CN105731433A - Function transformation method of breathable graphene film - Google Patents
Function transformation method of breathable graphene film Download PDFInfo
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- CN105731433A CN105731433A CN201610049004.8A CN201610049004A CN105731433A CN 105731433 A CN105731433 A CN 105731433A CN 201610049004 A CN201610049004 A CN 201610049004A CN 105731433 A CN105731433 A CN 105731433A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/24—Thermal properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The invention discloses a method for achieving function transformation of a breathable graphene film between the heat-conducting property and the electromagnetic shielding property. The breathable graphene film is formed by mutually overlapping planar orientated graphene sheets of which the mean size is greater than 100 microns through phi-pin conjugate action; the breathable graphene film comprises a graphene structure formed by 1-4 graphene sheets; the defects of the graphene sheets are extremely few, and ID/TG is smaller than 0.01; the transformation mode from the electromagnetic shielding property to the heat-conducting property is pressing the breathable graphene film with the electromagnetic shielding property for 5 minutes to 2 hours at 50-200MPa high voltage, and the heat conductivity is 1800-2600W/mK; and the transformation mode from the heat-conducting property to the electromagnetic shielding property is soaking the breathable graphene film with the heat-conducting property into a boiling breathing agent for 1-1,000 seconds, and the shielding effectiveness reaches 90-130dB within a range of 500MHz to 40GHz.
Description
Technical field
The present invention relates to Novel heat-conducting, inhale ripple and electromagnetic shielding material, particularly relate to one and can breathe stone
The function conversion method of ink alkene film.
Background technology
2010, two professor Andre GeiM and Konstantin of Univ Manchester UK
Novoselov obtains Nobel Prize in physics because being successfully separated out stable Graphene first, has started complete
The upsurge that Graphene is studied by the world.Graphene has excellent electric property, and (under room temperature, electron mobility can
Reach 2 × 105cM2/ Vs), prominent heat conductivility (5000W/ (MK), extraordinary specific surface area (2630
M2/ g), its Young's modulus (1100GPa) and fracture strength (125GPa).The conduction that Graphene is excellent
Heat conductivility is well beyond metal, and Graphene has the advantage of corrosion-and high-temp-resistant simultaneously, and it is good
Mechanical performance and relatively low density more allow it possess the potentiality at thermo electric material field substituted metal.
Macroscopic view assembles the master that the graphene film of graphene oxide or graphene nanometer sheet is nanoscale graphite alkene
Want application form.By further high-temperature process, it is possible to repair the defect of Graphene, it is possible to effective
Improve the electric conductivity of graphene film and thermal conductance, can be widely applied to smart mobile phone, intelligence hardware with oneself,
In panel computer, notebook computer contour radiating requirements accompanied electronic equipment.
The at present application of graphene film is limited to independent functional material, such as heat conducting film, conducting film,
Inhale ripple film, screened film.Single function substantially can not meet the demand that future technology progress is complicated.To this end,
We utilize super large sheet to do substrate without fragment Graphene and devise and can breathe graphene film, and one exhales between a suction
Complete heat-conductivity conducting and inhale wave screen cover between the conversion of function.For multifunction device design provide new
Thinking.
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 function breathing graphene film
Conversion method.
It is an object of the invention to be achieved through the following technical solutions: a kind of function breathing graphene film turns
Changing method, described power and energy is to change between heat conductivility and capability of electromagnetic shielding；Described electromagnetic wave shielding
Can be to the conversion regime of heat conductivility: the graphene film breathed with capability of electromagnetic shielding is existed
5min-2h is suppressed under the high pressure of 50-200MP；The mode that described heat conductivility is changed to capability of electromagnetic shielding is:
The graphene film breathed with heat conductivility is soaked 1-1000s in the breathing agent of boiling；Described breathing agent
For 2,3-dimethyl-1-butylene, 1,2-dichloroethylene (suitable), 1,2-dichloroethylene (instead), 1,5-hexadiene, 3-
Methyl-1-pentene, 4-methyl-1-pentene, 4-methyl-2-amylene (suitable), 4-methyl-2-amylene (instead), the chloro-1,3-of 2-
Butadiene, iodoethylene, n-propylamine, diethylamine, ether, acetone, dichloromethane, ethanol, ethyl acetate,
The common solvents such as liquid nitrogen, water, petroleum ether, normal hexane；Described breathe flat by planar orientation of graphene film
All sizes are mutually overlapped by the pi-conjugated effect of π more than the graphene film of 100 μm and form.Wherein comprise by 1-4
The graphene-structured that layer graphene sheet is constituted.And the defect of graphene film is few, its ID/TG＜ 0.01.
