CN102781831B - Method for preparing few-layer graphene and few-layer graphene film - Google Patents
Method for preparing few-layer graphene and few-layer graphene film Download PDFInfo
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- CN102781831B CN102781831B CN201080062867.XA CN201080062867A CN102781831B CN 102781831 B CN102781831 B CN 102781831B CN 201080062867 A CN201080062867 A CN 201080062867A CN 102781831 B CN102781831 B CN 102781831B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 69
- 229910021389 graphene Inorganic materials 0.000 title abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 89
- 239000010439 graphite Substances 0.000 claims description 89
- 238000010891 electric arc Methods 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 33
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- 235000011089 carbon dioxide Nutrition 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 63
- 239000002904 solvent Substances 0.000 abstract description 8
- 239000007787 solid Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract 2
- 239000011261 inert gas Substances 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 84
- 239000000047 product Substances 0.000 description 25
- 239000010408 film Substances 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000001105 regulatory effect Effects 0.000 description 13
- 230000005540 biological transmission Effects 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 238000000386 microscopy Methods 0.000 description 6
- 239000002356 single layer Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940117389 dichlorobenzene Drugs 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- -1 amino, carboxyl Chemical group 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- 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
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
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- Carbon And Carbon Compounds (AREA)
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Abstract
Provided is a method for preparing few-layer graphene, which comprises the following steps: (1) providing two carbon electrodes as cathode and anode; and (2) applying a voltage between the two electrodes under a mixed gas atmosphere containing inert gas and gas which is reactive to carbon. Also provided is a method for preparing few-layer graphene film, which comprises the following steps: (1) coating with the solid of few-layer graphene, or mixing the solid of few-layer graphene with solvent to give a solution and then coating with the solution; and (2) heating and reducing the formed film under an atmosphere of inert gas or reducing gas.
Description
field
The application relates to carbon material and preparation method thereof, relates to the preparation method of Graphene containing the different number of plies and solution and film particularly.
background
Carbon has multiple existence form, the carbon 60, carbon nanotube and the Graphene that comprise common graphite, diamond, agraphitic carbon and in recent years find.Although these materials are all made up of carbon, structures and characteristics very different.Wherein Graphene is the mono-layer graphite or Multi-layer graphite material that are made up of monolithic graphite.Grapheme material has much excellent character, such as has high conductive capability and mechanical property.Therefore, the thin film obtained by grapheme material has wide practical use.But also there is no good large-scale producing method at present.Therefore a kind of large-scale producing method of simple possible is all badly in need of from research and industrial application aspect.
general introduction
The one side of the application provides the method preparing few layer graphite, and described method comprises:
(1) two carbon dioxide process carbon electrodes are set to negative electrode and anode; And
(2) under the mixed-gas atmosphere comprising rare gas element and carbon is had to certain reactive gas, applied to the two poles of the earth suitable voltage for some time.
The another aspect of the application provides the method preparing few layer graphite film, and described method comprises: the few layer graphite solid obtained in preceding method and solvent are prepared into solution, described solution are carried out film, and is heated in rare gas element by the film of formation.
Accompanying drawing explanation
Fig. 1 is H
2with the transmission electron microscope(TEM) figure of the few layer graphite of arc process synthesis under the gas mixture atmosphere of He.
Fig. 2 is CO
2the Raman spectrogram of the few layer graphite of arc process synthesis under the gas mixture atmosphere of (30% dividing potential drop) and He.
Fig. 3 is CO
2the atomic force microscope figure of the few layer graphite of arc process synthesis under the gas mixture atmosphere of (30% dividing potential drop) and He.
Fig. 4 is the XRD figure of few layer graphite.
Fig. 5 is the thermal multigraph of few layer graphite.
Fig. 6 is CO
2the transmission electron microscope(TEM) figure of the few layer graphite of arc process synthesis under the gas mixture atmosphere of (25% dividing potential drop) and He.
