CN106185893B - A kind of application for breathing graphene film in light stability is detected - Google Patents
A kind of application for breathing graphene film in light stability is detected Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 107
- 230000029058 respiratory gaseous exchange Effects 0.000 title claims abstract description 6
- 238000001514 detection method Methods 0.000 claims abstract description 6
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- 238000006243 chemical reaction Methods 0.000 claims description 18
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- 238000009826 distribution Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- 229920002521 macromolecule Polymers 0.000 claims description 4
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- 150000003839 salts Chemical class 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
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- 230000009514 concussion Effects 0.000 claims description 3
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- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 108010010803 Gelatin Proteins 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
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- -1 poly- ammonia Ester Chemical class 0.000 claims description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 2
- 238000009288 screen filtration Methods 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
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- 239000010408 film Substances 0.000 description 55
- 239000000463 material Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 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
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 230000003019 stabilising effect Effects 0.000 description 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- 229920006266 Vinyl film Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change 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
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- 239000002305 electric material Substances 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 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
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
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- 238000001179 sorption measurement Methods 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K3/00—Materials not provided for elsewhere
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- 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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- Chemical & Material Sciences (AREA)
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- Microelectronics & Electronic Packaging (AREA)
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Abstract
The invention discloses a kind of application for breathing graphene film in light stability is detected, the application can breathe the capability of electromagnetic shielding of graphene film to realize by detection, it can breathe that the capability of electromagnetic shielding data of graphene film are more unstable, and light stability is lower.The graphene film that breathes with heat conductivility (1,800 2600 W/mK) is rapidly heated expansion under light illumination, and shield effectiveness improves.High-sensitivity detection to light stability can be realized by the graphene film.
Description
Technical field
The present invention relates to the application of novel heat-conducting, suction ripple and electromagnetic shielding material, more particularly to one kind can breathe graphite
Application of the alkene film in light stability is detected.
Background technology
2010, two of Univ Manchester UK professor Andre GeiM and Konstantin Novoselov because
Stable graphene is successfully separated out first and obtains Nobel Prize in physics, has started the upsurge that the whole world is studied graphene.
Graphene has excellent electric property, and (electron mobility is up to 2 × 10 at room temperature5cM2/ Vs), prominent heat conductivility (5000W/
(MK), extraordinary specific surface area (2630 M2/ g), its Young's modulus (1100GPa) and fracture strength (125GPa).Graphene is excellent
Different electrical and thermal conductivity performance is well beyond metal, while graphene has the advantages of corrosion-and high-temp-resistant, and its good machinery
Performance and relatively low density more allow it to possess the potentiality in thermo electric material field substituted metal.
The graphene film of macroscopic view assembling graphene oxide or graphene nanometer sheet is the main application of nanoscale graphite alkene
Form.By further high-temperature process, the defects 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 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 can not substantially meet the needs of future technology progress complexity.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 overcome the deficiencies in the prior art, there is provided one kind can breathe graphene film in detection stabilized intensity
Application in property.
The purpose of the present invention is achieved through the following technical solutions：One kind can breathe graphene film in detection stabilized intensity
Property in application, the application can breathe the capability of electromagnetic shielding of graphene film to realize by detection, can breathe graphene film
Capability of electromagnetic shielding data it is more unstable, light stability is lower.It is described to breathe graphene film being averaged by planar orientation
Graphene film of the size more than 100 μm is formed by the pi-conjugated effects of π mutually overlap joint.Wherein include and be made up of 1-4 layer graphene pieces
Graphene-structured.And the defects of graphene film, is few, its ID/TG＜ 0.01.
Further, it is described breathe graphene film preparation method it is as follows：
(1) it is 6~30mg/mL graphene oxide water graphene oxide of the average-size more than 100 μm to be configured into concentration
Solution, mass fraction 0.1-5% auxiliary agent (i.e. the mass fraction of auxiliary agent in the solution is 0.1-5%), institute are added in the solution
It is inorganic salts, organic molecule or macromolecule to state auxiliary agent；After ultrasonic disperse, 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 0.1-0.5 DEG C/min speed
500-700 DEG C, it is incubated 0.5-2h；
(3) 1000-1200 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, from
It so can obtain after cooling and porous breathe graphene film.
Described inorganic salts are selected from ammonium hydrogen carbonate, urea, thiocarbamide, azodicarbonamide；Organic molecule is selected from glycerine, gathered
Ethylene glycol 200, polyethylene glycol 400；Macromolecule is selected from cellulose, gelatin, chitosan, aqueous polyurethane, acrylic emulsion etc..
