CN105731435B - A kind of high tensile flexible graphene composite heat conduction film and preparation method thereof - Google Patents
A kind of high tensile flexible graphene composite heat conduction film and preparation method thereof Download PDFInfo
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/24—Thermal properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of high tensile flexible graphene composite heat conduction film and preparation method thereof, the film is made up of macroscopical multilayered fold graphene with micro-scale fold physical crosslinking, piece interlayer slip, therefore has high flexibility.Its graphene sheet layer perfect structure, lamella crystalline region is greatly and seldom containing defective, and structure is closely knit after high pressure is suppressed, and has the electric conductivity and thermal conductivity of superelevation.Meanwhile the cross-linking graphene sheet layer of presence of polymer composite, strengthen graphene film strength.This high tensile flexible graphene composite heat conduction film, intensity can reach 100 300MP, be resistant to bend repeatedly more than 1000 times, elongation at break is 6 16%, conductance is 6000 8600S/cm, and thermal conductivity is 1400 1800W/mK, can be widely used for high-strength programmable thermal conductivity device.
Description
Technical field
The present invention relates to novel heat-conducting material and preparation method thereof, more particularly to a kind of super flexible high heat conduction graphene film and
Its preparation method.
Background technology
2010, two of Univ Manchester UK professor Andre GeiM and Konstantin Novoselov because
Stable graphene is successfully separated out first and obtains Nobel Prize in physics, has started the upsurge that the whole world is studied graphene.
Graphene has excellent electric property, and (electron mobility is up to 2 × 10 at room temperature5cM2/ 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, while graphene has the advantages of corrosion-and high-temp-resistant, and its good machinery
Performance and relatively low density more allow it to possess the potentiality in thermo electric material field substituted metal.
The graphene film of macroscopic view assembling graphene oxide or graphene nanometer sheet is the main application of 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, the defects of graphene can be repaired, the electric conductivity and thermal conductance of graphene film can be effectively improved, can be widely applied to
Smart mobile phone, intelligence are with oneself in the high radiating requirements accompanied electronic equipment such as hardware, tablet personal computer, notebook computer.
But at present, undersize of graphene oxide used itself, and contain many fragments, make it in terms of heat conduction
Enough development are not obtained, heat conductivility is limited in 1400W/mK, it is impossible to meets the needs of rapid technological growth.And film
The deficiency of structure design causes its flexibility to be still not clear, and limits its application in terms of flexible device.Importantly, graphite
Alkene heat conduction film strength is less than 80MP so that its application is greatly limited.
The content of the invention
The purpose of the present invention is overcome the deficiencies in the prior art, there is provided a kind of high tensile flexible graphene composite heat conduction film and its
Preparation method.
The purpose of the present invention is 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, 100 μm of macromolecule composite stone is more than by the average-size of planar orientation
Black alkene piece is formed by the pi-conjugated effects of π mutually overlap joint.Wherein in macromolecule composite graphite alkene piece, macromolecule passes through the pi-conjugated works of π
With or chemical bond be compounded on graphene film.
Further, the graphene-structured being made up of the macromolecule composite graphite alkene piece of 1-4 layers is included in the heat conducting film.
And the defects of graphene film, is few, its ID/TG＜ 0.01.
A kind of preparation method of super flexible high heat conduction graphene film, is comprised the following steps：
(1) organic polymer of graphene oxide of the 1 mass parts average-size more than 100um and 0.01-1 mass parts is matched somebody with somebody
It is 6~30mg/mL graphene oxide water solutions that concentration, which is made, adds mass fraction 0.1-5% auxiliary agent in the solution, described to help
Agent is inorganic salts degradable at 2500 DEG C or degradable organic molecule at 2500 DEG C；After ultrasonic disperse, mould is poured on
Graphene oxide membrane is dried on tool plate, is then reduced with reducing agent；
(2) graphene film after reduction is first warming up under atmosphere of inert gases with 0.1-1 DEG C/min speed
500-800 DEG C, it is incubated 0.5-2h；
(3) 1000-1300 DEG C is warming up to 1-3 DEG C/min speed under atmosphere of inert gases, is incubated 0.5-3h；
(4) 2500-3000 DEG C is warming up to 5-8 DEG C/min speed under atmosphere of inert gases, is incubated 0.5-4h, it is natural
Porous graphene film is can obtain after cooling.
