CN102372268A - Preparation method of graphene material - Google Patents
Preparation method of graphene material Download PDFInfo
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- CN102372268A CN102372268A CN2011103159321A CN201110315932A CN102372268A CN 102372268 A CN102372268 A CN 102372268A CN 2011103159321 A CN2011103159321 A CN 2011103159321A CN 201110315932 A CN201110315932 A CN 201110315932A CN 102372268 A CN102372268 A CN 102372268A
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Abstract
The invention relates to a preparation method of a graphene material. The method comprises the following steps: mixing graphite with a methylcellulose aqueous solution to be prepared into ointment, then coating the ointment on an aluminum plate, drying in the shade, and then pressing and drying to obtain a negative electrode; based on a lithium sheet as a positive electrode, placing the negative electrode and the positive electrode in a closed electrolytic cell, and then injecting electrolyte so as to constitute a lithium-embedded electrolytic cell; charging with constant-current or constant-voltage power supply to implement lithium embedment on the negative electrode so as to form a carbon-lithium interlayer compound LiC6, and placing the carbon-lithium interlayer compound LiC6 in a steam or water environment so that lithium in the graphite reacts with water; and stripping a solid substance from the aluminum plate, washing, filtering, and drying, so as to obtain the graphene product. Compared with the method for preparing graphene by graphite reduction and oxidation, in the graphene preparation process of the invention, strong acid is not needed, and lithium can be embedded between graphite layers within a relatively short time, thereby being more beneficial for controlling the reaction and the quality of the product. The prepared high-purity graphene can be widely applied to the fields of nano electronic devices, electrical conducting materials, photon sensors, light high-strength materials and the like.
Description
Technical field
The present invention relates to a kind of carbon material preparation method of graphene, particularly metallic lithium is embedded graphite, adopt chemical process to produce volumetric expansion then and cause graphite linings to separate the method for preparing Graphene at graphite layers formation compound with electrochemical method.
Background technology
Graphite is a kind of allotropic substance of elemental carbon, and the periphery of each carbon atom links other three carbon atoms of work (arrangement mode is cellular a plurality of hexagons) with covalent bonds, constitutes laminate structure, has complete stratiform cleavage characteristic.Be separated by greatlyyer between graphite crystal middle level and the layer, combine with Van der Waals force, cleavage surface is main with molecular linkage, to van der Waals' force a little less than.But, because combination is very strong between the carbon atom on the same plane layer, extremely difficult destruction, so the molten point of graphite is also very high, chemical property is also stable.Each carbon atom all can be emitted an electronics in the layer, and those electronics can move freely, and belong to electrical conductor.And, because the graphite cleavage surface is main with molecular linkage, can embed lithium atom, therefore also be negative material commonly used in the lithium ion battery.Following electrochemical redox reaction takes place in the lithium ion battery charge and discharge process:
Graphene also is a kind of allotropic substance of elemental carbon, and the monolayer carbon atom material that can from graphite material, peel off out, carbon atom arrangement have cellular or the regular hexagon structure, is the two-dirnentional structure that carbon atom constitutes.The thickness of this graphite crystal film has only 0.335nm; Thickness be merely 200,000 of hairline/; Be the elementary cell that makes up other dimension blackings (like zero dimension soccerballene, one dimension carbon nanotube, three-dimensional graphite), have excellent crystallinity and electric property.2004, people such as the Novoselov of Univ Manchester UK and Geim utilized the method for mechanically peel in the laboratory, successfully to prepare single-layer graphene for the first time, and the Graphene that obtains not only quality is high, and can stable existence in external environment.The successful preparation of Graphene and superior stiffness structure thereof, good electrical conductivity bring a revolution will for fields such as physics, materialogy, electrocatalysis and bio-sensing.
Preparation method of graphene has multiple, peels off method, epitaxial growth method, vapour deposition process and reduction-oxidation graphite method but comparatively sophisticated compound method mainly contains micromechanics.