Graphene oxide of the average-size more than 100 μm obtains by the following method in the step 1：
(1) after the reaction solution dilution for the oxidized graphite flake for obtaining Modified-Hummer methods, enter in the mesh screen of 140 mesh
Row filtering, obtains filtration product；
(2) by the filtration product that step 1 obtains in frozen water according to volume ratio 1：After 10 is well mixed, 2h is stood, is added dropwise
Enter hydrogen peroxide (H2O2Mass fraction for 30%), until the color of mixed liquor no longer changes, (potassium permanganate i.e. in mixed liquor is
Remove completely)；
(3) concentrated hydrochloric acid (concentration 12mol/L) is added dropwise into the mixed liquor after step 2 processing, until cotton-shaped oxygen
Graphite disappears, then goes out graphite oxide chip with the screen filtration of 140 mesh；
(4) the graphite oxide chip that step 3 obtains is placed in shaking table, 20~80 turns/min, concussion washing so that oxidation
Graphite wafer is peeled off, and obtains the graphene oxide of no fragment super large piece, and average-size is more than 100 μm, and breadth coefficient is in 0.2-
Between 0.5.
Modified-Hummer methods in the step 1 are specially：At -10 DEG C, potassium permanganate is completely dissolved in matter
Measure in the concentrated sulfuric acid that fraction is 98%, add graphite, stop stirring after 60 revs/min of stirring 2h, under low temperature (- 10-20 DEG C)
6-48h is reacted, obtains the oxidized graphite flake reaction solution of wide distribution；Described graphite, potassium permanganate and concentrated sulfuric acid mass volume ratio
For：1g：2-4g：30-40ml, the granularity of graphite are more than 150 μm.
The mesh screen is the acidproof mesh screens such as titanium alloy.
In the step 1, the reaction solution of oxidized graphite flake is diluted by diluents such as the concentrated sulfuric acids, the volume of diluent
For 1-10 times of reaction solution volume.
Disclosure sets forth a kind of multifunctional graphite vinyl film that can be changed between heat conductivility and capability of electromagnetic shielding
New opplication, and the graphene film is mutual by the pi-conjugated effects of π by graphene film of the average-size of planar orientation more than 100 μm
Overlap joint forms.Big conjugated structure ensure that the unimpeded of the path between graphene, and the graphene that 1-4 layer graphenes piece is formed
The introducing of structure, it is greatly improved the electric conductivity of material；In non-lap-joint, cavity is formed between graphene film and piece, when
Graphene film is placed under the illumination of high intensity, passes through graphene quick conductive so that its intracavity gas is rapidly heated expansion, another
Aspect, under high temperature, fold has the trend unfolded in itself, meanwhile, under gas expansion effect, the fold of cavity wall is strutted by gas,
Gradually become smooth；Big cavity, smooth cavity wall auxiliary make its film have extremely strong electromagnetic wave shielding with preferable electric conductivity
Energy.Intensity of illumination is higher, and capability of electromagnetic shielding is better.When needing recycling, micro- air bag is pressed using condition of high voltage
Contracting.
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 exhales and inhaled state lower section figure for that can breathe graphene film.
Fig. 6 is the electromagnetic shielding curve map under different capacity illumination.
Embodiment
By the present invention in that with super large piece graphene oxide film forming, the wherein average-size of planar orientation is more than 100 μm
Graphene film important role during graphene film of the present invention is formed, the present invention wash it in graphite oxide crystal
Before, using the method for mesh screen separation, chip separation is gone out.And 10 times are used to be diluted with the frozen water of upper volume so that it is brilliant
Piece will not be destroyed because of the heat of solution of sulfuric acid.Further using shaking table concussion washing so that graphene oxide layer is being shelled
From when avoid the broken of mechanical force.Further, the present invention also prepares graphene film by cryogenic conditions, in low temperature
Under, potassium permanganate oxidation is weaker, and the speed that its selfdecomposition produces oxygen is slow, therefore gas is to graphite oxide crystal
Fragmentation is just very weak so that the graphene oxide of big lamella is preserved.And do not have in course of reaction and cleaning process
Violent stirring and ultrasonic procedure, thus lamella there is no it is broken.In summary some, we have obtained the nothing of super large piece
The graphene oxide of fragment, average-size is more than 87 μm, and for breadth coefficient between 0.2-0.5, 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 at -10 DEG C, after abundant dissolving, added
Graphite, 60 revs/min are slowly stirred stopping stirring after 2h, react 6h respectively at 20 DEG C, 50 DEG C, respectively obtain wide distribution
Graphite oxide crystal；As shown in figure 1, more fragment be present in the graphite oxide chip obtained at a temperature of two kinds, this causes
Its corresponding graphene oxide equally has many fragments (Fig. 2).