Further, the described thickness breathing graphene film is 1mm, and breathing agent is liquid nitrogen, soaks
300～400s.
Further, the described thickness breathing graphene film is 5mm, and breathing agent is water, soaks 800～1000s.
Further, the described thickness breathing graphene film is 0.1mm, and breathing agent is acetone, soaks
10～20s.
Further, the described preparation method breathing graphene film is as follows:
(1) more than the graphene oxide of 100 μm, average-size being configured to concentration is 6～30mg/mL oxidations
Graphene aqueous solution, adds the auxiliary agent of mass fraction 0.1-5% in the solution, and described auxiliary agent is inorganic salt, has
The little molecule of machine or macromolecule；After ultrasonic disperse, it is poured on Die and mould plate and is dried into graphene oxide membrane, then use
Reducing agent reduces；
(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, insulation under atmosphere of inert gases
0.5-3h；
(4) with the ramp to 2500-3000 DEG C of 5-8 DEG C/min, insulation under atmosphere of inert gases
0.5-4h, i.e. can get the graphene film breathed of porous after Temperature fall.
Further, described inorganic salt is selected from ammonium hydrogen carbonate, carbamide, thiourea, azodicarbonamide；Organic
Little molecule is selected from glycerol, polyethylene glycol 200, PEG400；Macromolecule is selected from cellulose, gelatin, shell
Polysaccharide, aqueous polyurethane, acrylic emulsion etc..
Further, in described step 1, average-size is more than the graphene oxide of 100um by the following method
Obtain:
(1) after the reactant liquor dilution of the oxidized graphite flake that Modified-Hummer method is obtained, in 140 mesh
Mesh screen filter, obtain 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 hydrogen peroxide (H2O2Mass fraction be 30%), until the color of mixed liquor no longer changes (i.e.
Potassium permanganate in mixed liquor is removed the most completely)；
(3) mixed liquor after step 2 processes is added dropwise over concentrated hydrochloric acid (concentration is 12mol/L), until
Cotton-shaped graphite oxide 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,
Graphite oxide wafer being peeled off, obtains the graphene oxide without fragment super large sheet, average-size is more than 87um,
Breadth coefficient is between 0.2-0.5.
Further, Modified-Hummer method in described step 1 is particularly as follows: at-10 DEG C, by height
Potassium manganate is completely dissolved in the concentrated sulphuric acid that mass fraction is 98%, adds graphite, 60 revs/min of stirring 2h
Rear stopping stirs, and reacts 6-48h under low temperature (-10-20 DEG C), obtains the oxidized graphite flake reaction of wide distribution
Liquid；Described graphite, potassium permanganate with concentrated sulphuric acid mass volume ratio is: 1g:2-4g:30-40ml, graphite
Granularity 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 carried out by diluent such as concentrated sulphuric acids
Dilution, the volume of diluent is 1-10 times of reactant liquor volume.
The present invention elaborate first a kind of can change between heat conductivility and capability of electromagnetic shielding multi-functional
Graphene film, and elaborate its function conversion method, this graphene film is big by the average-size of planar orientation
Graphene film in 100 μm is mutually overlapped formed by the pi-conjugated effect of π.Big conjugated structure ensure that stone
Path unimpeded between ink alkene, and the introducing of graphene-structured that 1-4 layer graphene sheet is constituted, greatly
Improve the electric conductivity of material；In non-lap-joint, form cavity between graphene film and sheet, work as cavity
During interior injection gas, forming the micro-air bag of Graphene, micro-airbag structure assists with preferable electric conductivity, makes
The graphene film obtaining the present invention has extremely strong capability of electromagnetic shielding.When using condition of high voltage, micro-air bag is entered
Row compression, forms fold so that the deformation of graphene film is remembered, and gives the flexibility of its superelevation and leads
Hot property.One exhales and is changed by the several functions of Graphene between a suction, carries to the design of future device
The new thinking of confession, is also the space of the application extension of graphene film.
