CN105731433B - A kind of function conversion method for breathing graphene film - Google Patents

A kind of function conversion method for breathing graphene film Download PDF

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CN105731433B
CN105731433B CN201610049004.8A CN201610049004A CN105731433B CN 105731433 B CN105731433 B CN 105731433B CN 201610049004 A CN201610049004 A CN 201610049004A CN 105731433 B CN105731433 B CN 105731433B
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graphene
graphene film
film
breathing
graphite
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CN105731433A (en
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高超
彭蠡
赵晓莉
刘英军
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Changxin De Technology Co Ltd
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Zhejiang University ZJU
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00Structure or properties of graphene
    • C01B2204/04Specific amount of layers or specific thickness
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00Structure or properties of graphene
    • C01B2204/20Graphene characterized by its properties
    • C01B2204/22Electronic properties
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00Structure or properties of graphene
    • C01B2204/20Graphene characterized by its properties
    • C01B2204/24Thermal properties
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00Structure or properties of graphene
    • C01B2204/20Graphene characterized by its properties
    • C01B2204/32Size or surface area

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Abstract

The method that graphene film realizes power and energy between heat conductivility and capability of electromagnetic shielding is breathed the invention discloses a kind of;The graphene film that graphene film is breathed by the average-size of planar orientation more than 100 μm is formed by the pi-conjugated effects of π mutually overlap joint.Wherein comprising the graphene-structured being made up of 14 layer graphene pieces.And the defect of graphene film is few, its ID/TG< 0.01;Capability of electromagnetic shielding is to the conversion regime of heat conductivility:The graphene film that breathes with capability of electromagnetic shielding is suppressed into 5min 2h under 50 200MP high pressure, its thermal conductivity is 1800 2600W/mK;The mode that the heat conductivility is changed to capability of electromagnetic shielding is:The graphene film that breathes with heat conductivility is soaked into 1 1000s in the breathing agent of boiling, it reaches 90 130dB in 500MHz 40GHz inner shield efficiency.

Description

A kind of function conversion method for breathing graphene film
Technical field
The present invention relates to novel heat-conducting, ripple and electromagnetic shielding material are inhaled, more particularly to a kind of graphene film that breathes Function conversion method.
Background technology
, two of Univ Manchester UK professor Andre GeiM and Konstantin Novoselov in 2010 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 that 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.By further high-temperature process, the defect of graphene can be repaired, the electric conductivity of graphene film can be effectively improved And thermal conductance, it can be widely applied to smart mobile phone, the intelligence high radiating requirements such as hardware, tablet personal computer, notebook computer with oneself In accompanied electronic equipment.
The application of current graphene film is limited to independent functional material, such as heat conducting film, conducting film, suction ripple film, screen Cover film.Single function can not substantially meet the complicated demand of future technology progress.Therefore, we utilize super large piece without fragment stone Black alkene, which does substrate and devised, can breathe graphene film, one exhale complete thermal conductivity between a suction and inhale wave screen cover between function turn Change.The new thinking provided for the design of multifunction device.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art there is provided a kind of power and energy side for breathing graphene film Method.
The purpose of the present invention is achieved through the following technical solutions:A kind of power and energy side for breathing graphene film Method, the power and energy is to be changed between heat conductivility and capability of electromagnetic shielding;The capability of electromagnetic shielding is to heat conductivility Conversion regime be:The graphene film that breathes with capability of electromagnetic shielding is suppressed into 5min-2h under 50-200MP high pressure; The mode that the heat conductivility is changed to capability of electromagnetic shielding is:Graphene film will be breathed in boiling with heat conductivility 1-1000s is soaked in breathing agent;The breathing agent is 2,3- dimethyl -1- butylene, 1,2- dichloroethylene (suitable), the chloroethenes of 1,2- bis- Alkene (anti-), 1,5- hexadienes, 3- Methyl-1-pentenes, 4-methyl-1-pentene, 4- methyl -2- amylenes (suitable), 4- methyl -2- amylenes The chloro- 1,3- butadiene of (anti-), 2-, iodoethylene, n-propylamine, diethylamine, ether, acetone, dichloromethane, ethanol, ethyl acetate, liquid The common solvents such as nitrogen, water, petroleum ether, n-hexane;The graphene film that breathes is more than 100 μm by the average-size of planar orientation Graphene film by π it is pi-conjugated effect mutually overlap joint form.Wherein comprising the graphene-structured being made up of 1-4 layer graphene pieces. And the defect of graphene film is few, its ID/TG< 0.01.
