CN106185893A - A kind of breathe graphene film detection light stability in application - Google Patents
A kind of breathe graphene film detection light stability in application Download PDFInfo
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- CN106185893A CN106185893A CN201610523338.4A CN201610523338A CN106185893A CN 106185893 A CN106185893 A CN 106185893A CN 201610523338 A CN201610523338 A CN 201610523338A CN 106185893 A CN106185893 A CN 106185893A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 105
- 238000001514 detection method Methods 0.000 title claims abstract description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 52
- 239000010439 graphite Substances 0.000 claims description 52
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 23
- 239000012286 potassium permanganate Substances 0.000 claims description 15
- 239000000376 reactant Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 235000011149 sulphuric acid Nutrition 0.000 claims description 14
- 239000012634 fragment Substances 0.000 claims description 13
- 239000001117 sulphuric acid Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000004575 stone Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 229920002521 macromolecule Polymers 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 230000029058 respiratory gaseous exchange Effects 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 3
- 235000013877 carbamide Nutrition 0.000 claims description 3
- 230000009514 concussion Effects 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 239000004156 Azodicarbonamide Substances 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 2
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 238000009288 screen filtration Methods 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims 1
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims 1
- 238000005286 illumination Methods 0.000 abstract description 9
- 239000010408 film Substances 0.000 description 53
- 239000000463 material Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 241000446313 Lamella Species 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000003019 stabilising effect Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920006266 Vinyl film Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- -1 graphite Alkene Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J1/00—Photometry, e.g. photographic exposure meter
- G01J1/42—Photometry, e.g. photographic exposure meter using electric radiation detectors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Electromagnetism (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of breathe graphene film detection light stability in application, the capability of electromagnetic shielding that described application can breathe graphene film by detection realizes, the capability of electromagnetic shielding data that can breathe graphene film are the most unstable, and light stability is the lowest.Having the graphene film breathed of heat conductivility (1,800 2600 W/mK) to be rapidly heated under light illumination expansion, shield effectiveness improves.The high-sensitivity detection to light stability can be realized by this graphene film.
Description
Technical field
The present invention relates to Novel heat-conducting, inhale ripple and the application of electromagnetic shielding material, particularly relate to one and can breathe graphite
The application in detection light stability of the alkene film.
Background technology
2010, two of Univ Manchester UK professor Andre GeiM and Konstantin Novoselov because
It is successfully separated out stable Graphene first and obtains Nobel Prize in physics, start the upsurge that Graphene is studied by the whole world.
Graphene has excellent electric property, and (under room temperature, electron mobility is up to 2 × 105cM2/ Vs), prominent heat conductivility (5000W/
(MK), extraordinary specific surface area (2630M2/ g), its Young's modulus (1100GPa) and fracture strength (125GPa).Graphene is excellent
Different electrical and thermal conductivity performance is well beyond metal, and Graphene has an advantage of corrosion-and high-temp-resistant simultaneously, and its good machinery
Performance and relatively low density more allow it possess the potentiality at thermo electric material field substituted metal.
Macroscopic view assembles the main application that the graphene film of graphene oxide or graphene nanometer sheet is nanoscale graphite alkene
Form.By further high-temperature process, it is possible to repair the defect of Graphene, it is possible to the effective electric conductivity improving graphene film
And thermal conductance, can be widely applied to smart mobile phone, intelligence hardware, panel computer, the contour radiating requirements of notebook computer with oneself
In accompanied electronic equipment.
The application of graphene film at present is limited to independent functional material, such as heat conducting film, conducting film, suction ripple film, screen
Cover film.Single function substantially can not meet the demand that future technology progress is complicated.To this end, we utilize super large sheet without fragment stone
Ink alkene does substrate and devises and can breathe graphene film, one exhale complete between a suction heat-conductivity conducting and inhale wave screen cover between the turning of function
Change.The new thinking provided for the design of multifunction device.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that one can breathe graphene film at detection stabilized intensity
Application in property.