By the present invention in that by super large sheet graphene oxide film forming, and allow under its mode at high temperature annealed,
Perfect reparation Graphene defect, and edge defect is preferably minimized, form perfect big conjugated structure,
Its conjugation size has even extended to the Graphene of full wafer, it is ensured that Graphene thermal conducting path unimpeded；Enter
One step temperature-rise period by three step independences so that the functional group of graphenic surface gradually disengages, and is mixed in
Auxiliary agent (perforating agent) between graphene film slowly decomposes, and both of which discharges the most step by step, with
Time, graphitizing process stepwise development, form the micro-air bag of Graphene；And in the forming process of micro-air bag, stone
The most stable functional group in ink alkene surface comes off the most therewith, adds gas expansion under high temperature, thereby produces
It is successfully introduced into the graphene-structured that 1-4 layer graphene sheet is constituted.
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 reaction under the graphene oxide distribution of sizes (left) obtained, 20 degree under 50 degree to obtain
Graphene oxide distribution of sizes (right).
Fig. 5 is for can breathe graphene film respiratory electromicroscopic photograph.
Fig. 6 is for can breathe graphene film respiratory sectional view.
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
The graphene film of μm is important role during constituting graphene film of the present invention, and the present invention is at oxidation stone
Before the washing of smoky quartz body, the way using mesh screen to separate, chip separation is gone out.And use 10 times with upper volume
Frozen water be diluted so that its wafer will not be destroyed because of the heat of solution of sulphuric acid.Use further and shake
Bed concussion washing so that graphene oxide lamella avoids the broken of mechanical force peeling off when.Further
Ground, the present invention prepares graphene film also by cryogenic conditions, and at low temperatures, potassium permanganate oxidation is more weak,
The speed that its selfdecomposition produces oxygen is slow, and therefore gas is the most weak to the fragmentation of graphite oxide crystal,
The graphene oxide making 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 super large
The graphene oxide without fragment of sheet, average-size is more than 87um, and breadth coefficient is between 0.2-0.5, broken
Sheet content is less than 1%.
Below in conjunction with the accompanying drawings and embodiment the invention will be further described.The present embodiment is served only for this
Invention is described further, it is impossible to be interpreted as limiting the scope of the invention, the technology of this area
Personnel make some nonessential change and adjustment according to the content of foregoing invention, belong to the guarantor of the present invention
Protect scope.
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, treats fully to dissolve
After, add graphite, 60 revs/min are slowly stirred after 2h and stop stirring, 20 DEG C, react respectively at 50 DEG C
6h, respectively obtains the graphite oxide crystal of wide distribution；As it is shown in figure 1, the oxidation stone obtained at a temperature of two kinds
All there is more fragment in smoky quartz sheet, this makes the graphene oxide of its correspondence have a lot of fragment (figures equally
2)。
(2) (extension rate can be any multiple to reactant liquor diluting concentrated sulfuric acid step 1 obtained, originally
Embodiment dilutes about 10 times), and stone will be aoxidized with the titanium alloy mesh screen of 150um aperture (140 mesh)
Smoky quartz body filters out (reactant liquor recovery), and be poured slowly into quickly stirring relative to filtration product 10 times
In the frozen water of volume, stand 2h, be slowly added to H2O2, to remove potassium permanganate unnecessary in reaction, add
Appropriate hydrochloric acid is until cotton-shaped graphite oxide disappears, then filters out graphite oxide with titanium alloy mesh screen (140 mesh)
Wafer；Shaking table slowly shakes washing, obtain the graphene oxide without fragment super large sheet (average-size is 87um,
Breadth coefficient is 0.5).Graphite, potassium permanganate with concentrated sulphuric acid mass volume ratio is: 1g:2g:40ml, stone
The granularity of ink is 200um.
As it is shown on figure 3, washing obtains after after the lower reaction of high temperature 50 degree, isolated graphite oxide wafer separates
Graphene oxide has a lot of fragments equally；From fig. 4, it can be seen that under low temperature after (20 DEG C) Reaction Separation
Large stretch of graphene oxide distribution of sizes 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
Entering graphite, 60 revs/min are slowly stirred stopping stirring after 2h, react 48h, obtain under low temperature (0 DEG C)
Reactant liquor；By reactant liquor respectively with dilute sulfur that the concentrated sulphuric acid of mass fraction more than 98%, mass fraction are 10%
Acid is diluted, and then with the titanium alloy mesh screen in 150um aperture, graphite oxide crystal filters out (reaction
Liquid reclaims), and be poured slowly in the frozen water relative to 10 times of volumes of filtration product of quickly stirring, stand 2h,
It is slowly added to H2O2, to remove potassium permanganate unnecessary in reaction, add appropriate hydrochloric acid until cotton-shaped oxidation
Graphite disappears, then leaches graphite oxide wafer with titanium alloy reticulated is sieved；Shaking table slowly shakes washing, obtains anti-
Answer 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 98 to the graphene oxide of the sheet of super large without fragment that reaction obtains
Um, breadth coefficient is 0.4), and dilute with dilute sulfuric acid, containing a large amount of fragments in the product obtained, size is divided
Cloth coefficient is more than 100%.This is due in dilute sulfuric acid dilution, highly exothermic, destroys graphite oxide brilliant
Body.