Further, the thickness for breathing graphene film is 1mm, and breathing agent is liquid nitrogen, soaks 300~400s.
Further, the thickness for breathing graphene film is 5mm, and breathing agent is water, soaks 800~1000s.
Further, the thickness for breathing graphene film is 0.1mm, and breathing agent is acetone, soaks 10~20s.
Further, the preparation method for breathing graphene film is as follows:
(1) graphene oxide that average-size is more than 100 μm is configured to concentration for 6~30mg/mL graphene oxide water Solution, adds mass fraction 0.1-5% auxiliary agent in the solution, and the auxiliary agent is inorganic salts, organic molecule or macromolecule;It is super After sound is scattered, it is poured on Die and mould plate and is dried into graphene oxide membrane, 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 It can obtain after cooling and porous breathe graphene film.
Further, described inorganic salts are selected from ammonium hydrogen carbonate, urea, thiocarbamide, azodicarbonamide;Organic molecule is selected From glycerine, polyethylene glycol 200, polyethylene glycol 400;Macromolecule is selected from cellulose, gelatin, chitosan, aqueous polyurethane, acrylic acid Emulsion etc..
Further, graphene oxide of the average-size more than 100um is obtained 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) filtration product for obtaining step 1 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 is 12mol/L) is added dropwise in the mixed liquor after being handled to step 2, 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 is 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 of no fragment super large piece, and 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%, stirring stopped after adding graphite, 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 is 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 present invention elaborates a kind of multifunctional graphite vinyl that can be changed between heat conductivility and capability of electromagnetic shielding first Film, and its function conversion method is elaborated, the graphene film that the graphene film is more than 100 μm by the average-size of planar orientation leads to The pi-conjugated effects of π mutually overlap joint is crossed to form.Big conjugated structure ensure that the unimpeded of the path between graphene, and 1-4 layer graphenes The introducing for the graphene-structured that piece is constituted, is greatly improved the electric conductivity of material;In non-lap-joint, graphene film and piece it Between form cavity, when injecting gas in cavity, form the micro- air bag of graphene, micro- airbag structure auxiliary is with preferable electric conductivity Can so that graphene film of the invention has extremely strong capability of electromagnetic shielding.Micro- air bag is compressed when using condition of high voltage, Form fold so that the deformation of graphene film is remembered, and assigns the flexibility and heat conductivility of its superelevation.One exhales general between a suction A variety of functions of graphene are changed, the new thinking that the design to future device is provided, and are also expanded for the application of graphene film The space of exhibition.
By the present invention in that with super large piece graphene oxide film forming, and allow under the mode that it anneals at high temperature, perfection is repaiied Multiple graphene defect, and edge defect is preferably minimized, perfect big conjugated structure is formed, it is conjugated size and even extended to The graphene of full wafer, it is ensured that graphene thermal conducting path it is unimpeded;Further pass through the temperature-rise period of three step independences so that stone The functional group on black alkene surface is gradually disengaged, and the auxiliary agent (perforating agent) being mixed between graphene film is slowly decomposed, and both of which is with gas Body form discharges step by step, meanwhile, graphitizing process stepwise development forms the micro- air bag of graphene;And in the forming process of micro- air bag, Graphenic surface the most stable functional group also comes off therewith, adds gas expansion under high temperature, thereby produces and be successfully introduced into The graphene-structured that 1-4 layer graphenes piece is constituted.