It is an object of the invention to be achieved through the following technical solutions: one can breathe graphene film at detection stabilized intensity
Application in property, the capability of electromagnetic shielding that described application can breathe graphene film by detection realizes, and can breathe graphene film
Capability of electromagnetic shielding data the most unstable, light stability is the lowest.Described breathe average by planar orientation of graphene film
Size is mutually overlapped more than the graphene film of 100 μm formed by the pi-conjugated effect of π.Wherein comprise and be made up of 1-4 layer graphene sheet
Graphene-structured.And the defect of graphene film is few, its ID/TG＜ 0.01.
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 graphene oxide water
Solution, adds the auxiliary agent (i.e. auxiliary agent mass fraction in the solution is 0.1-5%) of mass fraction 0.1-5%, institute in the solution
Stating auxiliary agent is inorganic salt, organic molecule or macromolecule；After ultrasonic disperse, it is poured on Die and mould plate and is dried into graphene oxide membrane,
Then reduce with reducing agent；
(2) graphene film after reduction is first arrived with the ramp of 0.1-0.5 DEG C/min under atmosphere of inert gases
500-700 DEG C, it is incubated 0.5-2h；
(3) with the ramp to 1000-1200 DEG C of 1-3 DEG C/min under atmosphere of inert gases, it is incubated 0.5-3h；
(4) with the ramp to 2500-3000 DEG C of 5-8 DEG C/min under atmosphere of inert gases, it is incubated 0.5-4h, natural
The graphene film breathed of porous is i.e. can get after cooling.
Described inorganic salt is selected from ammonium hydrogen carbonate, carbamide, thiourea, azodicarbonamide；Organic molecule is selected from glycerol, gathers
Ethylene glycol 200, PEG400；Macromolecule is selected from cellulose, gelatin, chitosan, aqueous polyurethane, acrylic emulsion etc..
In described step 1, the average-size graphene oxide more than 100um obtains by the following method:
(1), after the reactant liquor dilution of oxidized graphite flake Modified-Hummer method obtained, the mesh screen in 140 mesh enters
Row filters, and obtains filtration product；
(2) filtration product step 1 obtained is after frozen water is according to volume ratio 1:10 mix homogeneously, stands 2h, dropwise adds
Enter hydrogen peroxide (H2O2Mass fraction be 30%), until the color of mixed liquor no longer changes, (i.e. the potassium permanganate in mixed liquor is
Remove completely)；
(3) mixed liquor after step 2 processes is added dropwise over concentrated hydrochloric acid (concentration is 12mol/L), until cotton-shaped oxygen
Graphite disappears, then goes out graphite oxide wafer with the screen filtration of 140 mesh；
(4) graphite oxide wafer step 3 obtained is placed in shaking table, 20～80 turns/min, concussion washing so that oxidation
Graphite wafer is peeled off, and obtains the graphene oxide without fragment super large sheet, and average-size is more than 100um, and breadth coefficient is at 0.2-0.5
Between.
Modified-Hummer method in described step 1 is particularly as follows: at-10 DEG C, be completely dissolved in matter by potassium permanganate
Amount mark is in the concentrated sulphuric acid of 98%, adds graphite, stops stirring, under low temperature (-10-20 DEG C) after 60 revs/min of stirring 2h
Reaction 6-48h, obtains the oxidized graphite flake reactant liquor of wide distribution；Described graphite, potassium permanganate and concentrated sulphuric acid mass volume ratio
For: 1g:2-4g:30-40ml, the granularity of graphite is more than 150 μm.
Described mesh screen is the acidproof mesh screens such as titanium alloy.
In described step 1, the reactant liquor of oxidized graphite flake is diluted by diluent such as concentrated sulphuric acids, the volume of diluent
For reactant liquor volume 1-10 times.