(2) (extension rate can be any multiple to the reaction solution diluting concentrated sulfuric acid obtained step 1, and the present embodiment is dilute
Release 10 times or so), and graphite oxide crystal is filtered out into (reaction solution with the titanium alloy mesh screen of 150 μm of apertures (140 mesh)
Recovery), and be poured slowly into the frozen water relative to 10 times of volumes of filtration product quickly stirred, 2h is stood, is slowly added to H2O2,
Except potassium permanganate unnecessary in dereaction, to add appropriate hydrochloric acid until cotton-shaped graphite oxide disappears, then with titanium alloy mesh screen
(140 mesh) filters out graphite oxide chip；Shaking table slowly shakes washing, and the graphene oxide for obtaining no fragment super large piece is (average
Size is 87 μm, breadth coefficient 0.5).Graphite, potassium permanganate and concentrated sulfuric acid mass volume ratio are：1g：2g：40ml, graphite
Granularity be 200 μm.
As shown in figure 3, obtained oxidation stone is washed after the graphite oxide chip separation isolated after the lower reaction of 50 degree of high temperature
Black alkene equally has many fragments；From fig. 4, it can be seen that large stretch of graphene oxide size under low temperature after (20 DEG C) Reaction Separation
It is few to be distributed more uniform concentration, shive content.
Embodiment 1-2
Potassium permanganate is slowly added at -10 DEG C in the concentrated sulfuric acid quickly stirred, after abundant dissolving, adds stone
Ink, 60 revs/min are slowly stirred stopping stirring after 2h, react 48h under low temperature (0 DEG C), obtain reaction solution；By reaction solution point
It is not diluted with the concentrated sulfuric acid of mass fraction more than 98%, the dilute sulfuric acid that mass fraction is 10%, then with 150 μm of apertures
Titanium alloy mesh screen graphite oxide crystal is filtered out into (reaction solution recovery), and be poured slowly into quickly stir relative to filtering
In the frozen water of 10 times of volumes of product, 2h is stood, is slowly added to H2O2, except potassium permanganate unnecessary in dereaction, to add appropriate
Hydrochloric acid disappears until cotton-shaped graphite oxide, then is sieved through with titanium alloy reticulated and filters out graphite oxide chip；Shaking table slowly shakes washing, obtains
To reaction product.Graphite, potassium permanganate and concentrated sulfuric acid mass volume ratio are：1：4g：30ml；The granularity of graphite is 500 μm.
Using diluting concentrated sulfuric acid, react to obtain without fragment super large piece graphene oxide (average-size is 98 μm,
Breadth 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 due in dilute sulfuric acid dilution, highly exothermic, destroys graphite oxide crystal.
Embodiment 1-3
Potassium permanganate is slowly added at -10 DEG C in the concentrated sulfuric acid quickly stirred, after abundant dissolving, adds stone
Ink, 60 revs/min are slowly stirred stopping stirring after 2h, react 28h under low temperature (20 DEG C), the graphite oxide for obtaining wide distribution is brilliant
Body；Graphite oxide crystal is filtered out into (reaction by reaction solution with diluting concentrated sulfuric acid and with the titanium alloy mesh screen in 150 μm of apertures
Liquid reclaims), and be poured slowly into respectively quickly stir relative to 5 times of volumes of filtration product, 8 times of volumes, 10 times of volumes frozen water
In, 2h is stood, is slowly added to H2O2, except potassium permanganate unnecessary in dereaction, to add appropriate hydrochloric acid until cotton-shaped oxidation stone
Ink disappears, then is sieved through with titanium alloy reticulated and filters out graphite oxide chip；Shaking table slowly shakes washing, obtains reaction product；Graphite, height
Potassium manganate is with concentrated sulfuric acid mass volume ratio：1：5g：34ml, the granularity of graphite is 2mm.
Experimental result shows, the frozen water of 5 times of volumes and 8 times of volumes can not obtain the graphene film of size uniformity,
Can just be obtained under 10 times of volumes no fragment super large piece graphene oxide (average-size be 92 μm, breadth coefficient is 0.2).By
This understands that the amount of frozen water is too low, and the heat of mixing will be caused to concentrate release, destroys crystal structure.