(5) super flexible high heat conduction graphene film can be obtained by suppressing graphene film under high pressure.
Further, the degradable inorganic salts at 2500 DEG C are selected from ammonium hydrogen carbonate, urea, thiocarbamide, azo two
Formamide；Degradable organic molecule is selected from glycerine, polyethylene glycol 200, polyethylene glycol 400 at 2500 DEG C；Organic high score
Son mainly by hyperbranched polyglycidyl ether, it is hyperbranched copolymerization (ester-amine), hyperbranched polysulfones amine, hyperbranched poly Siloxysilane,
Cellulose, sodium cellulose glycolate, fibroin, sodium alginate, chitosan, gelatin, agar, urea-melamine, polyamides are sub-
Amine, polybutylene terephthalate (PBT), PTT, polyethylene, polypropylene, polybutene, phenylethylene tree
Fat, polyoxymethylene, polyamide, makrolon, 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 than mixing group
Into.
Further, described reducing agent includes hydrazine hydrate, amine, ascorbic acid, hydrogen iodide；Because hydrazine hydrate is reducing
Process can cause membrane material to expand, preferentially using hydrazine hydrate.
Further, described pressing process pressure is 50-200MP, time 6-300h.
Further, graphene oxide of the average-size more than 100um obtains by the following method in the step 1：
(1) after the reaction solution dilution for the oxidized graphite flake for obtaining Modified-Hummer methods, enter in the mesh screen of 140 mesh
Row filtering, obtains filtration product；
(2) by the filtration product that step 1 obtains in frozen water according to volume ratio 1：After 10 is well mixed, 2h is stood, is added dropwise
Enter hydrogen peroxide (H2O2Mass fraction for 30%), until the color of mixed liquor no longer changes, (potassium permanganate i.e. in mixed liquor is
Remove completely)；
(3) concentrated hydrochloric acid (concentration 12mol/L) is added dropwise into the mixed liquor after step 2 processing, until cotton-shaped oxygen
Graphite disappears, then goes out graphite oxide chip with the screen filtration of 140 mesh；
(4) the graphite oxide chip that step 3 obtains is placed in shaking table, 20~80 turns/min, concussion washing so that oxidation
Graphite wafer is peeled off, and obtains the graphene oxide of no fragment super large piece, average-size is more than 87um, and breadth coefficient is in 0.2-0.5
Between.
Further, the Modified-Hummer methods in the step 1 are specially：At -10 DEG C, potassium permanganate is filled
Point be dissolved in the concentrated sulfuric acid that mass fraction is 98%, add graphite, stop stirring after 60 revs/min of stirring 2h, low temperature (-
10-20 DEG C) under react 6-48h, obtain the oxidized graphite flake reaction solution of wide distribution；Described graphite, potassium permanganate and the concentrated sulfuric acid
Mass volume ratio is：1g：2-4g：30-40ml, the granularity of graphite are more than 150 μm.
Further, the mesh screen is the acidproof mesh screens such as titanium alloy.
Further, in the step 1, the reaction solution of oxidized graphite flake is diluted by diluents such as the concentrated sulfuric acids, dilute
The volume for releasing agent is 1-10 times of reaction solution volume.
The beneficial effects of the present invention are：By the present invention in that with super large piece graphene oxide film forming, and it is allowed in high temperature
Under the mode of lower annealing, graphene defect is repaired in perfection, and edge defect is preferably minimized, and forms perfect big conjugation knot
Structure, it is conjugated the graphene that size has even extended to full wafer, ensure that the unimpeded of graphene thermal conducting path；Further pass through 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 step by step in gaseous form, meanwhile, graphitizing process stepwise development, form the micro- gas of graphene
Capsule；Further micro- air bag is compressed using condition of high voltage, forms fold so that the deformation of graphene film is remembered, and assigns
Give the flexibility of its superelevation.The macromolecule on graphene is compound under conditions of nitrogen protection, functional group is progressively sloughed, with stone
The graphitization of black alkene and graphitization develops, crosslinking is formed in the form of conjugated structure or chemical bond between the layers, is greatly increased
Graphene film intensity is seen by force.