Embodiment 1-3
At-10 DEG C, potassium permanganate is slowly added in the concentrated sulphuric acid of quickly agitation, after fully dissolving, adds
Entering graphite, 60 revs/min are slowly stirred stopping stirring after 2h, react 28h, obtain under low temperature (20 DEG C)
The graphite oxide crystal of wide distribution；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 recovery), and be poured slowly into respectively quickly stirring relative to mistake
Filter in the frozen water of 5 times of volumes of product, 8 times of volumes, 10 times of volumes, 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 network is sieved through and leaches graphite oxide wafer；Shaking table slowly shakes washing, obtains product；Graphite, height
Potassium manganate with concentrated sulphuric acid mass volume ratio is: 1:5g:34ml, and 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 obtaining size uniformity
Sheet, just can obtain under 10 times of volumes graphene oxide without fragment super large sheet (average-size is 92um,
Breadth coefficient is 0.2).It follows that the amount of frozen water is too low, the heat of mixing will be made to concentrate release, destroy crystalline substance
Body structure.
Embodiment 2: the graphene oxide of the sheet of super large without fragment that employing embodiment 1 prepares is prepared respirable
Graphene film.
The average-size graphene oxide more than 100um is configured to concentration is 30mg/mL graphene oxide
Aqueous solution, adds mass fraction 5% carbamide in the solution, is poured on Die and mould plate and is dried into after ultrasonic disperse
Graphene oxide membrane, then reduces with hydrogen iodide reducing agent；Graphene film after reduction is at indifferent gas
Three step heat treatments are carried out according to the heat treatment mode shown in table 1～table 3 under body atmosphere；After Temperature fall
To the porous graphene thin film that thickness is 1mm.Graphene film is under high pressure suppressed super flexible high
Thermal conductivity graphene film.Described pressing process pressure is 200MP, and the time is 300h.
The graphene film of above-mentioned gained is suppressed under the high pressure of 50MP 2h；Record its thermal conductivity；Will pressure
Graphene film after system soaks 300s in the liquid nitrogen of boiling, records its capability of electromagnetic shielding, such as table 1-3
Shown in.
Table 1: the heat treatment mode of the first step
Table 2: the heat treatment mode of second step
The heat treatment mode of table 3: the three step
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 oxygen
Functionalized graphene chip architecture repairs coming off and the reparation of carbon conjugated structure under high temperature of situation, i.e. functional group.Its
Two, the seriality of material internal 3 D tropism structure, the i.e. connectivity of internal sheets Rotating fields.Its three, micro-gas
The flexibility forming guarantee material of capsule and the existence of graphene film Rotating fields.Three acts on increasing jointly
Add the performance of graphene film.
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
Go to the functional group that major part is degradable, cause gas in second step pyroprocess the most quickly to produce, at high temperature
Lower tearing sheet Rotating fields；E1 temperature is too high, produces gas too fast, can tear material internal structure in a large number, and two
Person can make deterioration in material properties.Having only at a temperature of B1, C1, D1, functional group can slowly the most thoroughly
Remove, to ensure material property.Relatively C1, F1, G1, H1, F1 heating rate is too low, and gas discharges
The slowest, it is impossible to make material internal form through hole, ensuing temperature-rise period is unfavorable for micro-air bag
Formation；H1 temperature-rise period is too fast, and gas release is too fast, tears material internal structure, is unfavorable for forming biography
Defeated passage.Have the formation that just can both ensure micro-air bag under CG heating rate only, 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 major part functional group
Degraded；M1 insulating process is long, can absorb the tar inside stove, 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, A2 heating rate is too low to be not enough to
Form small gap structure so that film can not form micro-air bag, has a strong impact on capability of electromagnetic shielding.E2 liter
Temperature speed is too high, can tear Graphene interlayer structure so that graphene film link property is deteriorated, heat conduction electromagnetic screen
Cover performance to be all deteriorated.Have only under the programming rate of B2, C2, D2, just capable can both ensure that micro-air bag is tied
Structure ensures again the seriality within graphene film.During relatively C2, I2, J2, K2, L2, M2, I2 insulation
Between too short, stable functional group can not fully come off；M2 overlong time, the easy tar adsorption of graphene film,
It is unfavorable for the lifting of film properties；And under the conditions of C2, J2, K2, M2, both can ensure that filling of stabilising functional group
Divide and come off, be avoided that again the puzzlement of tar.