Disclosure sets forth a kind of multifunctional graphite vinyl film can changed between heat conductivility and capability of electromagnetic shielding
New opplication, and this graphene film is mutual by the pi-conjugated effect of π more than the graphene film of 100 μm by the average-size of planar orientation
Overlap joint forms.Big conjugated structure ensure that the unimpeded of the path between Graphene, and the Graphene knot that 1-4 layer graphene sheet is constituted
The introducing of structure, is greatly improved the electric conductivity of material；In non-lap-joint, form cavity between graphene film and sheet, work as stone
Ink alkene film is placed under the illumination of high intensity, by Graphene quick conductive so that its intracavity gas is rapidly heated expansion, the opposing party
Face, under high temperature, fold itself has the trend unfolded, and meanwhile, under gas expansion effect, the fold of cavity wall is strutted by gas, by
Gradual change obtains smooth；Big cavity, smooth cavity wall assist with preferable electric conductivity so that it is film has extremely strong capability of electromagnetic shielding.
Intensity of illumination is the highest, and capability of electromagnetic shielding is the best.When needs reuse, condition of high voltage is used to be compressed i.e. by micro-air bag
Can.
Accompanying drawing explanation
Fig. 1 is the graphite oxide crystal (left) before filtering, the graphite oxide crystal (right) after filtration.
Fig. 2 is the graphene oxide (left) before filtering, the graphene oxide (right) after filtration.
Fig. 3 is to react the graphene oxide obtained under 50 degree.
Fig. 4 is to react the graphene oxide distribution of sizes (left) obtained under 50 degree, and 20 degree are reacted the graphite oxide obtained down
Alkene distribution of sizes (right).
Fig. 5 exhales for breathing graphene film and inhales state lower section figure.
Fig. 6 is the electromagnetic shielding curve chart under different capacity illumination.
Detailed description of the invention
By the present invention in that and use super large sheet graphene oxide film forming, wherein the average-size of planar orientation is more than 100 μm
Graphene film is important role during constituting graphene film of the present invention, and the present invention washes it at graphite oxide crystal
Before, the way using mesh screen to separate, chip separation is gone out.And using 10 times to be diluted with the frozen water of upper volume so that it is brilliant
Sheet will not be destroyed because of the heat of solution of sulphuric acid.Use shaking table concussion washing further so that graphene oxide lamella is in stripping
From when avoid the broken of mechanical force.Further, the present invention prepares graphene film also by cryogenic conditions, at low temperature
Under, potassium permanganate oxidation is more weak, and the speed that its selfdecomposition produces oxygen is slow, and therefore gas is to graphite oxide crystal
Fragmentation is the most weak so that the graphene oxide of big lamella is preserved.And course of reaction and cleaning process do not have
Violent stirring and ultrasonic procedure, therefore lamella there is no broken.The most what time, we have obtained the nothing of super large sheet
The graphene oxide of fragment, average-size is more than 87um, and breadth coefficient is between 0.2-0.5, and shive content is less than 1%.
Below in conjunction with the accompanying drawings and embodiment the invention will be further described.The present embodiment be served only for the present invention is done into
The explanation of one step, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according in foregoing invention
Hold and make some nonessential change and adjustment, belong to protection scope of the present invention.
Embodiment 1: without the preparation of the graphene oxide of fragment super large sheet
Embodiment 1-1
(1) at-10 DEG C, potassium permanganate is slowly added in the concentrated sulphuric acid of quickly agitation, after fully dissolving, adds
Graphite, 60 revs/min are slowly stirred after 2h and stop stirring, 20 DEG C, react 6h respectively at 50 DEG C, respectively obtain the oxygen of wide distribution
Graphite crystal；As it is shown in figure 1, all there is more fragment in the graphite oxide wafer obtained at a temperature of two kinds, this makes it
Corresponding graphene oxide has a lot of fragments (Fig. 2) equally.