Fig. 7 is CO
2the high-resolution electronic transmission microscopy figure of the few layer graphite of arc process synthesis under the gas mixture atmosphere of (25% dividing potential drop) and He.
Fig. 8 is CO
2the high-resolution electronic transmission microscopy figure of the few layer graphite of arc process synthesis under the gas mixture atmosphere of (25% dividing potential drop) and He.
Fig. 9 is CO
2the atomic force microscope figure of the few layer graphite of arc process synthesis under the gas mixture atmosphere of (40% dividing potential drop) and He.
Figure 10 is CO
2the high-resolution electronic transmission microscopy figure of the few layer graphite of arc process synthesis under the gas mixture atmosphere of (40% dividing potential drop) and He.
Figure 11 is the electroconductibility curve of the film be made up of few layer graphite solution.
describe in detail
In the following description, some concrete details is comprised to provide comprehensive understanding to each disclosed embodiment.But those skilled in the relevant art will appreciate that, do not adopt these concrete details one or more, and adopt when other method, parts, material etc. and can realize embodiment.
Unless other requirement in the application, in whole specification sheets and claims thereafter, word " comprises (comprise) " and English variant such as " comprises (comprises) " and " comprising (comprising) " should be interpreted as meaning that is open, that include formula, namely " includes but not limited to ".
" embodiment " mentioned in whole specification sheets or " embodiment " or " in another embodiment " or " in certain embodiments " mean to comprise and relevant concrete reference feature, structure or the feature described in this embodiment at least one embodiment.Therefore, the phrase " in one embodiment " that different positions occurs in whole specification sheets or " in embodiments " or " in another embodiment " or " in certain embodiments " need not all refer to same embodiment.In addition, concrete key element, structure or feature can combine in any suitable manner in one or more embodiment.
Should be appreciated that the article " " (corresponding to English " a ", " an " and " the ") of the singulative used in present specification and additional claims comprises the object of plural number, unless specified clearly in addition in literary composition.Therefore, the reaction that example comprises as mentioned " rare gas element " comprises a kind of rare gas element, or two or more rare gas elementes.It is also understood that term "or" usually comprises the implication of "and/or" with it and uses, unless specified clearly in addition in literary composition.
Term " few layer graphite (FG) " used in the present invention refers to multilayer (the being generally 2-30 layer) graphite material of serving as reasons its molecular composition unit " mono-layer graphite " being formed.Term " mono-layer graphite " refers to that its monolithic size is at 10nm by the former molecular two dimensional surface molecular skeleton of monolayer carbon
2to 1000 μm
2between, single-sheet thickness is between 0.34nm to 2nm.
" few layer graphite " can be connected different organo-functional groups with the difference of preparation condition, as hydroxyl, amino, carboxyl, epoxide group etc. with the carbon atom of the layer edge section in " mono-layer graphite " according to concrete preparation method.
The one side of the application provides the method preparing few layer graphite, and described method comprises:
(1) two carbon dioxide process carbon electrodes are set to negative electrode and anode; And
(2) under the mixed-gas atmosphere comprising rare gas element and carbon is had to certain reactive gas, applied to the two poles of the earth suitable voltage for some time.
The exemplary rare gas element that can be used in the application comprises N
2, He, Ne, Ar, Kr and Xe.In certain embodiments, rare gas element is He or Ar or its mixture.
To can be used in the application exemplary has certain reactive gas to carbon and includes but not limited to ammonia, hydrogen, carbonic acid gas, air, oxygen etc.
In certain embodiments, in mixed gas, rare gas element is 9: 95 to 95: 5 with the volume ratio having certain reactive gas to carbon.In some embodiment of the application, in mixed gas, rare gas element is 80: 20 to 20: 80 with the volume having certain reactive gas to carbon.In some embodiment of the application, in mixed gas, rare gas element is 75: 25 to 25: 75 with the volume having certain reactive gas to carbon.