From table 3 it is observed that compare A3, B3, C3, D3, E, A3 heating rate is too low, the most surely
That determines that functional group comes off is the slowest, is not enough to support the formation of micro-air bag during forming micro-air bag；E3 heats up
Process is too fast, and gas release and high-temperature expansion are too fast, are easily destroyed the formation of micro-air bag.Only B3, C3,
In the case of D3, the formation that micro-air bag could be stable, the structure on Graphene could be repaired slowly.Relatively
C3, F3, G3, H3, I3, F3 outlet temperature is too low, and graphene-structured is repaired the most perfect, thus various
Performance is the most very poor；I3 outlet temperature is too high, and Graphene can be vaporized；At a temperature of C3, G3, H3
Can both ensure the reparation of graphene-structured, will not be vaporized again.Relatively C3, J3, K3, L3, M3, J3
Temperature retention time is too low, and graphene-structured can not fully be repaired, and M3 temperature retention time is long, also can make to adsorb stove
Tar in body, affects the performance of film.
Embodiment 3: the graphene oxide of the sheet of super large without fragment that employing embodiment 1 prepares is prepared respirable
Graphene film.
The preparation method of graphene film can be breathed, it is characterised in that step is as follows: average-size be more than
It is 6mg/mL graphene oxide water solution that the graphene oxide of 100um is configured to concentration, with knifing or
Solution spins the method film forming of film, naturally dries film forming, and reduces with reducing agent；By the Graphene after reduction
Thin film the most progressively heats up 500 DEG C under atmosphere of inert gases, is incubated 0.5h；Under atmosphere of inert gases progressively
It is warmed up to 1000 DEG C, is incubated 0.5h；Under atmosphere of inert gases, progressively it is warmed up to 2500 DEG C, is incubated 0.5-4h,
I.e. can get after Temperature fall and can breathe graphene film.Described reducing agent is hydrazine hydrate.Described 500
At DEG C, heating rate is 0.1 DEG C/min, and at 1000 DEG C, heating rate is 1.3 DEG C/min, less than 2500 DEG C,
Heating rate is 8 DEG C/min.
Embodiment 4:
The preparation method of graphene film can be breathed, it is characterised in that step is as follows: average-size be more than
It is 10mg/mL graphene oxide water solution that the graphene oxide of 100um is configured to concentration, with knifing or
Solution spins the method film forming of film, naturally dries film forming, and reduces with reducing agent；By the Graphene after reduction
Thin film the most progressively heats up 500 DEG C under atmosphere of inert gases, is incubated 2h；Under atmosphere of inert gases progressively
It is warmed up to 1300 DEG C, is incubated 3h；Under atmosphere of inert gases, progressively it is warmed up to 3000 DEG C, is incubated 4h,
I.e. can get after Temperature fall and can breathe graphene film.Described reducing agent is ascorbic acid.Described
At 500 DEG C, heating rate is 0.1 DEG C/min, and at 1300 DEG C, heating rate is 1 DEG C/min, less than 3000 DEG C,
Heating rate is 5 DEG C/min.
By accompanying drawing:
Fig. 5, graphene film respiratory electromicroscopic photograph can be breathed, during exhaling under external force,
Graphene film is driven plain, and breathes pore and is remained by the form of fold；The mistake inhaled under gas effect
Cheng Zhong, fold is strutted by gas, gradually becomes smooth.
Fig. 6, graphene film respiratory sectional view can be breathed, during exhaling under external force, stone
Ink alkene film is driven plain, and its structure becomes closely knit；During inhaling under gas effect, fold is supportted by gas
Opening, its structure becomes loose.
