K3, L3, M3, J3 temperature retention time is too low, Graphene
Structure can not fully be repaired, and M3 temperature retention time is long, also can make to adsorb the tar in body of heater, affect the performance of film.
Embodiment 5: the graphene oxide of the sheet of super large without fragment that employing embodiment 1 prepares prepares super flexible high heat conduction
Graphene film.
The polyethers nitrile of 1 mass parts average-size is more than 100um graphene oxide and 0.5 mass parts is configured to concentration and is
16mg/mL graphene oxide water solution, adds mass fraction 4% azodicarbonamide in the solution, falls after ultrasonic disperse
Die and mould plate is dried into graphene oxide membrane, then reduces with ascorbic acid；Graphene film after reduction is in inertia
The most progressively heat up 500 DEG C under atmosphere, be incubated 2h；Under atmosphere of inert gases, progressively it is warmed up to 1000 DEG C, is incubated 0.5h；?
Progressively it is warmed up to 2500 DEG C under atmosphere of inert gases, is incubated 4h, after Temperature fall, i.e. can get porous graphene thin film.By graphite
Alkene thin film under high pressure suppresses to obtain super flexibility high thermal conductivity graphene film.
At described 500 DEG C, heating rate is 0.1 DEG C/min, and at 1000 DEG C, heating rate is 1 DEG C/min, 2500 DEG C with
Under, heating rate is 7 DEG C/min.
Described pressing process pressure is 50MP, and the time is 120h.
The film density obtained is 1.84g/cm3, it being resistant to repeatedly bend more than 1200 times, elongation at break is 9%, and intensity is
300MP, conductivity is 6500S/cm, and thermal conductivity is 1500W/mK.
Embodiment 6: the graphene oxide of the sheet of super large without fragment that employing embodiment 1 prepares prepares super flexible high heat conduction
Graphene film.
Graphene oxide and 0.08 mass parts polyether-ether-ketone that 1 mass parts average-size is more than 100um are configured to concentration
For 6mg/mL graphene oxide water solution, add 0.05 mass parts polyethylene glycol 200 in the solution, be poured on after ultrasonic disperse
It is dried into graphene oxide membrane on Die and mould plate, then reduces with hydrogen iodide；Graphene film after reduction is at noble gas
The most progressively heat up 800 DEG C under atmosphere, be incubated 2h；Under atmosphere of inert gases, progressively it is warmed up to 1300 DEG C, is incubated 3h；At indifferent gas
Progressively it is warmed up to 3000 DEG C under body atmosphere, is incubated 0.5h, after Temperature fall, i.e. can get porous graphene thin film.Graphene is thin
Film under high pressure suppresses to obtain super flexibility high thermal conductivity graphene film.
At described 800 DEG C, heating rate is 0.6 DEG C/min, and at 1300 DEG C, heating rate is 1.3 DEG C/min, 3000 DEG C with
Under, heating rate is 6.2 DEG C/min.
Described pressing process pressure is 150MP, and the time is 210h.
The film density obtained is 1.94g/cm3, it being resistant to repeatedly bend more than 890 times, elongation at break is 15%, and intensity is
173MP, conductivity is 7500S/cm, and thermal conductivity is 1460W/mK.
Embodiment 7: the graphene oxide of the sheet of super large without fragment that employing embodiment 1 prepares prepares super flexible high heat conduction
Graphene film.
1 mass parts average-size is more than graphene oxide and the 0.2 mass parts PTT of 100um
Being configured to concentration is 6～30mg/mL graphene oxide water solution, adds quality 0.02 mass parts PEG400 in the solution,
It is poured on after ultrasonic disperse on Die and mould plate and is dried into graphene oxide membrane, then use hydrazine hydrate reduction；Graphene after reduction
Thin film the most progressively heats up 600 DEG C under atmosphere of inert gases, is incubated 1h；1100 DEG C progressively it are warmed up under atmosphere of inert gases,
Insulation 2h；Under atmosphere of inert gases, progressively it is warmed up to 2700 DEG C, is incubated 1h, i.e. can get porous graphene after Temperature fall thin
Film.Graphene film is under high pressure suppressed to obtain super flexibility high thermal conductivity graphene film.
At described 600 DEG C, heating rate is 0.1 DEG C/min, and at 1100 DEG C, heating rate is 2.1 DEG C/min, 2700 DEG C with
Under, heating rate is 6.8 DEG C/min.
Described pressing process pressure is 220MP, and the time is 300h.
The film density obtained is 1.89g/cm3, it being resistant to repeatedly bend more than 1200 times, elongation at break is 9%, and intensity is
250MP, conductivity is 6100S/cm, and thermal conductivity is 1430W/mK.
Claims (10)
1. a high tensile flexible Graphene composite heat conduction film, it is characterised in that this high flexibility graphene film density is 1.8-2.0g/
cm3, the average-size of planar orientation mutually overlapped by the pi-conjugated effect of π more than the macromolecule composite graphite alkene sheet of 100 μm and
Become.Wherein in macromolecule composite graphite alkene sheet, macromolecule is compounded on graphene film by the pi-conjugated effect of π or chemical bond.