It is through a kind of method of mechanical force from the sur-face peeling Graphene lamella of fresh graphite crystal that micromechanics is peeled off method.After utilizing ionic fluid at first etching to be carried out on the thick height of 1mm orientation pyrolytic graphite surface, sample is attached on the glass substrate, the method for peeling off with micromechanics is torn repeatedly with scotch tape and is taken off.Then, glass substrate is ultrasonic with acetone, prepared grapheme material with monolithic layer distribution.At high vacuum (1.33x10
-10Pa), under high temperature (1300 ℃) environment, epitaxial growth method capable of using goes out one deck graphene film in the SiC surface growth.At C
2H
4Under the atmosphere, vapour deposition process capable of using has deposited a layer graphene at polycrystalline Ni substrate surface.Likewise at SiO
2Modify the layer of Ni film in the/Si substrate, at Ar and H
2After carrying out the roasting pre-treatment in the gas mixture, using CH
4And H
2Can grow a layer graphene under the atmosphere.Reduction-oxidation graphite method makes the suitability for industrialized production Graphene become possibility.This method is that graphite is generated graphite oxide through peroxo-, with ultra-sonic dispersion method in graphite oxide pyrolysis expansion that generates or the solution, prepares stable accurate two dimensional oxidation graphite suspension, forms grapheme material through reduction again.But graphite oxide needs under strong acid condition, could form after the long-time reaction usually.
It is generally acknowledged that the graphite oxide two-dimensional layer space structure that is as the criterion combines with strong covalent bond in the layer, interlayer contains a large amount of oxygen-containing functional groups and is connected with weak hydrogen bond.Graphite is the stronger material of a kind of hydrophobic nature, compares with it, has a large amount of oxygen-content active chemical groups in the graphite oxide, makes graphite oxide have stronger wetting ability, in polar solvent, disperses to form stable sols easily.In addition, after graphite was oxidized to hydrophilic graphite oxide by strong oxidizer, its interlamellar spacing increased, and increased to the 0.7-1.2nm after the oxidation by the 0.335nm before the oxidation.Apply certain external force, can graphene oxide dissociated out from the constraint of the Van der Waals force of graphite oxide forms the graphene oxide sheet.
Summary of the invention
The technical problem that the present invention will solve is; Provide a kind of pollution-free; Graphene preparation method easily fast; Be particularly related to electrochemical method metallic lithium is embedded graphite, adopt chemical process to produce volumetric expansion then and cause graphite linings to separate the method for preparing Graphene at graphite layers formation compound.
Be the technical solution problem, the invention provides a kind of preparation method of grapheme material, may further comprise the steps:
(1) methylated cellulose aqueous solution with natural flake graphite and 5wt% carries out mechanically mixing, is modulated into to be coated on the aluminium sheet behind the paste and to dry in the shade, and wherein the mass ratio of graphite and methylcellulose gum is 90: 10; Then at 100Kg cm
-2The moulding of pressure pressed, obtain negative electrode after the vacuum-drying;
(2) be positive electrode with the lithium sheet, negative electrode and anodic electrode materials side are fixed in airtight electrolyzer both sides in opposite directions, inject electrolytic solution, constitute embedding lithium electrolyzer;
Electrolytic solution is with LiPF
6Being solute, is that the miscellany of 4: 2: 4 NSC 11801, methyl carbonate and methylcarbonate is a solvent with mass ratio, the LiPF in the electrolytic solution
6Concentration be 1mol L
-1
(3) adopt constant current or constant voltage power supply that above-mentioned electrolyzer is charged and implement negative electrode embedding lithium, form carbon lithium intercalation compound LiC
6
(4) with carbon lithium intercalation compound LiC
6Place water vapour or water surrounding, make lithium and water reaction in the graphite generate hydrogen and Lithium Hydroxide MonoHydrate;
(5) solid substance that forms in the step (4) is peeled off from aluminium sheet, placed pure water to carry out ultrasonic cleaning, obtain the Graphene product after filtration, the drying.
Among the present invention, reaction described in the step (4) is carried out in nitrogen protection atmosphere.
Among the present invention, reaction described in the step (4) realizes through following mode: with carbon lithium intercalation compound LiC
6Change in the container, at the uniform velocity continue to drip pure water with the speed less than 1ml/min and take place until the no hydrogen bubble, the expression reaction finishes.
Among the present invention, reaction described in the step (4) realizes through following mode: with carbon lithium intercalation compound LiC
6Change in the container, this container places 100 ℃ of constant temperature oil baths; The water vapour that infeeds 100 ℃ with the speed less than 1ml/min continuously produces until no hydrogen, and the expression reaction finishes.