(2) (extension rate can be any multiple to reactant liquor diluting concentrated sulfuric acid step 1 obtained, and the present embodiment is dilute
Release about 10 times), and with the titanium alloy mesh screen of 150um aperture (140 mesh) graphite oxide crystal filtered out (reactant liquor returns
Receive), and be poured slowly in the frozen water relative to 10 times of volumes of filtration product of quickly stirring, stand 2h, be slowly added to H2O2, with
Remove potassium permanganate unnecessary in reaction, add appropriate hydrochloric acid until cotton-shaped graphite oxide disappears, then use titanium alloy mesh screen
(140 mesh) filters out graphite oxide wafer；Shaking table slowly shakes washing, obtains the graphene oxide without fragment super large sheet (average
A size of 87um, breadth coefficient is 0.5).Graphite, potassium permanganate with concentrated sulphuric acid mass volume ratio is: 1g:2g:40ml, graphite
Granularity is 200um.
As it is shown on figure 3, isolated graphite oxide wafer washs, after separating, the oxidation stone obtained after the lower reaction of high temperature 50 degree
Ink alkene has a lot of fragments equally；From fig. 4, it can be seen that large stretch of graphene oxide size after (20 DEG C) Reaction Separation under low temperature
Being distributed more uniform concentration, shive content is few.
Embodiment 1-2
At-10 DEG C, potassium permanganate is slowly added in the concentrated sulphuric acid of quickly agitation, after fully dissolving, adds stone
Ink, 60 revs/min are slowly stirred stopping stirring after 2h, react 48h, obtain reactant liquor under low temperature (0 DEG C)；Reactant liquor is divided
It is not diluted with the dilute sulfuric acid that the concentrated sulphuric acid of mass fraction more than 98%, mass fraction are 10%, then with 150um aperture
Graphite oxide crystal is filtered out (reactant liquor recovery) by titanium alloy mesh screen, and is poured slowly into producing relative to filtering of quickly stirring
In the frozen water of 10 times of volumes of thing, stand 2h, be slowly added to H2O2, to remove potassium permanganate unnecessary in reaction, add appropriate salt
Acid is until cotton-shaped graphite oxide disappears, then leaches graphite oxide wafer with titanium alloy reticulated is sieved；Shaking table slowly shakes washing, obtains
Product.Graphite, potassium permanganate with concentrated sulphuric acid mass volume ratio is: 1:4g:30ml；The granularity of graphite is 500um.
Using diluting concentrated sulfuric acid, (average-size is 98um to the graphene oxide of the sheet of super large without fragment that reaction obtains, distribution
Coefficient is 0.4), and dilute with dilute sulfuric acid, containing a large amount of fragments in the product obtained, distribution of sizes coefficient is more than 100%.This is
Due in dilute sulfuric acid dilution, highly exothermic, destroy graphite oxide crystal.
Embodiment 1-3
At-10 DEG C, potassium permanganate is slowly added in the concentrated sulphuric acid of quickly agitation, after fully dissolving, adds stone
Ink, 60 revs/min are slowly stirred stopping stirring after 2h, react 28h under low temperature (20 DEG C), obtain the graphite oxide crystalline substance of wide distribution
Body；By reactant liquor diluting concentrated sulfuric acid and with the titanium alloy mesh screen in 150um aperture, graphite oxide crystal is filtered out (reactant liquor
Reclaim), and be poured slowly into respectively quickly stirring relative to 5 times of volumes of filtration product, 8 times of volumes, 10 times of volumes frozen water in,
Stand 2h, be slowly added to H2O2, to remove potassium permanganate unnecessary in reaction, add appropriate hydrochloric acid until cotton-shaped graphite oxide
Disappear, then leach graphite oxide wafer with titanium alloy reticulated is sieved；Shaking table slowly shakes washing, obtains product；Graphite, Gao Meng
Acid potassium with concentrated sulphuric acid mass volume ratio is: 1:5g:34ml, the granularity of graphite is 2mm.
Experimental result shows, the frozen water of 5 times of volumes and 8 times of volumes all can not the graphene film obtaining size uniformity,
Graphene oxide without fragment super large sheet (average-size is 92um, breadth coefficient 0.2) just can be obtained under 10 times of volumes.Thus
Understanding, the amount of frozen water is too low, the heat of mixing will be made to concentrate release, destroy crystal structure.