And in the forming process of micro- air bag, graphenic surface functional group the most stable also comes off therewith, plus under high temperature
Gas expansion, thereby produce the graphene-structured being made up of 1-4 layer graphene pieces；The few Rotating fields of graphene are successfully introduced into,
It is greatly improved the electrical and thermal conductivity performance of material.Super-high heat-conductive thermal conductivity and flexible combination so that the heat conducting film is in high frequency
There is extremely wide application potential in terms of flexible electronic device.
Brief description of the drawings
Fig. 1 is the graphite oxide crystal (left side) before filtering, the graphite oxide crystal (right side) after filtering.
Fig. 2 is the graphene oxide (left side) before filtering, the graphene oxide (right side) after filtering.
Fig. 3 is 50 degree and reacts obtained graphene oxide down.
Fig. 4 is 50 degree and reacts obtained graphene oxide Size Distribution (left side) down, and 20 degree are reacted obtained graphite oxide down
Alkene Size Distribution (right side).
Fig. 5 is graphene film sectional view.
Fig. 6 is graphene membrane surface and inner scanning electron microscopic picture.
Fig. 7 is the elongation at break of graphene film and the relation schematic diagram of intensity.
Embodiment
By the present invention in that with super large piece graphene oxide film forming, the wherein average-size of planar orientation is more than 100 μm
Graphene film important role during graphene film of the present invention is formed, the present invention wash it in graphite oxide crystal
Before, using the method for mesh screen separation, chip separation is gone out.And 10 times are used to be diluted with the frozen water of upper volume so that it is brilliant
Piece will not be destroyed because of the heat of solution of sulfuric acid.Further using shaking table concussion washing so that graphene oxide layer is being shelled
From when avoid the broken of mechanical force.Further, the present invention also prepares graphene film by cryogenic conditions, in low temperature
Under, potassium permanganate oxidation is weaker, and the speed that its selfdecomposition produces oxygen is slow, therefore gas is to graphite oxide crystal
Fragmentation is just very weak so that the graphene oxide of big lamella is preserved.And do not have in course of reaction and cleaning process
Violent stirring and ultrasonic procedure, thus lamella there is no it is broken.In summary some, we have obtained the nothing of super large piece
The graphene oxide of fragment, average-size is more than 87um, and for breadth coefficient between 0.2-0.5, shive content is less than 1%.And stone
The defects of black alkene piece, 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 being the present invention 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
Appearance makes some nonessential changes and adjustment, belongs to protection scope of the present invention.
Embodiment 1：The preparation of graphene oxide without fragment super large piece
Embodiment 1-1
(1) potassium permanganate is slowly added into the concentrated sulfuric acid quickly stirred at -10 DEG C, after abundant dissolving, added
Graphite, 60 revs/min are slowly stirred stopping stirring after 2h, react 6h respectively at 20 DEG C, 50 DEG C, respectively obtain the oxygen of wide distribution
Graphite crystal；As shown in figure 1, more fragment be present in the graphite oxide chip obtained at a temperature of two kinds, this causes it
Corresponding graphene oxide equally has many fragments (Fig. 2).
(2) (extension rate can be any multiple to the reaction solution diluting concentrated sulfuric acid obtained step 1, and the present embodiment is dilute
Release 10 times or so), and graphite oxide crystal is filtered out into (reaction solution time with the titanium alloy mesh screen of 150um apertures (140 mesh)
Receive), and be poured slowly into the frozen water relative to 10 times of volumes of filtration product quickly stirred, 2h is stood, is slowly added to H2O2, with
Except potassium permanganate unnecessary in dereaction, appropriate hydrochloric acid is added until cotton-shaped graphite oxide disappears, then with titanium alloy mesh screen
(140 mesh) filters out graphite oxide chip；Shaking table slowly shakes washing, and the graphene oxide for obtaining no fragment super large piece is (average
Size is 87um, breadth coefficient 0.5).Graphite, potassium permanganate and concentrated sulfuric acid mass volume ratio are：1g：2g：40ml, graphite
Granularity is 200um.
As shown in figure 3, obtained oxidation stone is washed after the graphite oxide chip separation isolated after the lower reaction of 50 degree of high temperature
Black alkene equally has many fragments；From fig. 4, it can be seen that large stretch of graphene oxide size under low temperature after (20 DEG C) Reaction Separation
It is few to be distributed more uniform concentration, shive content.