Embodiment 5:
The preparation method of graphene film can be breathed, it is characterised in that step is as follows: average-size be more than
It is 6mg/mL graphene oxide water solution that the graphene oxide of 100um is configured to concentration, with knifing or
Solution spins the method film forming of film, naturally dries film forming, and reduces with reducing agent；By the Graphene after reduction
Thin film the most progressively heats up 800 DEG C under atmosphere of inert gases, is incubated 0.5h；Under atmosphere of inert gases progressively
It is warmed up to 1100 DEG C, is incubated 3h；Under atmosphere of inert gases, progressively it is warmed up to 2500 DEG C, is incubated 4h,
I.e. can get after Temperature fall and can breathe graphene film.Described reducing agent is hydrogen iodide.Described 800
At DEG C, heating rate is 0.1 DEG C/min, and at 1100 DEG C, heating rate is 2 DEG C/min, less than 2500 DEG C,
Heating rate is 6 DEG C/min.
Embodiment 6:
The preparation method of graphene film can be breathed, it is characterised in that step is as follows: average-size be more than
It is 12mg/mL graphene oxide water solution that the graphene oxide of 100um is configured to concentration, with knifing or
Solution spins the method film forming of film, naturally dries film forming, and reduces with reducing agent；By the Graphene after reduction
Thin film the most progressively heats up 500 DEG C under atmosphere of inert gases, is incubated 1h；Under atmosphere of inert gases progressively
It is warmed up to 1000 DEG C, is incubated 1h；Under atmosphere of inert gases, progressively it is warmed up to 3000 DEG C, is incubated 0.5-4h,
I.e. can get after Temperature fall and can breathe graphene film.Described reducing agent comprise hydrazine hydrate, amine,
Ascorbic acid, hydrogen iodide.At described 500 DEG C, heating rate is 0.4 DEG C/min, and heat up at 1000 DEG C speed
Rate is 1 DEG C/min, less than 3000 DEG C, and heating rate is 6 DEG C/min.
Embodiment 7:
The preparation method of graphene film can be breathed, it is characterised in that step is as follows: average-size be more than
It is 10mg/mL graphene oxide water solution that the graphene oxide of 100um is configured to concentration, with knifing or
Solution spins the method film forming of film, naturally dries film forming, and reduces with reducing agent；By the Graphene after reduction
Thin film the most progressively heats up 800 DEG C under atmosphere of inert gases, is incubated 2h；Under atmosphere of inert gases progressively
It is warmed up to 1300 DEG C, is incubated 0.5-3h；Under atmosphere of inert gases, progressively it is warmed up to 3000 DEG C, is incubated 2h,
I.e. can get after Temperature fall and can breathe graphene film.Described reducing agent comprise hydrazine hydrate, amine,
Ascorbic acid, hydrogen iodide.At described 800 DEG C, heating rate is 1 DEG C/min, and heat up at 1300 DEG C speed
Rate is 1 DEG C/min, less than 3000 DEG C, and heating rate is 5 DEG C/min.
Embodiment 8:
The preparation method of graphene film can be breathed, it is characterised in that step is as follows: average-size be more than
It is 20mg/mL graphene oxide water solution that the graphene oxide of 100um is configured to concentration, with knifing or
Solution spins the method film forming of film, naturally dries film forming, and reduces with reducing agent；By the Graphene after reduction
Thin film the most progressively heats up 500 DEG C under atmosphere of inert gases, is incubated 2h；Under atmosphere of inert gases progressively
It is warmed up to 1300 DEG C, is incubated 0.5h；Under atmosphere of inert gases, progressively it is warmed up to 2500 DEG C, is incubated 1h,
I.e. can get after Temperature fall and can breathe graphene film.Described reducing agent comprise hydrazine hydrate, amine,
Ascorbic acid, hydrogen iodide.At described 500 DEG C, heating rate is 0.4 DEG C/min, and heat up at 1300 DEG C speed
Rate is 1 DEG C/min, less than 2500 DEG C, and heating rate is 5.8 DEG C/min.
