CN107651673A - A kind of nanometer grade thickness independent self-supporting fold graphene film and preparation method thereof - Google Patents
A kind of nanometer grade thickness independent self-supporting fold graphene film and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 128
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000007547 defect Effects 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 45
- 239000007787 solid Substances 0.000 claims description 43
- 239000012528 membrane Substances 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000137 annealing Methods 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000000859 sublimation Methods 0.000 claims description 4
- 230000008022 sublimation Effects 0.000 claims description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 4
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 3
- 241000723346 Cinnamomum camphora Species 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 229960000846 camphor Drugs 0.000 claims description 3
- 229930008380 camphor Natural products 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- LPHGQDQBBGAPDZ-UHFFFAOYSA-N Isocaffeine Natural products CN1C(=O)N(C)C(=O)C2=C1N(C)C=N2 LPHGQDQBBGAPDZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229960001948 caffeine Drugs 0.000 claims description 2
- VJEONQKOZGKCAK-UHFFFAOYSA-N caffeine Natural products CN1C(=O)N(C)C(=O)C2=C1C=CN2C VJEONQKOZGKCAK-UHFFFAOYSA-N 0.000 claims description 2
- 238000003958 fumigation Methods 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 2
- 230000000704 physical effect Effects 0.000 claims description 2
- 150000003384 small molecules Chemical class 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims 1
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000011229 interlayer Substances 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000002356 single layer Substances 0.000 abstract 1
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- -1 graphite alkene Chemical class 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Substances [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of nanometer grade thickness independent self-supporting fold graphene film and preparation method thereof, the graphene film is obtained by graphene oxide by filtering the steps such as film forming, electronation and high-temperature process.The graphene film is made up of single-layer graphene physical crosslinking, wherein graphene-based meta structure is complete, without open defect, rich in fold, piece interlayer Turbostratic content is more than 30%.Its very thin thickness (16 130nm), surface has a large amount of gauffers, thus has fabulous flexibility.
Description
Technical field
The present invention relates to high-performance nano material and preparation method thereof, more particularly to a kind of nanometer grade thickness independent self-supporting
Fold graphene film and preparation method thereof.
Background technology
2010, two of Univ Manchester UK professor Andre GeiM and Konstantin Novoselov because
Stable graphene is successfully separated out first and obtains Nobel Prize in physics, has started the upsurge that the whole world is studied graphene.
Graphene has excellent electric property, and (electron mobility is up to 2 × 10 at room temperature5cM2/ Vs), prominent heat conductivility (5000W/
(MK), extraordinary specific surface area (2630M2/ g), its Young's modulus (1100GPa) and fracture strength (125GPa).Graphene is excellent
Different electrical and thermal conductivity performance is well beyond metal, while graphene has the advantages of corrosion-and high-temp-resistant, and its good machinery
Performance and relatively low density more allow it to possess the potentiality in thermo electric material field substituted metal.
The graphene film of macroscopic view assembling graphene oxide or graphene nanometer sheet is the main application of nanoscale graphite alkene
Form, conventional preparation method is suction method, scrape embrane method, spin-coating method, spraying process and dip coating etc..At further high temperature
Reason, the defects of graphene can be repaired, the electric conductivity and thermal conductance of graphene film can be effectively improved, can be widely applied to
Smart mobile phone, intelligence are with oneself in the accompanied electronic equipment such as hardware, tablet personal computer, notebook computer.
But at present, the graphene film thickness that high temperature sintering is crossed is typically in more than 1um, many gas of enclosed inside,
During high pressure is suppressed, the stomata of closing is remained in the form of fold, causes the graphene film degree of orientation to be deteriorated, density
Diminish.In addition, the regular stacking of graphene can cause graphene film easily to bubble at high temperature, graphite can be adjusted by introducing fold
Alkene film starts the thickness of foaming.
Further, there is presently no the preparation of nanoscale graphite alkene film of the work report based on graphene oxide.Normal conditions
Under, nanoscale graphite alkene film is generally referred to as the polycrystalline graphite alkene film of chemical gaseous phase depositing process preparation, its using wet method or
It is fixed on after dry method transfer in some substrate, it is impossible to realize self-supporting independent in atmosphere.This graphene film is in itself
Polycrystalline structure, its performance are influenceed very big by crystal boundary.
The content of the invention
The purpose of the present invention is overcome the deficiencies in the prior art, there is provided a kind of nanometer grade thickness independent self-supporting fold graphite
Alkene film and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions：A kind of nanometer grade thickness independent self-supporting fold graphite
Alkene film, the thickness of the graphene film is 16-130nm, and transparency is less than 50%；It is made up of the graphene film of random fold, AB
Stacking rate 50~70%；Graphene film defect is few, its ID/IG＜ 0.01.