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 that can breathe graphene film respiratory electromicroscopic photograph.
Fig. 6 is that can breathe graphene film respiratory sectional view.
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 constituted, the present invention washes it in graphite oxide crystal Before, the method separated using mesh screen is gone out chip separation.And using 10 times 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.Washing is further shaken using shaking table so that graphene oxide layer is in stripping 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 breadth coefficient is between 0.2-0.5, and shive content is less than 1%.
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, after after abundant dissolving, added at -10 DEG C Graphite, 60 revs/min are slowly stirred stopping stirring after 2h, and 6h is reacted respectively at 20 DEG C, 50 DEG C, respectively obtain the oxygen of wide distribution Graphite crystal;As shown in figure 1, there is more fragment 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 filters out to the titanium alloy mesh screen of 150um apertures (140 mesh) (reaction solution is returned Receive), and be poured slowly into the frozen water relative to 10 times of volumes of filtration product quickly stirred, 2h is stood, H is slowly added to2O2, with Except potassium permanganate unnecessary in dereaction, the appropriate hydrochloric acid of addition disappears until cotton-shaped graphite oxide, then uses 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, and 0.5) breadth coefficient is.Graphite, potassium permanganate and concentrated sulfuric acid mass volume ratio are:1g:2g:40ml, graphite Granularity is 200um.
As shown in figure 3, washing obtained oxidation stone 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 Distribution more uniform concentration, shive content is few.
Embodiment 1-2
Potassium permanganate is slowly added at -10 DEG C in the concentrated sulfuric acid quickly stirred, after 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%, mass fraction for 10% dilute sulfuric acid, 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 production In the frozen water of 10 times of volumes of thing, 2h is stood, H is slowly added to2O2, except potassium permanganate unnecessary in dereaction, to add appropriate salt Acid disappears until cotton-shaped graphite oxide, then filters out graphite oxide chip with titanium alloy reticulated is sieved;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, (average-size is 98um to the graphene oxide without fragment super large piece that reaction is obtained, distribution 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 after abundant dissolving, adds stone Ink, 60 revs/min are slowly stirred stopping stirring after 2h, and 28h is reacted under low temperature (20 DEG C), and the graphite oxide for obtaining wide distribution is brilliant Body;Reaction solution with diluting concentrated sulfuric acid and is filtered out into (reaction solution with the titanium alloy mesh screen in 150um apertures by graphite oxide crystal Reclaim), and be poured slowly into respectively quickly stir relative in 5 times of volumes of filtration product, 8 times of volumes, the frozen water of 10 times of volumes, 2h is stood, H is slowly added to2O2, except potassium permanganate unnecessary in dereaction, to add appropriate hydrochloric acid until cotton-shaped graphite oxide Disappear, then graphite oxide chip is filtered out with titanium alloy reticulated is sieved;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 the graphene film for obtaining size uniformity, The graphene oxide of no fragment super large piece can be just obtained under 10 times of volumes, and (average-size is 92um, and breadth coefficient is 0.2).Thus Understand, the amount of frozen water is too low, the heat of mixing will be caused to concentrate release, destroy crystal structure.
Embodiment 2:The graphene oxide without fragment super large piece prepared using embodiment 1 prepares respirable graphite Alkene film.
The graphene oxide that average-size is more than 100um is configured to concentration for 30mg/mL graphene oxide water solutions, The urea of mass fraction 5% is added in solution, is poured on after ultrasonic disperse on Die and mould plate and is dried into graphene oxide membrane, Ran Houyong Hydrogen iodide reducing agent is reduced;Graphene film after reduction under atmosphere of inert gases according to the heat shown in 1~table of table 3 at Reason mode carries out three step heat treatments;The porous graphene film that thickness is 1mm is can obtain after Temperature fall.By graphene film Compacting can obtain super flexible high heat conduction graphene film under high pressure.Described pressing process pressure is 200MP, and the time is 300h.