Embodiment 1-2
Potassium permanganate is slowly added at -10 DEG C in the concentrated sulfuric acid quickly stirred, after abundant dissolving, adds stone
Ink, 60 revs/min are slowly stirred stopping stirring after 2h, react 48h under low temperature (0 DEG C), obtain reaction solution；By reaction solution point
It is not diluted with the concentrated sulfuric acid of mass fraction more than 98%, the dilute sulfuric acid that mass fraction is 10%, then with 150um apertures
Graphite oxide crystal is filtered out (reaction solution recovery) by titanium alloy mesh screen, and be poured slowly into quickly stir relative to filtering produce
In the frozen water of 10 times of volumes of thing, 2h is stood, is slowly added to H2O2, except potassium permanganate unnecessary in dereaction, to add appropriate salt
Acid disappears until cotton-shaped graphite oxide, then is sieved through with titanium alloy reticulated and filters out graphite oxide chip；Shaking table slowly shakes washing, obtains
Reaction product.Graphite, potassium permanganate and concentrated sulfuric acid mass volume ratio are：1：4g：30ml；The granularity of graphite is 500um.
Using diluting concentrated sulfuric acid, obtained graphene oxide (average-size 98um, the distribution without fragment super large piece is reacted
Coefficient is diluted with dilute sulfuric acid 0.4), a large amount of fragments is contained in obtained product, Size Distribution coefficient is more than 100%.This is
It is highly exothermic due in dilute sulfuric acid dilution, destroy graphite oxide crystal.
Embodiment 1-3
Potassium permanganate is slowly added at -10 DEG C in the concentrated sulfuric acid quickly stirred, after abundant dissolving, adds stone
Ink, 60 revs/min are slowly stirred stopping stirring after 2h, react 28h under low temperature (20 DEG C), the graphite oxide for obtaining wide distribution is brilliant
Body；Graphite oxide crystal is filtered out into (reaction solution by reaction solution with diluting concentrated sulfuric acid and with the titanium alloy mesh screen in 150um apertures
Recovery), and be poured slowly into respectively quickly stir relative to 5 times of volumes of filtration product, 8 times of volumes, 10 times of volumes frozen water in,
2h is stood, is slowly added to H2O2, except potassium permanganate unnecessary in dereaction, to add appropriate hydrochloric acid until cotton-shaped graphite oxide
Disappear, then be sieved through with titanium alloy reticulated and filter out graphite oxide chip；Shaking table slowly shakes washing, obtains reaction product；Graphite, Gao Meng
Sour potassium is with concentrated sulfuric acid mass volume ratio：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 can not obtain the graphene film of size uniformity,
The graphene oxide of no fragment super large piece can be just obtained under 10 times of volumes, and (average-size 92um, breadth coefficient is 0.2).Thus
Understand, the amount of frozen water is too low, and the heat of mixing will be caused to concentrate release, destroys crystal structure.
Embodiment 2：The graphene oxide without fragment super large piece being prepared using embodiment 1 prepares super flexible high heat conduction
Graphene film.
The fibroin of graphene oxide of the 1 mass parts average-size more than 100um and 1 mass parts is configured into concentration is
30mg/mL graphene oxide water solutions, the urea of mass fraction 5% is added in the solution, Die and mould plate is poured on after ultrasonic disperse
On be dried into graphene oxide membrane, then reduced with hydrogen iodide reducing agent；Graphene film after reduction is in inert gas
First progressively heated up 500 DEG C under atmosphere, be incubated 0.5h；1000 DEG C are progressively warming up under atmosphere of inert gases, is incubated 0.5h；Lazy
Property atmosphere under be progressively warming up to 3000 DEG C, be incubated 0.5h, porous graphene film can obtain after Temperature fall.By graphite
Alkene film is suppressed under high pressure can obtain super flexible high heat conduction graphene film.
Heating rate is 1 DEG C/min at described 500 DEG C, and heating rate is 3 DEG C/min at 1000 DEG C, less than 3000 DEG C,
Heating rate is 8 DEG C/min.
Described pressing process pressure is 200MP, time 300h.
Obtained film density is 1.8g/cm3, it is resistant to bend repeatedly more than 900 times, elongation at break 14%, intensity is
210MP, conductance 6000S/cm, thermal conductivity 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 height
Intensity lays the foundation.