Claims (10)
1. the function conversion method that can breathe graphene film, it is characterised in that, described power and energy is for lead
Change between hot property and capability of electromagnetic shielding；Described capability of electromagnetic shielding to the conversion regime of heat conductivility is:
The graphene film breathed with capability of electromagnetic shielding is suppressed 5min-2h under the high pressure of 50-200MP；Institute
Stating the mode that heat conductivility changes to capability of electromagnetic shielding is: will have the graphene film breathed of heat conductivility
1-1000s is soaked in the breathing agent of boiling；Described breathing agent is 2,3-dimethyl-1-butylene, 1,2-bis-chloroethene
Alkene (suitable), 1,2-dichloroethylene (instead), 1,5-hexadiene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 4-
Methyl-2-amylene (suitable), 4-methyl-2-amylene (instead), 2-chloro-1,3-butadiene, iodoethylene, n-propylamine, two
Ethamine, ether, acetone, dichloromethane, ethanol, ethyl acetate, liquid nitrogen, water, petroleum ether, normal hexane
Deng common solvents；Described graphene film of breathing is more than the Graphene of 100 μm by the average-size of planar orientation
Sheet is mutually overlapped by the pi-conjugated effect of π and forms.Wherein comprise the Graphene knot being made up of 1-4 layer graphene sheet
Structure.And the defect of graphene film is few, its ID/TG＜ 0.01.
The function conversion method breathing graphene film the most according to claim 1, it is characterised in that, institute
Stating and can breathing the thickness of graphene film is 1mm, and breathing agent is liquid nitrogen, soaks 300～400s.
The function conversion method breathing graphene film the most according to claim 1, it is characterised in that, institute
Stating and can breathing the thickness of graphene film is 5mm, and breathing agent is water, soaks 800～1000s.
The function conversion method breathing graphene film the most according to claim 1, it is characterised in that, institute
Stating and can breathing the thickness of graphene film is 0.1mm, and breathing agent is acetone, soaks 10～20s.
The function conversion method breathing graphene film the most according to claim 1, it is characterised in that, institute
State that can to breathe the preparation method of graphene film as follows:
(1) more than the graphene oxide of 100 μm, average-size being configured to concentration is 6～30mg/mL oxidations
Graphene aqueous solution, the auxiliary agent of addition mass fraction 0.1-5% (i.e. divide by auxiliary agent quality in the solution in the solution
Number is 0.1-5%), described auxiliary agent is inorganic salt, organic molecule or macromolecule；After ultrasonic disperse, it is poured on mould
It is dried into graphene oxide membrane on tool plate, then reduces 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, insulation under atmosphere of inert gases
0.5-3h；
(4) with the ramp to 2500-3000 DEG C of 5-8 DEG C/min, insulation under atmosphere of inert gases
0.5-4h, i.e. can get the graphene film breathed of porous after Temperature fall.
The preparation method of a kind of super flexibility the most according to claim 5 high thermal conductivity graphene thin film, its feature
Being, described inorganic salt is selected from ammonium hydrogen carbonate, carbamide, thiourea, azodicarbonamide；Organic molecule
Selected from glycerol, polyethylene glycol 200, PEG400；Macromolecule selected from cellulose, gelatin, chitosan,
Aqueous polyurethane, acrylic emulsion etc..
The function conversion method breathing graphene film the most according to claim 5, it is characterised in that, institute
State the average-size graphene oxide more than 100um in step 1 to obtain by the following method:
(1) after the reactant liquor dilution of the oxidized graphite flake that Modified-Hummer method is obtained, in 140 mesh
Mesh screen filter, obtain 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 hydrogen peroxide (H2O2Mass fraction be 30%), until the color of mixed liquor no longer changes (i.e.
Potassium permanganate in mixed liquor is removed the most completely)；
(3) mixed liquor after step 2 processes is added dropwise over concentrated hydrochloric acid (concentration is 12mol/L), until
Cotton-shaped graphite oxide 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,
Graphite oxide wafer being peeled off, obtains the graphene oxide without fragment super large sheet, average-size is more than 87um,
Breadth coefficient is between 0.2-0.5.
Method the most according to claim 7, it is characterised in that in described step 1
Modified-Hummer method is particularly as follows: at-10 DEG C, it is 98% that potassium permanganate is completely dissolved in mass fraction
Concentrated sulphuric acid in, add graphite, 60 revs/min stirring 2h after stop stirring, under low temperature (-10-20 DEG C)
Reaction 6-48h, obtains 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.
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, oxidized graphite flake
Reactant liquor is diluted by diluent such as concentrated sulphuric acids, and the volume of diluent is 1-10 times of reactant liquor volume.
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| CN110668434A (en) * | 2019-11-29 | 2020-01-10 | 苏州世华新材料科技股份有限公司 | Heat-conducting graphene film with adjustable vertical and in-plane heat conductivity coefficients and preparation method thereof |
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