Embodiment 2：The graphene oxide without fragment super large piece being prepared using embodiment 1 prepares respirable graphite
Alkene film.
It is 28mg/mL graphene oxide water solutions that graphene oxide of the average-size more than 100 μm is configured into concentration,
The urea of mass fraction 5.4% is added in the solution, is poured on after ultrasonic disperse on Die and mould plate and is dried into graphene oxide membrane, so
Reduced afterwards with hydrogen iodide reducing agent；Graphene film after reduction is under atmosphere of inert gases according to shown in 1~table of table 3
Heat treatment mode carries out three step heat treatments；The porous graphene film that thickness is 1mm is can obtain after Temperature fall.By graphene
Film is suppressed under high pressure can obtain super flexible high heat conduction graphene film.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 measures its capability of electromagnetic shielding in 400 degree of environment is placed in, and high thermal conductivity and highly sensitive graphite are prepared with acquisition
The parameter of alkene film；As shown in table 1-3.Fig. 5 is can breathe graphene film respiratory electromicroscopic photograph, exhaling under external force
During, graphene film is driven plain, and breathing stomata is remained by the form of fold；The process inhaled under photic heat effect
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
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, and it is most of degradable to be not enough to removing
Functional group, cause gas in second step pyroprocess largely quickly to produce, tear lamellar structure at high temperature；E1 temperature mistakes
Height, generation gas is too fast, can largely tear material internal structure, both can cause deterioration in material properties.Have only B1, C1,
At a temperature of D1, functional group can slowly and thoroughly remove, to ensure material property.Compare C1, F1, G1, H1, F1 heating rate mistakes
Low, gas release is excessively slow, it is impossible to so that material internal forms through hole, is unfavorable for micro- air bag in ensuing temperature-rise period
Formation；H1 temperature-rise periods are too fast, and gas release is too fast, tear material internal structure, are unfavorable for forming transmission channel.Have CG only
It just can both ensure the formation of micro- air bag under heating rate, and can ensures the complete of passage.Compare C1, I1, J1, K1, L1, M1,
I1 soaking times are too short, it is impossible to ensure the degraded of most of functional group；M1 insulating processes are long, can absorb Jiao inside stove
Oil, it is unfavorable for the lifting of performance.C1, J1, K1, L1 just avoid both of the above.
From Table 2, it can be seen that comparing A2, B2, C2, D2, E2, A2 heating rates are too low to be not enough to form small space
Structure so that film can not form micro- air bag, have a strong impact on capability of electromagnetic shielding.E2 programming rates are too high, can tear graphene layer
Between structure so that graphene film link property is deteriorated, and heat conduction capability of electromagnetic shielding is all deteriorated.Have B2, C2, D2 programming rate only
Under, it just capable can not only ensure micro- airbag structure but also ensure the continuity inside graphene film.Compare C2, I2, J2, K2, L2,
M2, I2 soaking time are too short, and stable functional group can not fully come off；M2 overlong times, the easy tar adsorption of graphene film, no
Beneficial to the lifting of film properties；And can both ensure fully coming off for stabilising functional group under the conditions of C2, J2, K2, M2, and can avoids Jiao
The puzzlement of oil.
From table 3 it is observed that comparing A3, B3, C3, D3, E, A3 heating rates are too low, the mistake that most stabilising functional group comes off
Slowly, it is not enough to support the formation of micro- air bag during forming micro- air bag；E3 temperature-rise periods are too fast, and gas release and high temperature are swollen
It is swollen too fast, it is easily destroyed the formation of micro- air bag.Only in the case of B3, C3, D3, micro- air bag could stablize formation, graphene
On structure could slowly repair.Compare C3, F3, G3, H3, I3, F3 outlet temperatures are too low, and graphene-structured is repaired inadequate
It is perfect, so various performances are all very poor；I3 outlet temperatures are too high, and graphene can be vaporized；Ability at a temperature of C3, G3, H3
Both the reparation of graphene-structured had been ensured, will not be vaporized again.Compare C3, J3, K3, L3, M3, J3 soaking times are too low, graphite
Alkene 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：Graphene film is used to detect light intensity.
First, it is as follows can to breathe graphene film for preparation
(1) it is 6mg/mL graphene oxide water solutions graphene oxide of the average-size more than 100 μm to be configured into concentration,
The glycerine of mass fraction 5% is added in the solution；After ultrasonic disperse, 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 to 700 under atmosphere of inert gases with 0.5 DEG C/min speed
DEG C, it is incubated 1h；
(3) 1200 DEG C are warming up to 2 DEG C/min speed under atmosphere of inert gases, are incubated 1h；
(4) 2500 DEG C are warming up to 7 DEG C/min speed under atmosphere of inert gases, are incubated 1h, after Temperature fall
Obtain porous breathing graphene film.