Fig. 6 is graphene membrane surface scanning electron microscopic picture.Having figure that its surface and inside can be seen has many folds,
This lays a good foundation for the flexibility of graphene film.
Fig. 7 is the elongation at break and intensity of graphene film.From figure, the fracture for 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 6% or so,
Intensity is less than 100MP.After doubling repeatedly, conductivity variations are little, illustrate that it is flexible very well, and repeatedly after calendering, its property
Energy and can is recovered as before, and this explanation, the graphene film that we prepare is that real graphene macroscopic view assembles.
Comparative example 1：Such as the step of embodiment 1, by the quantitative change of fibroin into 2 mass parts, then the film density obtained is 1.6g/
cm3, it is resistant to bend repeatedly more than 100 times, elongation at break 6%, intensity 60MP, conductance 2500S/cm, thermal conductivity
For 600W/mK.
Comparative example 2：Such as the step of embodiment 1,3000 are heated to by direct 100 degree of graphene oxide membrane after reduction is per minute
Degree, then the film density obtained is 1.63g/cm3, it is resistant to bend repeatedly more than 400 times, elongation at break 5%, intensity is
90MP, conductance 4000S/cm, thermal conductivity 700W/mK.
Comparative example 3：The raw material for shown in example 1, changing its graphene oxide used is performed as described above, it is left 20% with shive content
Right graphene oxide.Then the density of prepared film is 1.63g/cm3, the damage of 240 caudacorias is bent repeatedly, and elongation at break is
6%, intensity 84MP, conductance 2400S/cm, thermal conductivity 800W/mK.
Embodiment 3：The graphene oxide without fragment super large piece being prepared using embodiment 1 prepares super flexible high heat conduction
Graphene film.
1 mass parts average-size is more than to 100um graphene oxide and 0.01 mass parts hyperbranched polyglycidyl ether
The concentration that is configured to be 6mg/mL graphene oxide water solutions, in the solution add the ammonium hydrogen carbonate of mass fraction 0.1, by ultrasound
It is poured on after scattered on Die and mould plate and is dried into graphene oxide membrane, is then reduced with hydrazine hydrate reduction agent；Graphite after reduction
Alkene film first progressively heats up 700 DEG C under atmosphere of inert gases, is incubated 2h；1100 are progressively warming up under atmosphere of inert gases
DEG C, it is incubated 3h；3000 DEG C are progressively warming up under atmosphere of inert gases, 4h is incubated, porous graphite is can obtain after Temperature fall
Alkene film.Graphene film is suppressed under high pressure can obtain super flexible high heat conduction graphene film.
Heating rate is 0.2 DEG C/min at described 700 DEG C, and heating rate is 1 DEG C/min at 1100 DEG C, 3000 DEG C with
Under, heating rate is 5 DEG C/min.
Described pressing process pressure is 200MP, time 100h.
Obtained film density is 2.0g/cm3, it is resistant to bend repeatedly more than 1000 times, elongation at break 16%, intensity is
100MP, conductance 8600S/cm, thermal conductivity 1800W/mK.
Embodiment 4：The graphene oxide without fragment super large piece being prepared using embodiment 1 prepares super flexible high heat conduction
Graphene film.
Graphene oxide of the 1 mass parts average-size more than 100um and 0.1 mass parts polyphenylene sulfide are configured into concentration is
16mg/mL graphene oxide water solutions, the glycerine of mass fraction 1% is added in the solution, Die and mould plate is poured on after ultrasonic disperse
On be dried into graphene oxide membrane, then reduced with Vitamin C bolt；Graphene film after reduction is according to the institute of 1-table of table 3
The heat treatment mode shown is heat-treated, and porous graphene film is can obtain after Temperature fall.By graphene film in high pressure
Lower compacting can obtain super flexible high heat conduction graphene film.Described pressing process pressure is 50MP, time 6h.
Table 1:First step Elevated Temperature Conditions
Table 2:Second step Elevated Temperature Conditions
Table 3:3rd step Elevated Temperature Conditions
From 1~table of table 3 as can be seen that being determined in terms of the performance of this material mainly has three, one material internal graphite oxide
Alkene chip architecture repair situation, i.e., functional group come off and high temperature under carbon conjugated structure reparation.Second, material internal three-dimensional takes
To the continuity of structure, i.e., the connectivity of internal lamellar structure.Third, the formation of micro- air bag just can guarantee that material flexibility and
The presence of graphene film Rotating fields.Three's collective effect is to increase the performance of graphene film.