In certain embodiments, the total pressure of mixed gas is 0.02MPa to 0.4MPa.In certain embodiments, the total pressure of mixed gas is 0.05MPa to 0.3MPa.In certain embodiments, the total pressure of mixed gas is 0.07MPa to 0.2MPa.
In certain embodiments, two electrodes are the electrode that carbon material is formed.In certain embodiments, two electrodes are the electrode that graphite is formed.
In certain embodiments, in the method for the few layer graphite of preparation, arc discharge process can adopt alternating current arc to discharge or DC arc discharge, and sparking voltage is 10-200V, and electric current is 10-250A.In certain embodiments, in the method for the few layer graphite of preparation, arc discharge process can adopt alternating current arc to discharge or DC arc discharge, and sparking voltage is 10-80V, electric current 50-200A.
In certain embodiments, arc discharge process adopts DC arc discharge, and sparking voltage is 15-50V, and electric current is 80-180A.In certain embodiments, arc discharge process adopts DC arc discharge, and sparking voltage is 15-40V, and electric current is 100-150A.
Electric current in discharge process passes through Energy control, and by regulating the distance between two electrodes to regulate the voltage between two electrodes.
In certain embodiments, anode is sacrificial electrode.
In certain embodiments, between negative electrode and anode to be discharged to anode consumption complete.
In certain embodiments, prepare the method for few layer graphite, described method comprises:
(1) two carbon dioxide process carbon electrodes are set to negative electrode and anode, what wherein diameter was larger is negative electrode, and what diameter was less is anode; And
(2) under the mixed-gas atmosphere comprising rare gas element and carbon is had to certain reactive gas, applied to the two poles of the earth suitable voltage for some time.
In certain embodiments, the diameter of negative electrode is 3mm to 10cm.In certain embodiments, the diameter of negative electrode is 1cm.In certain embodiments, the diameter of anode is 2mm to 8cm.In certain embodiments, the diameter of anode is 5mm.
In certain embodiments, mixed gas is by rare gas element with have certain reactive gas to carbon and form.
In certain embodiments, described method is carried out in electric furnace.
The few layer graphite that the method obtains can containing the graphene film of the different number of plies.
The another aspect of the application provides the method preparing few layer graphite film, described method comprises: above-mentioned few layer graphite solid is directly smeared film forming, or be prepared into solution with solvent, described solution is carried out film, and the film of formation is heated in rare gas element, functional group on controlling removing graphene film and rectification of defects, to recover the intrinsic conductivity of Graphene, obtain high conductivity film.Similarly, can reductive agent be utilized, comprise gaseous reducing agent to reduce, obtain graphene conductive film.
The solvent used when preparing few layer graphite solution can be any volatilizable solvent, and exemplary solvent includes but not limited to: water; The amidess such as DMF (DMF), N,N-dimethylacetamide; The alcohols such as ethanol, methyl alcohol, Virahol; Methyl-sulphoxide (DMSO); The chlorinated solvent classes such as chlorobenzene, dichlorobenzene, methylene dichloride; The ester classes such as ethyl acetate, methyl acetate, dimethyl phthalate (DMP).
Preparing in the method for few layer graphite film in the application, coating method well known in the art can be adopted, include but not limited to spin coating, spraying, impregnating.
Preparing in the method for few layer graphite film in the application, be optionally included in the step adding the auxiliary agent such as dispersion agent, thickening material in the solution prepared to above-mentioned few layer graphite solution or above-mentioned few layer graphite solid and solvent before carrying out film.
Preparing in the method for few layer graphite film in the application, recycle reductive agent after being optionally included in film to reduce the step improving film conductivity.
In certain embodiments, described reductibility steam is hydrazine hydrate steam.
Below by embodiment, the application is specifically described; the present embodiment is only for being further detailed the application; the restriction to the application's protection domain can not be interpreted as; those skilled in the art makes some nonessential improvement and adjustment according to the content of above-mentioned the application, all belongs to the application's protection domain.