A kind of nanometer grade thickness independent self-supporting fold graphene film and preparation method thereof, is comprised the following steps：
(1) it is 0.5-10ug/mL graphene oxide organic solutions graphene oxide to be configured into concentration, and uses poor solvent
Graphene oxide sheet is precipitated, is finally that substrate filters film forming to anodised aluminium (AAO).
(2) graphene oxide membrane for being attached at AAO films is placed in closed container, 60-100 degree high temperature fumigation HI steam 1-
10h。
(3) solid transfer agent even application is turned in graphene membrane surface, and in less than solid with the methods of evaporation, curtain coating
The temperature moved below 5 degree of agent fusing point is heated so that solid transfer agent solidifies.
(4) graphene film for being coated with solid transfer agent is placed at room temperature, graphene film automatically with AAO UF membranes.
(5) graphene film of solid transfer agent obtained above support is vapored away at a temperature of solid transfer agent volatilizees
Solid transfer agent, obtain the redox graphene film of independent self-supporting.
(6) the redox graphene film of independent self-supporting is placed in the annealing of high temperature furnace high temperature, annealing temperature 2400-
3000 DEG C, hold time and be not more than 20 DEG C/min for 1-12h, heating rate.
Further, in the step 1, organic solution is acetone, tetrahydrofuran, DMF, methanol, ethanol, ethylene glycol,
NMP, DMSO；Poor solvent is ethyl acetate, toluene, ortho-xylene, acetonitrile, ethyl acetate, ether, n-hexane etc..
Further, in the step 4, the AAO films not separated with graphene film are etched away using 1-10% phosphoric acid, are carved
The erosion time is 1-10min.
Further, described solid transfer agent, selected from following material, such as paraffin, camphor, aluminium chloride, iodine, naphthalene, three
Aoxidize two arsenic, phosphorus pentachloride, acrylamide, ferric trichloride, sulphur, red phosphorus, ammonium chloride, ammonium hydrogen carbonate, KI, ENB,
The small molecule that caffeine, melamine, water, rosin, the tert-butyl alcohol, sulfur trioxide etc. can distil or volatilize under certain conditions is consolidated
State material.
Further, the sublimation temperature of described solid transfer agent will be controlled below 320 degree；Sublimation pressure and environment
Oxygen content is depending on physical property.
In general solid transfer agent is macromolecule in common technology at present, because it has characteristic easy to operate, easy to attach,
And it can remove by solution etches or high temperature sintering.But surface tension can tear graphene film during solution etches, from
There must also be substrate support when being taken out in solution.The presence of solution prevents graphene film to exist from independent self-supporting, can only paste
Close on base surface.High temperature sintering can cause graphene film to shrink, it is impossible to maintain the pattern of graphene in itself, and can cause
Graphene is bonded with substrate.By the present invention in that with easy distillation solid-state transfer agent so that nanoscale graphite alkene film can be in air
In support alone.In the process, solid-state transfer agent is removed according to the principle of distillation, the problem of in the absence of surface tension, therefore
Graphene film will not be mutually adhered with substrate.Based on resulting graphene film piece interlayer is stacked by AB, stacking degree can lead to
Peroxidating graphene fold degree is adjusted, and all these structures lay the foundation for the excellent properties of graphene film.According to stone
The thickness of black alkene film, the graphene film have certain transparency, and thickness is smaller, and the transparency is better, and this undoubtedly extends graphene
The potential application of film.
Brief description of the drawings
Fig. 1 is the nano-graphene film (10nm) for removing solid-state transfer agent.
Fig. 2 is the nano-graphene film of 3000 degree of annealings.
Embodiment
Embodiment 1：
(1) it is 0.5ug/mL graphene oxide DMF solutions graphene oxide to be configured into concentration, and slow with ethyl acetate
Graphene oxide sheet is precipitated, is that substrate filters film forming with anodised aluminium (AAO).
(2) graphene oxide membrane for being attached at AAO films is placed in closed container, 60 degree of lower HI steam fumigate 1h.
(3) it is the graphene oxide membrane of above-mentioned reduction is uniform by solid transfer agent camphor with the method for 100 DEG C of distillation evaporations
Coated in graphene membrane surface, and in less than 5 degree of temperature below heating a period of times of solid transfer agent fusing point.It is coated with solid
The graphene film of transfer agent is placed at room temperature, and graphene film is automatically in AAO UF membranes.
(4) graphene film that solid transfer agent obtained above supports slowly is vapored away into solid transfer agent at room temperature,
Obtain the redox graphene film of independent self-supporting.