As it can be seen from table 1 comparing A1, B1, C1, D1, E1, A1 temperature is too low, and it is most of degradable to be not enough to removing
Functional group, cause gas in second step pyroprocess largely quickly to produce, tear lamellar structure at high temperature；E1 temperature mistakes
Height, generation gas is too fast, can largely tear material internal structure, both can cause deterioration in material properties.Have only B1, C1,
At a temperature of D1, functional group can slowly and thoroughly remove, to ensure material property.Compare C1, F1, G1, H1, F1 heating rate mistakes
Low, gas release is excessively slow, it is impossible to so that material internal forms through hole, is unfavorable for micro- air bag in ensuing temperature-rise period
Formation；H1 temperature-rise periods are too fast, and gas release is too fast, tear material internal structure, are unfavorable for forming transmission channel.Have CG only
It just can both ensure the formation of micro- air bag under heating rate, and can ensures the complete of passage.Compare C1, I1, J1, K1, L1, M1,
I1 soaking times are too short, it is impossible to ensure the degraded of most of functional group；M1 insulating processes are long, can absorb Jiao inside stove
Oil, it is unfavorable for the lifting of performance.C1, J1, K1, L1 just avoid both of the above.
From Table 2, it can be seen that comparing A2, B2, C2, D2, E2, A2 heating rates are too low to be not enough to form small space
Structure so that film can not form micro- air bag, have a strong impact on capability of electromagnetic shielding.E2 programming rates are too high, can tear graphene layer
Between structure so that graphene film link property is deteriorated, and heat conduction capability of electromagnetic shielding is all deteriorated.Have B2, C2, D2 programming rate only
Under, it just capable can not only ensure micro- airbag structure but also ensure the continuity inside graphene film.Compare C2, I2, J2, K2, L2,
M2, I2 soaking time are too short, and stable functional group can not fully come off；M2 overlong times, the easy tar adsorption of graphene film, no
Beneficial to the lifting of film properties；And can both ensure fully coming off for stabilising functional group under the conditions of C2, J2, K2, M2, and can avoids Jiao
The puzzlement of oil.
From table 3 it is observed that comparing A3, B3, C3, D3, E, A3 heating rates are too low, the mistake that most 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 periods are too fast, and gas release and high temperature are swollen
It is swollen too fast, it is easily destroyed the formation of micro- air bag.Only in the case of B3, C3, D3, micro- air bag could stablize formation, graphene
On structure could slowly repair.Compare C3, F3, G3, H3, I3, F3 outlet temperatures are too low, and graphene-structured is repaired not complete enough
It is kind, so various performances are all very poor；I3 outlet temperatures are 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.Compare C3, J3, K3, L3, M3, J3 soaking times are too low, graphene
Structure can not be repaired fully, and M3 soaking times are long, can also to adsorb the tar in body of heater, be influenceed the performance of film.
Embodiment 5：The graphene oxide without fragment super large piece being prepared using embodiment 1 prepares super flexible high heat conduction
Graphene film.
The polyethers nitrile of graphene oxide of the 1 mass parts average-size more than 100um and 0.5 mass parts is configured into concentration is
16mg/mL graphene oxide water solutions, the azodicarbonamide of mass fraction 4% is added in the solution, fallen after ultrasonic disperse
Graphene oxide membrane is dried on Die and mould plate, is then reduced with ascorbic acid；Graphene film after reduction is in inertia
First progressively heated up 500 DEG C under atmosphere, be incubated 2h；1000 DEG C are progressively warming up under atmosphere of inert gases, is incubated 0.5h；
2500 DEG C are progressively warming up under atmosphere of inert gases, 4h is incubated, porous graphene film is can obtain after Temperature fall.By graphite
Alkene film is suppressed under high pressure can obtain super flexible high heat conduction graphene film.
Heating rate is 0.1 DEG C/min at described 500 DEG C, and heating rate is 1 DEG C/min at 1000 DEG C, 2500 DEG C with
Under, heating rate is 7 DEG C/min.