The graphene film of above-mentioned gained is suppressed into 2h under 50MP high pressure;Measure its thermal conductivity;By the graphite after compacting Alkene film soaks 300s in the liquid nitrogen of boiling, measures its capability of electromagnetic shielding, as shown in table 1-3.
Table 1:The heat treatment mode of the first step
Table 2:The heat treatment mode of second step
Table 3:The heat treatment mode of 3rd step
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, is not enough to removing most of degradable Functional group, cause gas in second step pyroprocess largely quickly to produce, lamellar structure torn 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 formation 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, the complete of passage is can guarantee that again.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, 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, Jiao is avoided that again 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, the formation that micro- air bag could be stablized, graphene On structure could slowly repair.Compare C3, F3, G3, H3, I3, F3 outlet temperatures are too low, 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 3:The graphene oxide without fragment super large piece prepared using embodiment 1 prepares respirable graphite Alkene film.
The preparation method of graphene film can be breathed, it is characterised in that step is as follows:Average-size is more than to 100um oxygen Graphite alkene is configured to concentration for 6mg/mL graphene oxide water solutions, and the method film forming of film is spun with knifing or solution, natural Film forming is dried, and is reduced with reducing agent;Graphene film after reduction is first progressively heated up 500 DEG C under atmosphere of inert gases, It is incubated 0.5h;1000 DEG C are progressively warming up under atmosphere of inert gases, 0.5h is incubated;Progressively it is warming up under atmosphere of inert gases 2500 DEG C, graphene film can be breathed by being incubated to can obtain after 0.5-4h, Temperature fall.Described reducing agent is hydrazine hydrate.Institute Heating rate is 0.1 DEG C/min at 500 DEG C stated, and heating rate is 1.3 DEG C/min at 1000 DEG C, and less than 2500 DEG C, heating is fast 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 is more than to 100um oxygen Graphite alkene is configured to concentration for 10mg/mL graphene oxide water solutions, and the method film forming of film is spun with knifing or solution, natural Film forming is dried, and is reduced with reducing agent;Graphene film after reduction is first progressively heated up 500 DEG C under atmosphere of inert gases, It is incubated 2h;1300 DEG C are progressively warming up under atmosphere of inert gases, 3h is incubated;3000 are progressively warming up under atmosphere of inert gases DEG C, graphene film can be breathed by being incubated to can obtain after 4h, Temperature fall.Described reducing agent is ascorbic acid.Described 500 Heating rate is 0.1 DEG C/min at DEG C, and heating rate is 1 DEG C/min at 1300 DEG C, less than 3000 DEG C, heating rate for 5 DEG C/ min。
By accompanying drawing:
Fig. 5, graphene film respiratory electromicroscopic photograph can be breathed, during exhaling under external force, graphene film It is driven plain, breathing stomata is remained by the form of fold;During being inhaled under gas effect, fold is strutted by gas, Gradually become smooth.