Embodiment 2: the graphene oxide of the sheet of super large without fragment that employing embodiment 1 prepares prepares respirable graphite
Alkene film.
The average-size graphene oxide more than 100um is configured to concentration is 28mg/mL graphene oxide water solution,
Solution adds mass fraction 5.4% carbamide, is poured on after ultrasonic disperse on Die and mould plate and is dried into graphene oxide membrane, then
Reduce with hydrogen iodide reducing agent；Graphene film after reduction under atmosphere of inert gases according to the heat shown in table 1～table 3
Processing mode carries out three step heat treatments；The porous graphene thin film that thickness is 1mm is i.e. can get after Temperature fall.Graphene is thin
Film under high pressure suppresses to obtain super flexibility 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；By the graphite after compacting
Alkene film, in being placed in the environment of 400 degree, records its capability of electromagnetic shielding, prepares high thermal conductivity and highly sensitive graphite with acquisition
The parameter of alkene film；As shown in table 1-3.Fig. 5 for graphene film respiratory electromicroscopic photograph can be breathed, exhaling under external force
During, graphene film is driven plain, and breathes pore and is remained by the form of fold；The process inhaled under light pyrogenic action
In, fold is strutted by gas, gradually becomes smooth.
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 graphite oxide
Alkene chip architecture repairs coming off and the reparation of carbon conjugated structure under high temperature of situation, i.e. functional group.Its two, material internal three-dimensional takes
To the seriality of structure, the i.e. connectivity of internal sheets Rotating fields.Its three, micro-air bag formed guarantee material flexibility and
The existence of graphene film Rotating fields.Three acts on increasing the performance of graphene film jointly.
As it can be seen from table 1 compare A1, B1, C1, D1, E1, the temperature of A1 is too low, is not enough to remove major part degradable
Functional group, cause gas in second step pyroprocess the most quickly to produce, at high temperature tearing sheet Rotating fields；E1 temperature mistake
Height, produces gas too fast, can tear material internal structure in a large number, both can make deterioration in material properties.Have only B1, C1,
At a temperature of D1, functional group can slowly and thoroughly remove, to ensure material property.Relatively C1, F1, G1, H1, F1 heating rate mistake
Low, gas release is the slowest, it is impossible to makes material internal form through hole, is unfavorable for micro-air bag in ensuing temperature-rise period
Formation；H1 temperature-rise period is too fast, and gas release is too fast, tears material internal structure, is unfavorable for forming transmission channel.Have CG only
Just can both ensure the formation of micro-air bag under heating rate, can guarantee that again the complete of passage.Relatively C1, I1, J1, K1, L1, M1,
I1 temperature retention time is too short, it is impossible to ensure the degraded of major part functional group；M1 insulating process is long, can absorb Jiao inside stove
Oil, is unfavorable for the lifting of performance.C1, J1, K1, L1 just avoid both.
From Table 2, it can be seen that compare A2, B2, C2, D2, E2, too low being not enough to of A2 heating rate forms small space
Structure so that film can not form micro-air bag, has a strong impact on capability of electromagnetic shielding.E2 programming rate is too high, can tear graphene layer
Between structure so that graphene film link property be deteriorated, heat conduction capability of electromagnetic shielding is all deteriorated.Have the programming rate of B2, C2, D2 only
Under, just capable not only can ensure micro-airbag structure but also ensure the seriality within graphene film.Relatively C2, I2, J2, K2, L2,
M2, I2 temperature retention time is too short, and stable functional group can not fully come off；M2 overlong time, the easy tar adsorption of graphene film, no
It is beneficial to the lifting of film properties；And under the conditions of C2, J2, K2, M2, both can ensure that fully coming off of stabilising functional group, it is avoided that again Jiao
The puzzlement of oil.