Described pressing process pressure is 50MP, time 120h.
Obtained film density is 1.84g/cm3, it is resistant to bend repeatedly more than 1200 times, elongation at break 9%, intensity is
300MP, conductance 6500S/cm, thermal conductivity 1500W/mK.
Embodiment 6：The graphene oxide without fragment super large piece being prepared using embodiment 1 prepares super flexible high heat conduction
Graphene film.
Graphene oxide of the 1 mass parts average-size more than 100um and 0.08 mass parts polyether-ether-ketone are configured to concentration
For 6mg/mL graphene oxide water solutions, 0.05 mass parts polyethylene glycol 200 is added in the solution, is poured on after ultrasonic disperse
Graphene oxide membrane is dried on Die and mould plate, is then reduced with hydrogen iodide；Graphene film after reduction is in inert gas
First progressively heated up 800 DEG C under atmosphere, be incubated 2h；1300 DEG C are progressively warming up under atmosphere of inert gases, is incubated 3h；In indifferent gas
3000 DEG C are progressively warming up under body atmosphere, 0.5h is incubated, porous graphene film is can obtain after Temperature fall.Graphene is thin
Film is suppressed under high pressure can obtain super flexible high heat conduction graphene film.
Heating rate is 0.6 DEG C/min at described 800 DEG C, and heating rate is 1.3 DEG C/min at 1300 DEG C, 3000 DEG C with
Under, heating rate is 6.2 DEG C/min.
Described pressing process pressure is 150MP, time 210h.
Obtained film density is 1.94g/cm3, it is resistant to bend repeatedly more than 890 times, elongation at break 15%, intensity is
173MP, conductance 7500S/cm, thermal conductivity 1460W/mK.
Embodiment 7：The graphene oxide without fragment super large piece being prepared using embodiment 1 prepares super flexible high heat conduction
Graphene film.
1 mass parts average-size is more than to 100um graphene oxide and 0.2 mass parts PTT
It is 6~30mg/mL graphene oxide water solutions to be configured to concentration, adds the mass parts polyethylene glycol 400 of quality 0.02 in the solution,
It is poured on after ultrasonic disperse on Die and mould plate and is dried into graphene oxide membrane, then uses hydrazine hydrate reduction；Graphene after reduction
Film first progressively heats up 600 DEG C under atmosphere of inert gases, is incubated 1h；1100 DEG C are progressively warming up under atmosphere of inert gases,
It is incubated 2h；2700 DEG C are progressively warming up under atmosphere of inert gases, is incubated 1h, it is thin to can obtain porous graphene after Temperature fall
Film.Graphene film is suppressed under high pressure can obtain super flexible high heat conduction graphene film.
Heating rate is 0.1 DEG C/min at described 600 DEG C, and heating rate is 2.1 DEG C/min at 1100 DEG C, 2700 DEG C with
Under, heating rate is 6.8 DEG C/min.
Described pressing process pressure is 220MP, time 300h.
Obtained film density is 1.89g/cm3, it is resistant to bend repeatedly more than 1200 times, elongation at break 9%, intensity is
250MP, conductance 6100S/cm, thermal conductivity 1430W/mK.
Claims (8)
1. a kind of preparation method of super flexible high heat conduction graphene film, it is characterised in that comprise the following steps：
（1）The organic polymer of graphene oxide of the 1 mass parts average-size more than 100 μm and 0.01-1 mass parts is configured to
Concentration is 6 ~ 30mg/mL graphene oxide water solutions, adds mass fraction 0.1-5% auxiliary agent in the solution, the auxiliary agent be
2500oDegradable inorganic salts or 2500 under CoDegradable organic molecule under C；After ultrasonic disperse, it is poured on Die and mould plate and dries
Graphene oxide membrane is done into, is then reduced with reducing agent；
（2）By the graphene film after reduction under atmosphere of inert gases first with 0.1-1oC/min speed is warming up to 500-
800oC, it is incubated 0.5-2h；
（3）With 1-3 under atmosphere of inert gasesoC/min speed is warming up to 1000-1300oC, it is incubated 0.5-3h；
（4）With 5-8 under atmosphere of inert gasesoC/min speed is warming up to 2500-3000oC, it is incubated 0.5-4h, Temperature fall
It can obtain porous graphene film afterwards；
（5）Graphene film is suppressed under high pressure can obtain super flexible high heat conduction graphene film.