Embodiment
the synthesis of few layer graphite
Embodiment 1
Using pure carbon-point as anode.H is passed in electric arc furnace
2be 0.07MPa with the gas mixture (pressure ratio 1: 1) of He to pressure in stove.Arranging outward current is 100A.By regulating cathode anode spacing to maintain about 30V from by voltage after electric discharge starts, maintaining pressure in stove is about 0.07MPa.Anode consumption is complete, and reaction terminates.The product collected in electric arc furnace is few layer graphite.
Embodiment 2
Using pure carbon-point as anode.H is passed in electric arc furnace
2with the gas mixture (pressure ratio 1: 1) of He to pressure 0.07MPa in stove.Arranging outward current is 150A.By regulating cathode anode spacing to maintain about 37V from by voltage after electric discharge starts, maintaining pressure in stove is about 0.07MPa.Anode consumption is complete, and reaction terminates.The product collected in electric arc furnace is few layer graphite.
Fig. 1 is H
2with the transmission electron microscope(TEM) figure of the few layer graphite of arc process synthesis under the gas mixture atmosphere of He.Can be seen by figure, product is sheet is few layer graphite-structure, and part sheet structure is bent to form fold, can find out laminate structure.
Embodiment 3
Using pure carbon-point as anode.CO is passed in electric arc furnace
2with the gas mixture (CO of He
2account for 5% dividing potential drop) to pressure in stove be 0.07MPa.Arranging outward current is 150A.By regulating cathode anode spacing to maintain about 32V from by voltage after electric discharge starts, maintaining pressure in stove is about 0.07MPa.Anode consumption is complete, and reaction terminates.The product collected in electric arc furnace is few layer graphite.
Embodiment 4
Using pure carbon-point as anode.CO is passed in electric arc furnace
2with the gas mixture (CO of He
2account for 30% dividing potential drop) to pressure in stove be 0.07MPa.Arranging outward current is 150A.By regulating cathode anode spacing to maintain about 22V from by voltage after electric discharge starts, maintaining pressure in stove is about 0.07MPa.Anode consumption is complete, and reaction terminates.The product collected in electric arc furnace is few layer graphite.
Embodiment 5
Using pure carbon-point as anode.CO is passed in electric arc furnace
2with the gas mixture (CO of He
2account for 30% dividing potential drop) to pressure in stove be 0.07MPa.Arranging outward current is 200A.By regulating cathode anode spacing to maintain about 20V from by voltage after electric discharge starts, maintaining pressure in stove is about 0.07MPa.Anode consumption is complete, and reaction terminates.The product collected in electric arc furnace is few layer graphite.
Embodiment 6
Using pure carbon-point as anode.CO is passed in electric arc furnace
2with the gas mixture (CO of He
2account for 30% dividing potential drop) to pressure in stove be 0.17MPa.Arranging outward current is 150A.By regulating cathode anode spacing to maintain about 20V from by voltage after electric discharge starts, maintaining pressure in stove is about 0.17MPa.Anode consumption is complete, and reaction terminates.The product collected in electric arc furnace is few layer graphite.
Fig. 2 is CO
2the Raman spectrogram of the few layer graphite of arc process synthesis under the gas mixture atmosphere of (30% dividing potential drop) and He.Can estimate that product is mainly the few layer graphite of 4 layers from the peak width at half height at its 2D peak and peak type.
Fig. 3 is CO
2the atomic force microscope figure of the few layer graphite of arc process synthesis under the gas mixture atmosphere of (30% dividing potential drop) and He, can be seen by figure, the local thickness of product graphite flake is about 2.62nm, illustrates that product is few layer graphite sheet structure.
Embodiment 7
Using pure carbon-point as anode.CO is passed in electric arc furnace
2with the gas mixture (CO of He
2account for 30% dividing potential drop) to pressure in stove be 0.10MPa.Arranging outward current is 150A.By regulating cathode anode spacing to maintain about 20V from by voltage after electric discharge starts, maintaining pressure in stove is about 0.10MPa.Anode consumption is complete, and reaction terminates.Collecting cotton-shaped product in electric arc furnace is few layer graphite.