Among the present invention; Mode with electrochemistry embedding lithium embeds graphite layers with the metallic lithium atom, can react the principle that generates Lithium Hydroxide MonoHydrate and hydrogen with water according to metallic lithium, produces air pressure in graphite layers; The bulging force that causes causes the graphite layers molecular scission, and the graphite individual layer is peeled off.The Lithium Hydroxide MonoHydrate that remains on the graphite linings can be avoided forming graphite-structure again forming molecular linkage again between the monolithic graphite after the release hydrogen.But ultrasonic cleaning and subsequently filtration wash-out Lithium Hydroxide MonoHydrate and MC obtain pure Graphene product after the drying.
The beneficial effect that the present invention has:
The present invention utilizes graphite can carry out the characteristic of electrochemistry embedding lithium, forms a kind of carbon lithium intercalation compound.The air pressure that utilizes the hydrogen of metallic lithium and water reaction generation and produce carries out peeling off of plumbago single slice.The ionogen that electrochemistry embedding lithium uses can recycle.Being equipped with Graphene with reduction-oxidation graphite legal system compares; The present invention prepares in the process of Graphene and need not strong acid; In the relatively short time, can lithium be embedded graphite layers, form graphite oxide and then need use strong acid and graphite to react for a long time, be difficult to control the level of response of graphite oxide.Electrochemistry embedding lithium then can form the amount of carbon lithium intercalation compound according to the charge volume accurate calculation, thereby more helps the control of reacting and carry out production quality control.Preparing highly purified Graphene can be widely used in fields such as nanometer electronic device, electro-conductive material, photon sensor, light-weight high-strength materials.
Description of drawings
Fig. 1 is the airtight embedding lithium electrolyzer sketch plan that uses among the embodiment two.
Fig. 2 is the Graphene stereoscan photograph of embodiment three preparations.
Reference numeral among Fig. 1 is: 1 airtight embedding lithium electrolyzer shell, 2 aluminium sheets, 3 graphite and methylcellulose gum mixture layer, 4 electrolytic solution, 5 hollow clapboards, 6 lithium sheets, 7 anodes, 8 negative electrodes.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail:
Embodiment one: the graphite cathode preparation
Got purity and be 99.99% crystalline flake graphite and methylcellulose gum (MC) aqueous solution (5wt%) mechanically mixing 30 minutes, and be modulated into paste, crystalline flake graphite and MC mass ratio are 90: 10, are coated on the aluminium sheet, dry in the shade; At 100Kgcm
-2The moulding of pressure pressed, obtained graphite cathode in 3 hours 120 ℃ of following vacuum-dryings.
Embodiment two: graphite embedding lithium
With the lithium sheet is positive electrode, and negative electrode and anodic electrode materials side are fixed in airtight electrolyzer both sides in opposite directions, injects electrolytic solution, constitutes embedding lithium electrolyzer, as shown in Figure 1.Negative electrode and anodic are long and wide to be respectively 5 and 2 centimetres.Cathode coverage crystalline flake graphite 0.5 gram, electrolytic solution is with LiPF
6Be solute, the miscellany of NSC 11801, methyl carbonate and methylcarbonate is a solvent, NSC 11801: methyl carbonate: the mass ratio of methylcarbonate is 4: 2: 4, the LiPF in the electrolytic solution
6Concentration be 1mol L
-1
With 18.6mA/cm
2Current density carry out constant current charge, carry out the embedding lithium.Charged 10 hours, and formed carbon lithium intercalation compound LiC on the negative electrode
6
Embodiment three: Graphene preparation ()
Get the carbon lithium intercalation compound LiC that obtains among the embodiment two
6Powder 0.5 gram places in the three neck round-bottomed flasks, charges into high pure nitrogen (purity 99.999%), makes to be full of nitrogen atmosphere in the flask, drips pure water in round-bottomed flask with the speed less than 1ml/min then.This moment LiC
6With the water generation hydrogen that reacts.Continuing to drip pure water does not produce to there being bubble again.Flask is moved to the UW tank carry out ultrasonic cleaning, pass through suction filtration, clean suction filtration more again, obtain filter cake.With obtaining high purity graphite alkene behind the filtration cakes torrefaction, as shown in Figure 2.