From table 3 it is observed that compare A3, B3, C3, D3, E, A3 heating rate is too low, the mistake that stabilising functional group comes off
Slowly, it is not enough to support the formation of micro-air bag during forming micro-air bag；E3 temperature-rise period is too fast, and gas release and high temperature are swollen
Swollen too fast, it is easily destroyed the formation of micro-air bag.Only in the case of B3, C3, D3, the formation that micro-air bag could be stable, Graphene
On structure could repair slowly.Relatively C3, F3, G3, H3, I3, F3 outlet temperature is too low, and graphene-structured is repaired the completeest
It is kind, so various performance is the most very poor；I3 outlet temperature is too high, and Graphene can be vaporized；Could both at a temperature of C3, G3, H3
Ensure the reparation of graphene-structured, will not be vaporized again.Relatively C3, J3, K3, L3, M3, J3 temperature retention time is too low, Graphene
Structure can not fully be repaired, and M3 temperature retention time is long, also can make to adsorb the tar in body of heater, affect the performance of film.
Embodiment 3: be used for detecting light intensity by graphene film.
First, can to breathe graphene film as follows in preparation
(1) more than the graphene oxide of 100 μm, average-size being configured to concentration is 6mg/mL graphene oxide water solution,
Add the glycerol of mass fraction 5% in the solution；After ultrasonic disperse, it is poured on Die and mould plate and is dried into graphene oxide membrane, then
Reduce with reducing agent；
(2) by the graphene film after reduction under atmosphere of inert gases first with the ramp of 0.5 DEG C/min to 700
DEG C, it is incubated 1h；
(3) with the ramp to 1200 DEG C of 2 DEG C/min under atmosphere of inert gases, it is incubated 1h；
(4) with the ramp to 2500 DEG C of 7 DEG C/min under atmosphere of inert gases, it is incubated 1h, after Temperature fall
Obtain the graphene film breathed of porous.
Then, the graphene film prepared is respectively placed in dark situation I～VII, respectively with same in each dark situation
The laser instrument of series carries out illumination, and the laser power in dark situation I～VII is as shown in the table.
| I | II | III | IV | V | VI | VII |
| 5× 103lux | 80×103lux | 150× 103lux | 220× 103lux | 300× 103lux | 400× 103lux | 500× 103lux |
Illumination 10min, the electromagnetic shielding data recorded are as shown in Figure 6.
As can be seen from Figure 6, graphene film has the thermal conductivity of superelevation, substantially completes heat conduction work, sensitivity in 1 minute
High.Additionally, the graphene film capability of electromagnetic shielding size discrimination under different capacity illumination is obvious, explanation can differentiate different illumination ring
Border, intensity of illumination is the biggest, and capability of electromagnetic shielding is the biggest.Therefore, light stability can be carried out efficient evaluations.
Claims (7)
1. can breathe graphene film application in detection light stability for one kind, it is characterised in that described application is by detection
The capability of electromagnetic shielding that can breathe graphene film realizes, and the capability of electromagnetic shielding data that can breathe graphene film are the most unstable,
Light stability is the lowest；Described graphene film of breathing is passed through π by the average-size of planar orientation more than the graphene film of 100 μm
Pi-conjugated effect mutually overlaps and forms；Wherein comprise the graphene-structured being made up of 1-4 layer graphene sheet；And graphene film lack
Fall into few, its ID/TG＜ 0.01.
Application the most according to claim 1, it is characterised in that, 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 graphene oxide water solution,
Adding the auxiliary agent (i.e. auxiliary agent mass fraction in the solution is 0.1-5%) of mass fraction 0.1-5% in the solution, described auxiliary agent is
Inorganic salt, organic molecule or macromolecule；After ultrasonic disperse, it is poured on Die and mould plate and is dried into graphene oxide membrane, then with also
Former dose is reduced；
(2) graphene film after reducing is first with 0.1-0.5 under atmosphere of inert gasesoThe ramp of C/min is to 500-
700oC, is incubated 0.5-2h；
(3) with 1-3 under atmosphere of inert gasesoThe ramp of C/min is to 1000-1200oC, is incubated 0.5-3h；
(4) with 5-8 under atmosphere of inert gasesoThe ramp of C/min is to 2500-3000oC, is incubated 0.5-4h, Temperature fall
After i.e. can get the graphene film breathed of porous.