Embodiment 8
Using pure carbon-point as anode.CO is passed in electric arc furnace
2with the gas mixture (CO of He
2account for 25% dividing potential drop) to pressure in stove be 0.20MPa.Arranging outward current is 150A.By regulating cathode anode spacing to maintain about 20V from by voltage after electric discharge starts, maintaining pressure in stove is about 0.20MPa.Anode consumption is complete, and reaction terminates.The product collected in electric arc furnace is few layer graphite.
Fig. 4 is the XRD figure of the few layer graphite of gained.Can be seen by figure, two peaks represent that the distance between product lamella is respectively 3.4nm and 4.2nm, wherein peak, 3.4nm place is comparatively sharp-pointed, illustrate in product to there is comparatively complete common graphite laminated structure, and peak, 4.2nm place is wider, illustrate in product and also have interlamellar spacing to be greater than the structure of common graphite sheet, and in metamict, meet the structure for few layer graphite.
Fig. 5 is the thermal multigraph of the few layer graphite of gained.Can be seen by figure, product is little at the thermal weight loss of whole warm area, illustrates that the functional group contained by product is less, the mono-layer graphite obtained much smaller than regular solution method and few layer graphite.
Fig. 6 is CO
2the transmission electron microscope(TEM) figure of the few layer graphite of arc process synthesis under the gas mixture atmosphere of (25% dividing potential drop) and He.Can see that product is the few layer graphite of flaky texture by figure, part graphite flake layer forms fold.
Fig. 7 is CO
2the high-resolution electronic transmission microscopy figure of the few layer graphite of arc process synthesis under the gas mixture atmosphere of (25% dividing potential drop) and He.Can see that product is the few layer graphite of flaky texture by figure, edge shown in arrow is the graphite platelet structure of three layers.
Fig. 8 is CO
2the high-resolution electronic transmission microscopy figure of the few layer graphite of arc process synthesis under the gas mixture atmosphere of (25% dividing potential drop) and He.The flake graphite alkene of formation can be found out from Electronic Speculum figure, the number of plies at the fold of graphene sheet layer shown in arrow place is respectively two-layer, four layers, five layers.
Embodiment 9
Using pure carbon-point as anode.CO is passed in electric arc furnace
2with the gas mixture (CO of He
2account for 25% dividing potential drop) to pressure in stove be 0.17MPa.Arranging outward current is 150A.By regulating cathode anode spacing to maintain about 20V from by voltage after electric discharge starts, maintaining pressure in stove is about 0.17MPa.Anode consumption is complete, and reaction terminates.Collecting cotton-shaped product in electric arc furnace is few layer graphite.
Embodiment 10
Using pure carbon-point as anode.CO is passed in electric arc furnace
2with the gas mixture (CO of He
2account for 40% dividing potential drop) to pressure in stove be 0.17MPa.Arranging outward current is 150A.By regulating cathode anode spacing to maintain about 20V from by voltage after electric discharge starts, maintaining pressure in stove is about 0.17MPa.Anode consumption is complete, and reaction terminates.The product collected in electric arc furnace is few layer graphite.
Fig. 9 is CO
2the atomic force microscope figure of the few layer graphite of arc process synthesis under the gas mixture atmosphere of (40% dividing potential drop) and He.Can be seen by figure, the local thickness of product graphite flake is 2.80nm, illustrates that product is few layer graphite sheet structure.
Figure 10 is CO
2the high-resolution electronic transmission microscopy figure of the few layer graphite of arc process synthesis under the gas mixture atmosphere of (40% dividing potential drop) and He.Can see that product is the few layer graphite of flaky texture by figure, edge shown in arrow is the graphite platelet structure of six layers.