2. a kind of preparation method of super flexible high heat conduction graphene film as claimed in claim 1, it is characterised in that described
2500oDegradable inorganic salts are selected from ammonium hydrogen carbonate under C；2500oDegradable organic molecule is selected from glycerine, urine under C
Element, thiocarbamide, azodicarbonamide, polyethylene glycol 200, polyethylene glycol 400；Organic polymer by hyperbranched polyglycidyl ether,
Hyperbranched copolymerization (ester-amine), hyperbranched polysulfones amine, hyperbranched poly Siloxysilane, cellulose, sodium cellulose glycolate, silk
It is albumen, sodium alginate, chitosan, gelatin, agar, urea-melamine, polyimides, polybutylene terephthalate (PBT), poly-
Propylene glycol ester terephthalate, polyethylene, polypropylene, polybutene, styrene resin, polyoxymethylene, polyamide, poly- carbon
In acid esters, polymethyl methacrylate, polyphenylene sulfide, polyphenylene oxide, Noryl, polysulfones, polyketone, polyarylate, polyethers nitrile
It is one or more to be formed according to any than mixing.
3. a kind of preparation method of super flexible high heat conduction graphene film as claimed in claim 1, it is characterised in that described
Reducing agent includes amine, ascorbic acid, hydrogen iodide.
4. a kind of preparation method of super flexible high heat conduction graphene film as claimed in claim 1, it is characterised in that described
Pressing process pressure is 50-200MPa, and the time is 6-300 h.
A kind of 5. preparation method of super flexible high heat conduction graphene film as claimed in claim 1, it is characterised in that the step
Graphene oxide of the average-size more than 100 μm obtains by the following method in rapid 1：
（a）After the reaction solution dilution for the oxidized graphite flake that Modified-Hummer methods are obtained, carried out in the mesh screen of 140 mesh
Filter, obtains filtration product；
（b）By step（a）The filtration product of acquisition is with frozen water according to volume ratio 1：After 10 is well mixed, 2h is stood, is added dropwise
Mass fraction is 30% hydrogen peroxide, until the color of mixed liquor no longer changes；
（c）To step（b）The concentrated hydrochloric acid that concentration is 12mol/L is added dropwise in mixed liquor after processing, until cotton-shaped oxidation
Graphite disappears, then goes out graphite oxide chip with the screen filtration of 140 mesh；
（d）By step（c）The graphite oxide chip of acquisition is placed in shaking table, 20 ~ 80 turns/min, concussion washing so that oxidation stone
Smoky quartz piece is peeled off, and obtains the graphene oxide of no fragment super large piece, and average-size is more than 87 μm, breadth coefficient 0.2-0.5 it
Between.
6. according to the method for claim 5, it is characterised in that the step（a）In Modified-Hummer methods it is specific
For：- 10oUnder C, potassium permanganate is completely dissolved in the concentrated sulfuric acid that mass fraction is 98%, adds graphite, 60 revs/min are stirred
Stop stirring after mixing 2h, in -10-20o6-48h is reacted in a low temperature of C, obtains the oxidized graphite flake reaction solution of wide distribution；It is described
Graphite, potassium permanganate and concentrated sulfuric acid mass volume ratio be：1g：2-4g：30-40ml, the granularity of graphite are more than 150 μm.
7. according to the method for claim 5, it is characterised in that the mesh screen is the acidproof mesh screen of titanium alloy.
8. according to the method for claim 5, it is characterised in that the step（a）In, the reaction solution of oxidized graphite flake passes through
Diluting concentrated sulfuric acid agent is diluted, and the volume of diluent is 1-10 times of reaction solution volume.
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| CN104528707A (en) * | 2015-01-23 | 2015-04-22 | 青岛科技大学 | Preparation method of high-conductivity graphene membrane |
| CN104609410A (en) * | 2015-01-30 | 2015-05-13 | 浙江碳谷上希材料科技有限公司 | Preparation method of high-performance graphene porous membrane |
| CN104925794A (en) * | 2015-06-11 | 2015-09-23 | 青岛大学 | Method for growing three-dimensional nitrogen-doped graphene by taking nanoporous graphene as substrate |
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