Fig. 6, graphene film respiratory sectional view can be breathed, during exhaling under external force, graphene film quilt Flatten, its structure becomes closely knit;During being inhaled under gas effect, fold is strutted by gas, and 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 is more than to 100um oxygen Graphite alkene is configured to concentration for 6mg/mL graphene oxide water solutions, and the method film forming of film is spun with knifing or solution, natural Film forming is dried, and is reduced with reducing agent;Graphene film after reduction is first progressively heated up 800 DEG C under atmosphere of inert gases, It is incubated 0.5h;1100 DEG C are progressively warming up under atmosphere of inert gases, 3h is incubated;Progressively it is warming up under atmosphere of inert gases 2500 DEG C, graphene film can be breathed by being incubated to can obtain after 4h, Temperature fall.Described reducing agent is hydrogen iodide.Described Heating rate is 0.1 DEG C/min at 800 DEG C, and heating rate is 2 DEG C/min at 1100 DEG C, and less than 2500 DEG C, heating rate is 6 ℃/min。
Embodiment 6:
The preparation method of graphene film can be breathed, it is characterised in that step is as follows:Average-size is more than to 100um oxygen Graphite alkene is configured to concentration for 12mg/mL graphene oxide water solutions, and the method film forming of film is spun with knifing or solution, natural Film forming is dried, and is reduced with reducing agent;Graphene film after reduction is first progressively heated up 500 DEG C under atmosphere of inert gases, It is incubated 1h;1000 DEG C are progressively warming up under atmosphere of inert gases, 1h is incubated;3000 are progressively warming up under atmosphere of inert gases DEG C, graphene film can be breathed by being incubated to can obtain after 0.5-4h, Temperature fall.Described reducing agent comprising hydrazine hydrate, amine, Ascorbic acid, hydrogen iodide.Heating rate is 0.4 DEG C/min at described 500 DEG C, and heating rate is 1 DEG C/min at 1000 DEG C, Less than 3000 DEG C, 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 is more than to 100um oxygen Graphite alkene is configured to concentration for 10mg/mL graphene oxide water solutions, and the method film forming of film is spun with knifing or solution, natural Film forming is dried, and is reduced with reducing agent;Graphene film after reduction is first progressively heated up 800 DEG C under atmosphere of inert gases, It is incubated 2h;1300 DEG C are progressively warming up under atmosphere of inert gases, 0.5-3h is incubated;Progressively it is warming up under atmosphere of inert gases 3000 DEG C, graphene film can be breathed by being incubated to can obtain after 2h, Temperature fall.Described reducing agent comprising hydrazine hydrate, amine, Ascorbic acid, hydrogen iodide.Heating rate is 1 DEG C/min at described 800 DEG C, and heating rate is 1 DEG C/min, 3000 at 1300 DEG C Below DEG C, 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 is more than to 100um oxygen Graphite alkene is configured to concentration for 20mg/mL graphene oxide water solutions, and the method film forming of film is spun with knifing or solution, natural Film forming is dried, and is reduced with reducing agent;Graphene film after reduction is first progressively heated up 500 DEG C under atmosphere of inert gases, It is incubated 2h;1300 DEG C are progressively warming up under atmosphere of inert gases, 0.5h is incubated;Progressively it is warming up under atmosphere of inert gases 2500 DEG C, graphene film can be breathed by being incubated to can obtain after 1h, Temperature fall.Described reducing agent comprising hydrazine hydrate, amine, Ascorbic acid, hydrogen iodide.Heating rate is 0.4 DEG C/min at described 500 DEG C, and heating rate is 1 DEG C/min at 1300 DEG C, Less than 2500 DEG C, heating rate is 5.8 DEG C/min.

Claims (10)

1. a kind of function conversion method for breathing graphene film, it is characterised in that, the power and energy be in heat conductivility and Changed between capability of electromagnetic shielding;The capability of electromagnetic shielding is to the conversion regime of heat conductivility:There to be electromagnetic wave shielding The graphene film that breathes of energy suppresses 5min-2 h under 50-200MPa high pressure;The heat conductivility is to capability of electromagnetic shielding The mode of conversion is:The graphene film that breathes with heat conductivility is soaked into 1-1000s in the breathing agent of boiling;It is described to exhale Vapor is 2,3- dimethyl -1- butylene, 1,2- dichloroethylene(It is suitable), 1,2- dichloroethylene(Instead), 1,5- hexadienes, 3- methyl- 1- amylenes, 4-methyl-1-pentene, 4- methyl -2- amylenes(It is suitable), 4- methyl -2- amylenes(Instead), the chloro- 1,3- butadiene of 2-, iodine second Alkene, n-propylamine, diethylamine, ether, acetone, dichloromethane, ethanol, ethyl acetate, liquid nitrogen, water, petroleum ether, n-hexane;It is described Graphene film can be breathed the pi-conjugated effects of π mutually overlap joint is passed through by graphene film of the average-size more than 100 μm of planar orientation Form;Wherein comprising the graphene-structured being made up of 1-4 layer graphene pieces;And the defect of graphene film is few, its ID/IG< 0.01。
2. the function conversion method according to claim 1 for breathing graphene film, it is characterised in that, it is described to breathe stone The thickness of black alkene film is 1mm, and breathing agent is liquid nitrogen, soaks 300 ~ 400s.