Embodiment 11
Using after pure carbon-point mechanical workout as anode.CO is passed in electric arc furnace
2with the gas mixture (CO of Ar
2account for 33% dividing potential drop) to pressure in stove be 0.17MPa.Arranging outward current is 150A.By regulating cathode anode spacing to maintain about 30V from by voltage after electric discharge starts, maintaining pressure in stove is about 0.17MPa.Anode consumption is complete, and reaction terminates.The product collected in electric arc furnace is few layer graphite.
Embodiment 12
Using after pure carbon-point mechanical workout as anode.The gas mixture (air accounts for 50% dividing potential drop) passing into air and He in electric arc furnace is 0.17-0.20MPa to pressure in stove.Arranging outward current is 150A.By regulating cathode anode spacing to maintain about 30V from by voltage after electric discharge starts, maintaining pressure in stove is 0.17-0.20MPa.Anode consumption is complete, and reaction terminates.The product collected in electric arc furnace is few layer graphite.
the preparation of few layer graphite solution
Embodiment 13
By the few layer graphite 1mg generated in example 1-12 with 1ml DMF is ultrasonic mixes, namely obtain the DMF solution of few layer graphite.
Embodiment 14
The few layer graphite 1.7mg generated in example 1-12 and 1ml dichlorobenzene are mixed, namely obtains the dichlorobenzene solution of few layer graphite.
conduct electricity the preparation of few layer graphite film
By the few layer graphite solution generated in example 13 or 14, by spin coating on the quartz plate cleaned up, after heat drying, namely obtain few layer graphite film.
Figure 11 is the electroconductibility curve of the film be made up of few layer graphite solution.Specific conductivity is ~ 10
3s/m, is better than the electroconductibility of the few layer graphite film that additive method obtains.
Claims (16)
1. prepare the method for few layer graphite, described method comprises:
(1) two carbon dioxide process carbon electrodes are set to negative electrode and anode; And
(2) under the mixed-gas atmosphere comprising rare gas element and carbon is had to certain reactive gas, applied to the two poles of the earth suitable voltage for some time,
Wherein sparking voltage is 15-40V, and electric current is 100-150A; And
It is described that to have certain reactive gas to carbon be carbonic acid gas.
2. the method for claim 1, wherein said rare gas element is selected from N
2, He, Ne, Ar, Kr or Xe.
3. the method for claim 1, wherein said rare gas element is He or Ar or its mixture.
4. the method for claim 1, wherein said rare gas element and the described volume ratio having certain reactive gas to carbon are 5:95 to 95:5.
5. the method for claim 1, wherein said rare gas element and the described volume ratio having certain reactive gas to carbon are 80:20 to 20:80.
6. the method for claim 1, wherein said rare gas element and the described volume ratio having certain reactive gas to carbon are 75:25 to 25:75.
7. the method for claim 1, the total gas pressure of wherein said mixed gas is 0.02MPa to 0.4MPa.
8. the method for claim 1, the total gas pressure of wherein said mixed gas is 0.05MPa to 0.3MPa.
9. the method for claim 1, the total gas pressure of wherein said mixed gas is 0.07MPa to 0.2MPa.
10. the method for claim 1, wherein discharge process adopts DC arc discharge.
11. methods as described in claim arbitrary in claim 1 to 10, wherein between negative electrode and anode to be discharged to anode consumption complete.
12. methods as described in claim arbitrary in claim 1 to 10, the diameter of wherein said negative electrode is greater than the diameter of described anode.
13. methods as described in claim arbitrary in claim 1 to 10, the diameter of wherein said negative electrode is 3mm to 10cm.
14. methods as described in claim arbitrary in claim 1 to 10, the diameter of wherein said negative electrode is 1cm.
15. methods as described in claim arbitrary in claim 1 to 10, the diameter of wherein said anode is 2mm to 8cm.
16. methods as described in claim arbitrary in claim 1 to 10, the diameter of wherein said anode is 5mm.
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