Then, the graphene film being prepared is respectively placed in dark situation I~VII, respectively with same in each dark situation
The laser 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 measured are as shown in Figure 6.
As can be seen from Figure 6, graphene film has the thermal conductivity of superelevation, and heat conduction work, sensitivity are completed substantially in 1 minute
It is high.In addition, the graphene film capability of electromagnetic shielding size discrimination under different capacity illumination is obvious, explanation can differentiate different illumination rings
Border, intensity of illumination is bigger, and capability of electromagnetic shielding is bigger.Therefore, efficient evaluations can be carried out to light stability.
Claims (7)
1. a kind of application for breathing graphene film in light stability is detected, it is characterised in that the application passes through detection
The capability of electromagnetic shielding of graphene film can be breathed to realize, it is more unstable to breathe the capability of electromagnetic shielding data of graphene film,
Light stability is lower；The graphene film that breathes passes through π by graphene film of the average-size of planar orientation more than 100 μm
Pi-conjugated effect mutually overlap joint forms, and in non-lap-joint, cavity is formed between graphene film and piece, has fold in cavity wall；And wherein
Include the graphene-structured being made up of 1-4 layer graphene pieces；And the defects of graphene film, is few, its ID/IG＜ 0.01.
2. application according to claim 1, it is characterised in that, it is described breathe graphene film preparation method it is as follows：
(1) it is 6~30mg/mL graphene oxide water solutions graphene oxide of the average-size more than 100 μm to be configured into concentration,
Mass fraction 0.1-5% auxiliary agent is added in the solution, and the auxiliary agent is inorganic salts, organic molecule or macromolecule；Ultrasound point
After dissipating, 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 to 500- under atmosphere of inert gases with 0.1-0.5 DEG C/min speed
700 DEG C, it is incubated 0.5-2h；
(3) 1000-1200 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, Temperature fall
It can obtain afterwards and porous breathe graphene film.
3. application according to claim 2, it is characterised in that described inorganic salts are selected from ammonium hydrogen carbonate；Organic molecule
Selected from glycerine, gelatin, acrylic acid, urea, thiocarbamide, azodicarbonamide, macromolecule is selected from cellulose, chitosan, water-based poly- ammonia
Ester, polyethylene glycol 200, polyethylene glycol 400.
4. application according to claim 2, it is characterised in that, average-size is more than 100 μm of oxidation in the step 1
Graphene obtains by the following method：
(1) after the reaction solution dilution for the oxidized graphite flake for obtaining Modified-Hummer methods, carried out in the mesh screen of 140 mesh
Filter, obtains filtration product；
(2) by the filtration product that step 1 obtains in frozen water according to volume ratio 1：After 10 is well mixed, 2h is stood, matter is added dropwise
The hydrogen peroxide that fraction is 30% is measured, until the color of mixed liquor no longer changes；
(3) concentrated hydrochloric acid that concentration is 12mol/L is added dropwise into the mixed liquor after step 2 processing, until cotton-shaped oxidation stone
Ink disappears, then goes out graphite oxide chip with the screen filtration of 140 mesh；
(4) the graphite oxide chip that step 3 obtains is placed in shaking table, 20~80 turns/min, concussion washing so that graphite oxide
Chip is peeled off, and obtains the graphene oxide of no fragment super large piece, and average-size is more than 100 μm, and breadth coefficient is in 0.2-0.5
Between.
5. application according to claim 4, it is characterised in that the Modified-Hummer methods in the step 1 are specific
For：At -10 DEG C, potassium permanganate is completely dissolved in the concentrated sulfuric acid that mass fraction is 98%, addition graphite, 60 revs/min
Stop stirring after stirring 2h, 6-48h is reacted in a low temperature of -10-20 DEG C, obtain the oxidized graphite flake reaction solution of wide distribution；Institute
Graphite, potassium permanganate and the concentrated sulfuric acid mass volume ratio stated be：1g：2-4g：30-40ml, the granularity of graphite are more than 150 μm.
6. application according to claim 4, it is characterised in that the mesh screen is the acidproof mesh screen of titanium alloy.
7. application according to claim 4, it is characterised in that in the step 1, the reaction solution of oxidized graphite flake passes through dense
Sulfuric acid diluent is diluted, and the volume of diluent is 1-10 times of reaction solution volume.
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