High tensile flexible Graphene composite heat conduction film the most according to claim 1, it is characterised in that comprise in described heat conducting film
The graphene-structured being made up of the macromolecule composite graphite alkene sheet of 1-4 layer.And the defect of graphene film is few, its ID/TG＜
0.01。
3. the preparation method of a super flexible high thermal conductivity graphene thin film, it is characterised in that comprise the steps of:
(1) organic polymer of the graphene oxide and 0.01-1 mass parts that 1 mass parts average-size is more than 100um is configured to
Concentration is 6～30mg/mL graphene oxide water solution, and (i.e. auxiliary agent is molten for the auxiliary agent of addition mass fraction 0.1-5% in the solution
Mass fraction in liquid is 0.1-5%), described auxiliary agent be at 2500 DEG C degradable inorganic salt or at 2500 DEG C degradable
Organic molecule；After ultrasonic disperse, it is poured on Die and mould plate and is dried into graphene oxide membrane, then reduce with reducing agent；
(2) by the graphene film after reduction under atmosphere of inert gases first with the ramp of 0.1-1 DEG C/min to 500-800
DEG C, it is incubated 0.5-2h；
(3) with the ramp to 1000-1300 DEG C of 1-3 DEG C/min under atmosphere of inert gases, it is incubated 0.5-3h；
(4) with the ramp to 2500-3000 DEG C of 5-8 DEG C/min under atmosphere of inert gases, it is incubated 0.5-4h, Temperature fall
After i.e. can get porous graphene thin film.
(5) graphene film is under high pressure suppressed to obtain super flexibility high thermal conductivity graphene film.
The preparation method of a kind of super flexibility the most as claimed in claim 3 high thermal conductivity graphene thin film, it is characterised in that described
At 2500 DEG C, degradable inorganic salt is selected from ammonium hydrogen carbonate, carbamide, thiourea, azodicarbonamide；Degradable at 2500 DEG C
Organic molecule selected from glycerol, polyethylene glycol 200, PEG400；Organic polymer is mainly by Hyperbranched Polyglycidol
Ether, hyperbranched copolymerization (ester-amine), hyperbranched polysulfones amine, hyperbranched poly Siloxysilane, cellulose, Carboxymethyl cellulose sodium, silkworm
Fibroin, sodium alginate, chitosan, gelatin, agar, urea-melamine, polyimides, polybutylene terephthalate (PBT),
PTT, polyethylene, polypropylene, polybutene, styrene resin, polyoxymethylene, polyamide, poly-
Carbonic ester, polymethyl methacrylate, polyphenylene sulfide, polyphenylene oxide, Noryl, polysulfones, polyether sulfone, polyketone, polyether-ketone, poly-
One or more in ether ether ketone, polyarylate, polyethers nitrile are according to arbitrarily than mixing composition.
The preparation method of a kind of super flexibility the most as claimed in claim 3 high thermal conductivity graphene thin film, it is characterised in that described
Reducing agent comprises hydrazine hydrate, amine, ascorbic acid, hydrogen iodide；Owing to hydrazine hydrate can make membrane material expand in reduction process, excellent
First use hydrazine hydrate.
The preparation method of a kind of super flexibility the most as claimed in claim 3 high thermal conductivity graphene thin film, it is characterised in that described
Pressing process pressure is 50-200MP, and the time is 6-300h.
The preparation method of a kind of super flexibility the most as claimed in claim 3 high thermal conductivity graphene thin film, it is characterised in that described step
In rapid 1, the average-size graphene oxide more than 100um obtains by the following method:
(1), after the reactant liquor dilution of oxidized graphite flake Modified-Hummer method obtained, the mesh screen in 140 mesh was carried out
Filter, obtains filtration product；
(2) filtration product step 1 obtained is after frozen water is according to volume ratio 1:10 mix homogeneously, stands 2h, is added dropwise over double
Oxygen water (H2O2Mass fraction be 30%), until the color of mixed liquor no longer changes, (i.e. potassium permanganate in mixed liquor is the most complete
Remove)；
(3) mixed liquor after step 2 processes is added dropwise over concentrated hydrochloric acid (concentration is 12mol/L), until cotton-shaped oxidation stone
Ink disappears, then goes out graphite oxide wafer with the screen filtration of 140 mesh；
(4) graphite oxide wafer step 3 obtained is placed in shaking table, 20～80 turns/min, concussion washing so that graphite oxide
Wafer is peeled off, and obtains the graphene oxide without fragment super large sheet, and average-size is more than 87um, and breadth coefficient is between 0.2-0.5.
Method the most according to claim 7, it is characterised in that the Modified-Hummer method in described step 1 is concrete
For: at-10 DEG C, potassium permanganate is completely dissolved in the concentrated sulphuric acid that mass fraction is 98%, addition graphite, 60 revs/min
Stop stirring after stirring 2h, under low temperature (-10-20 DEG C), react 6-48h, obtain the oxidized graphite flake reactant liquor of wide distribution；Institute
Graphite, the potassium permanganate stated with concentrated sulphuric acid mass volume ratio is: 1g:2-4g:30-40ml, and the granularity of graphite is more than 150 μm.
Method the most according to claim 7, it is characterised in that described mesh screen is the acidproof mesh screens such as titanium alloy.
Method the most according to claim 7, it is characterised in that in described step 1, the reactant liquor of oxidized graphite flake passes through
The diluent such as concentrated sulphuric acid are diluted, and the volume of diluent is 1-10 times of reactant liquor volume.
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