(5) the redox graphene film of independent self-supporting is placed in the annealing of high temperature furnace high temperature, annealing temperature 3000
DEG C, it is 20 DEG C/min to hold time as 1h, heating rate.
Obtained graphene film can independent self-supporting in atmosphere, its thickness is 130nm, transparency 47%；By random
The graphene film composition of fold, AB stackings rate 50%；Graphene film defect is few, its ID/IG＜ 0.01.
Embodiment 2：
(1) it is 10ug/mL graphene oxide DMSO solutions graphene oxide to be configured into concentration, and slow with ethyl acetate
Graphene oxide sheet is precipitated, is that substrate filters film forming with anodised aluminium (AAO).
(2) graphene oxide membrane for being attached at AAO films is placed in closed container, 100 degree of lower HI steam fumigate 5h.
(3) graphene oxide membrane of above-mentioned reduction low temperature is melted into the method for coating (52 degree) by solid transfer agent paraffin
Even application heats for a period of time in graphene membrane surface, and in less than 5 degree of temperature below of solid transfer agent fusing point.It is coated with
The graphene film of solid transfer agent is placed at room temperature, and graphene film is automatically in AAO UF membranes.
(4) graphene film that solid transfer agent obtained above supports slowly is vapored away into solid transfer agent at 120 DEG C,
Obtain the redox graphene film of independent self-supporting；If reducing uneven in step 2, or hydrogen iodide steam directly contacts
AAO films are arrived, during solid transfer agent shifts, graphene will not be automatically separated with AAO films, now be needed with 5%
Phosphoric acid etches away AAO films, etch period 2min.
(5) the redox graphene film of independent self-supporting is placed in the annealing of high temperature furnace high temperature, annealing temperature 2400
DEG C, it is 20 DEG C/min to hold time as 12h, heating rate.
Obtained graphene film can independent self-supporting in atmosphere, its thickness is 16nm, transparency 48%；By random pleat
The graphene film composition of wrinkle, AB stackings rate 70%；Graphene film defect is few, its ID/IG＜ 0.01.
Embodiment 3：
(1) it is 2ug/mL graphene oxide acetone solns graphene oxide to be configured into concentration, and is slowly sunk with n-hexane
Shallow lake graphene oxide sheet, it is that substrate filters film forming with anodised aluminium (AAO).
(2) graphene oxide membrane for being attached at AAO films is placed in closed container, 80 degree of lower HI steam fumigate 10h.
(3) by the graphene oxide membrane of above-mentioned reduction with the method that solution applies by solid transfer agent aluminium chloride even application
In graphene membrane surface, and in less than 5 degree of temperature below heating a period of times of solid transfer agent fusing point.It is coated with solid transfer
The graphene film of agent is placed at room temperature, and graphene film is automatically in AAO UF membranes.
(4) graphene film that solid transfer agent obtained above supports slowly is vapored away into solid transfer agent at 180 DEG C,
Obtain the redox graphene film of independent self-supporting；If reducing uneven in step 2, or hydrogen iodide steam directly contacts
AAO films are arrived, during solid transfer agent shifts, graphene will not be automatically separated with AAO films, now need to use 1-10%
Phosphoric acid etch away AAO films, etch period 1-10min.
(5) the redox graphene film of independent self-supporting is placed in the annealing of high temperature furnace high temperature, annealing temperature 2600
DEG C, it is 10 DEG C/min to hold time as 2h, heating rate.
Obtained graphene film can independent self-supporting in atmosphere, its thickness is 39nm, transparency 36%；By random pleat
The graphene film composition of wrinkle, AB stackings rate 66%；Graphene film defect is few, its ID/IG＜ 0.01.
Embodiment 4：
(1) it is 10ug/mL graphene oxide tetrahydrofuran solutions graphene oxide to be configured into concentration, and slow with toluene
Graphene oxide sheet is precipitated, is that substrate filters film forming with anodised aluminium (AAO).
(2) graphene oxide membrane for being attached at AAO films is placed in closed container, 90 degree of lower HI steam fumigate 10h.
(3) method that the graphene oxide membrane of above-mentioned reduction is cast to (130 DEG C) with high temperature is uniform by solid transfer agent sulphur
Coated in graphene membrane surface, and in less than 5 degree of temperature below heating a period of times of solid transfer agent fusing point.It is coated with solid
The graphene film of transfer agent is placed at room temperature, and graphene film is automatically in AAO UF membranes.
(4) graphene film of solid transfer agent obtained above support is fallen into solid using the method slow vaporization of low pressure distillation
Transfer agent, obtain the redox graphene film of independent self-supporting；If uneven, or hydrogen iodide steam is reduced in step 2
AAO films are directly contacted, during solid transfer agent shifts, graphene will not be automatically separated with AAO films, now be needed
AAO films, etch period 1-10min are etched away with 1-10% phosphoric acid.