3. the function conversion method according to claim 1 for breathing graphene film, it is characterised in that, it is described to breathe stone The thickness of black alkene film is 5mm, and breathing agent is water, soaks 800 ~ 1000s.
4. the function conversion method according to claim 1 for breathing graphene film, it is characterised in that, it is described to breathe stone The thickness of black alkene film is 0.1mm, and breathing agent is acetone, soaks 10 ~ 20s.
5. the function conversion method according to claim 1 for breathing graphene film, it is characterised in that, it is described to breathe stone The preparation method of black alkene film is as follows:
(1)The graphene oxide that average-size is more than 100 μm is configured to concentration for 6 ~ 30mg/mL graphene oxide water solutions, Mass fraction 0.1-5% auxiliary agent is added in the solution, and the auxiliary agent is inorganic salts, organic molecule or macromolecule;Ultrasonic disperse Afterwards, it is poured on Die and mould plate and is dried into graphene oxide membrane, 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 500-800 oC, is incubated 0.5-2h;
(3)With 1-3 under atmosphere of inert gasesoC/min speed is warming up to 1000-1300oC, is incubated 0.5-3h;
(4)With 5-8 under atmosphere of inert gasesoC/min speed is warming up to 2500-3000oC, is incubated 0.5-4h, Temperature fall It can obtain afterwards and porous breathe graphene film.
6. the function conversion method according to claim 5 for breathing graphene film, it is characterised in that described inorganic salts Selected from ammonium hydrogen carbonate, urea, thiocarbamide, azodicarbonamide;Organic molecule is selected from glycerine, polyethylene glycol 200, polyethylene glycol 400;Macromolecule is selected from cellulose, gelatin, chitosan, aqueous polyurethane, acrylic emulsion.
7. the function conversion method according to claim 5 for breathing graphene film, it is characterised in that, in the step 1 The graphene oxide that average-size is more than 100 um is obtained by the following method:
(1)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;
(2)The filtration product that step 1 is obtained is in frozen water according to volume ratio 1:After 10 is well mixed, 2h is stood, is added dropwise double Oxygen water, until the color of mixed liquor no longer changes;
(3)Concentrated hydrochloric acid is added dropwise in mixed liquor after being handled to step 2, until cotton-shaped graphite oxide disappearance, then 140 mesh are used Screen filtration go out graphite oxide chip;
(4)The graphite oxide chip that step 3 is obtained is placed in shaking table, 20 ~ 80 turns/min, concussion washing so that graphite oxide Chip is peeled off, and obtains the graphene oxide of no fragment super large piece, and average-size is more than 87 um, breadth coefficient 0.2-0.5 it Between.
8. method according to claim 7, it is characterised in that the Modified-Hummer methods in the step 1 are 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 Mix and stop stirring after 2h, in -10-20o6-48h is reacted in a low temperature of C, the oxidized graphite flake reaction solution of wide distribution is obtained;It is described Graphite, potassium permanganate and concentrated sulfuric acid mass volume ratio be:1 g:2-4g:30-40ml, the granularity of graphite is more than 150 μm.
9. method according to claim 7, it is characterised in that the mesh screen is acidproof mesh screen.
10. method according to claim 7, it is characterised in that in the step 1, the reaction solution of oxidized graphite flake passes through The concentrated sulfuric acid is diluted, and the volume of diluent is 1-10 times of reaction solution volume.
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