Application the most according to claim 2, it is characterised in that described inorganic salt selected from ammonium hydrogen carbonate, carbamide, thiourea,
Azodicarbonamide；Organic molecule is selected from glycerol, polyethylene glycol 200, PEG400；Macromolecule is selected from cellulose, bright
Glue, chitosan, aqueous polyurethane, acrylic emulsion etc..
Application the most according to claim 2, it is characterised in that, the average-size oxidation more than 100 um in described step 1
Graphene obtains by the following method:
(1), after the reactant liquor dilution of oxidized graphite flake Modified-Hummer method obtained, the mesh screen in 140 mesh was carried out
Filter, obtains filtration product；
(2) filtration product step 1 obtained is after frozen water is according to volume ratio 1:10 mix homogeneously, stands 2h, is added dropwise over double
Oxygen water (H2O2Mass fraction be 30%), until the color of mixed liquor no longer changes, (i.e. potassium permanganate in mixed liquor is the most complete
Remove)；
(3) mixed liquor after step 2 processes is added dropwise over concentrated hydrochloric acid (concentration is 12mol/L), until cotton-shaped oxidation stone
Ink disappears, then goes out graphite oxide wafer with the screen filtration of 140 mesh；
(4) graphite oxide wafer step 3 obtained is placed in shaking table, 20 ~ 80 turns/min, concussion washing so that graphite oxide
Wafer is peeled off, and obtains the graphene oxide without fragment super large sheet, average-size more than 100 um, breadth coefficient 0.2-0.5 it
Between.
Application the most according to claim 4, it is characterised in that the Modified-Hummer method in described step 1 is concrete
For :-10oUnder C, being completely dissolved in by potassium permanganate in the concentrated sulphuric acid that mass fraction is 98%, add graphite, 60 revs/min are stirred
Stirring is stopped, at low temperature (-10-20 after mixing 2hoC) react 6-48h under, obtain the oxidized graphite flake reactant liquor of wide distribution；Described
Graphite, potassium permanganate with concentrated sulphuric acid mass volume ratio be: 1 g:2-4g:30-40ml, the granularity of graphite be more than 150 μm.
Application the most according to claim 4, it is characterised in that described mesh screen is the acidproof mesh screens such as titanium alloy.
Application the most according to claim 4, it is characterised in that in described step 1, the reactant liquor of oxidized graphite flake is by dense
The diluent such as sulphuric acid are diluted, and the volume of diluent is 1-10 times of reactant liquor volume.
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| JP2001284880A (en) * | 2000-03-31 | 2001-10-12 | Furuya Kinzoku:Kk | Electromagnetic wave shield |
| JP2005260214A (en) * | 2004-02-12 | 2005-09-22 | Toray Ind Inc | Electromagnetic wave shield material, stereo structure, electromagnetic wave shield property interior material, and image display device |
| CN105523547A (en) * | 2016-01-25 | 2016-04-27 | 浙江大学 | Graphene film with ultrahigh flexibility and high thermal conductivity and preparation method of graphene film |
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| JP2001284880A (en) * | 2000-03-31 | 2001-10-12 | Furuya Kinzoku:Kk | Electromagnetic wave shield |
| JP2005260214A (en) * | 2004-02-12 | 2005-09-22 | Toray Ind Inc | Electromagnetic wave shield material, stereo structure, electromagnetic wave shield property interior material, and image display device |
| CN105523547A (en) * | 2016-01-25 | 2016-04-27 | 浙江大学 | Graphene film with ultrahigh flexibility and high thermal conductivity and preparation method of graphene film |
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