(5) the redox graphene film of independent self-supporting is placed in the annealing of high temperature furnace high temperature, annealing temperature 2500
DEG C, it is 10 DEG C/min to hold time as 12h, heating rate.
Obtained graphene film can independent self-supporting in atmosphere, its thickness is 109nm, transparency 41%；By random
The graphene film composition of fold, AB stackings rate 59%；Graphene film defect is few, its ID/IG＜ 0.01.
Claims (6)
1. a kind of nanometer grade thickness independent self-supporting fold graphene film, it is characterised in that the thickness of the graphene film is 16-
130nm, transparency are less than 50%；It is made up of the graphene film of random fold, AB stackings rate 50~70%；Graphene film defect pole
It is few, its ID/IG＜ 0.01.
2. a kind of nanometer grade thickness independent self-supporting fold graphene film and preparation method thereof, it is characterised in that include following step
Suddenly：
(1) it is 0.5-10ug/mL graphene oxide organic solutions graphene oxide to be configured into concentration, and is precipitated with poor solvent
Graphene oxide sheet, it is finally that substrate filters film forming to anodised aluminium (AAO).
(2) graphene oxide membrane for being attached at AAO films is placed in closed container, 60-100 degree high temperature fumigation HI steam 1-10h.
(3) use the methods of being deposited, being cast by solid transfer agent even application in graphene membrane surface, and in less than solid transfer agent
Temperature below 5 degree of fusing point is heated so that solid transfer agent solidifies.
(4) graphene film for being coated with solid transfer agent is placed at room temperature, graphene film automatically with AAO UF membranes.
(5) graphene film of solid transfer agent obtained above support is vapored away into solid at a temperature of solid transfer agent volatilizees
Transfer agent, obtain the redox graphene film of independent self-supporting.
(6) the redox graphene film of independent self-supporting is placed in the annealing of high temperature furnace high temperature, annealing temperature 2400-3000
DEG C, hold time and be not more than 20 DEG C/min for 1-12h, heating rate.
3. according to the method for claim 2, it is characterised in that in the step 1, organic solution is acetone, tetrahydrofuran,
DMF, methanol, ethanol, ethylene glycol, NMP, DMSO；Poor solvent is ethyl acetate, toluene, ortho-xylene, acetonitrile, ethyl acetate,
Ether, n-hexane etc..
4. according to the method for claim 2, it is characterised in that in the step 4, etched away not using 1-10% phosphoric acid
The AAO films separated with graphene film, etch period 1-10min.
5. method as claimed in claim 2, it is characterised in that described solid transfer agent, selected from following material, such as stone
Wax, camphor, aluminium chloride, iodine, naphthalene, arsenic trioxide, phosphorus pentachloride, acrylamide, ferric trichloride, sulphur, red phosphorus, ammonium chloride, carbon
Sour hydrogen ammonium, KI, ENB, caffeine, melamine, water, rosin, the tert-butyl alcohol, sulfur trioxide etc. can be in certain conditions
The small molecule solid matter of lower distillation or volatilization.
6. method as claimed in claim 2, it is characterised in that the sublimation temperature of described solid transfer agent will be controlled 320
Below degree；Sublimation pressure and environment oxygen content are depending on physical property.
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| CN201710955058.5A CN107651673B (en) | 2017-10-13 | 2017-10-13 | Nano-scale thickness independent self-supporting folded graphene film and preparation method thereof |
| JP2020510549A JP2020531387A (en) | 2017-10-13 | 2018-05-08 | Self-supporting graphene film and its manufacturing method |
| RU2020115707A RU2753510C1 (en) | 2017-10-13 | 2018-05-08 | Independent freely located graphene film and method for production thereof |
| PCT/CN2018/086085 WO2019071943A1 (en) | 2017-10-13 | 2018-05-08 | Independent self-supporting graphene film and preparation method therefor |
| US16/476,117 US11834336B2 (en) | 2017-10-13 | 2018-05-08 | Independent free-standing graphene film and method of preparing the same |
| EP18866208.4A EP3620435B1 (en) | 2017-10-13 | 2018-05-08 | Independent free-standing graphene film and preparation method therefor |
| KR1020207006088A KR102316218B1 (en) | 2017-10-13 | 2018-05-08 | Independent self-supporting graphene film and method for manufacturing the same |
| JP2021086043A JP7186464B2 (en) | 2017-10-13 | 2021-05-21 | Free-standing graphene film and method for producing same |
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