Embodiment four: Graphene preparation (two)
Got purity and be 99.99% crystalline flake graphite and methylcellulose gum (MC) aqueous solution (5wt%) mechanically mixing 30 minutes, and be modulated into paste, crystalline flake graphite and MC mass ratio are 90: 5, are coated on the aluminium sheet, dry in the shade; At 100Kgcm
-2The moulding of pressure pressed, obtained graphite cathode in 5 hours 120 ℃ of following vacuum-dryings.
With the lithium sheet is positive electrode, and negative electrode and anodic electrode materials side are fixed in airtight electrolyzer both sides in opposite directions, injects electrolytic solution, constitutes embedding lithium electrolyzer.Negative electrode and anodic are long and wide to be respectively 5 and 2 centimetres.Cathode coverage crystalline flake graphite 0.5 gram, electrolytic solution is with LiPF
6Be solute, the miscellany of NSC 11801, methyl carbonate and methylcarbonate is a solvent, NSC 11801: methyl carbonate: the mass ratio of methylcarbonate is 4: 2: 4, the LiPF in the electrolytic solution
6Concentration be 1mol L
-1
Anode and cathode voltage is set at 0.3V, implements constant voltage charge, carry out the embedding lithium.Charged 5 hours, and formed carbon lithium intercalation compound LiC on the negative electrode
6Solid substance on the aluminium sheet is peeled off, placed in the three neck round-bottomed flasks, charge into high pure nitrogen (purity 99.999%), make to be full of nitrogen atmosphere in the flask, then to infeed 100 ℃ water vapour continuously less than the speed of 1ml/min.Round-bottomed flask places constant temperature oil bath, and control reaction temperature is 100 ℃.This moment LiC
6With the water vapour generation hydrogen that reacts.React after 30 minutes, add 50 milliliters of pure water, flask is moved to the UW tank carry out ultrasonic cleaning, pass through suction filtration, clean suction filtration more again, obtain filter cake.With obtaining high purity graphite alkene behind the filtration cakes torrefaction.
What more than announce at last, only is specific embodiment of the present invention.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (4)
1. the preparation method of a grapheme material is characterized in that, may further comprise the steps:
(1) methylated cellulose aqueous solution with natural flake graphite and 5wt% carries out mechanically mixing, is modulated into to be coated on the aluminium sheet behind the paste and to dry in the shade, and wherein the mass ratio of graphite and methylcellulose gum is 90: 10; Then at 100Kg cm
-2The moulding of pressure pressed, obtain negative electrode after the vacuum-drying;
(2) be positive electrode with the lithium sheet, negative electrode and anodic electrode materials side are fixed in airtight electrolyzer both sides in opposite directions, inject electrolytic solution, constitute embedding lithium electrolyzer;
Electrolytic solution is with LiPF
6Being solute, is that the miscellany of 4: 2: 4 NSC 11801, methyl carbonate and methylcarbonate is a solvent with mass ratio, the LiPF in the electrolytic solution
6Concentration be 1mol L
-1
(3) adopt constant current or constant voltage power supply that above-mentioned electrolyzer is charged and implement negative electrode embedding lithium, form carbon lithium intercalation compound LiC
6
(4) with carbon lithium intercalation compound LiC
6Place water vapour or water surrounding, make lithium and water reaction in the graphite generate hydrogen and Lithium Hydroxide MonoHydrate;
(5) solid substance that forms in the step (4) is peeled off from aluminium sheet, placed pure water to carry out ultrasonic cleaning, obtain the Graphene product after filtration, the drying.
2. the preparation method of grapheme material according to claim 1 is characterized in that, reaction described in the step (4) is carried out in nitrogen protection atmosphere.
3. the preparation method of grapheme material according to claim 1 is characterized in that, reaction described in the step (4) realizes through following mode: with carbon lithium intercalation compound LiC
6Change in the container, at the uniform velocity continue to drip pure water with the speed less than 1ml/min and take place until the no hydrogen bubble, the expression reaction finishes.
4. the preparation method of grapheme material according to claim 1 is characterized in that, reaction described in the step (4) realizes through following mode: with carbon lithium intercalation compound LiC
6Change in the container, this container places 100 ℃ of constant temperature oil baths; The water vapour that infeeds 100 ℃ with the speed less than 1ml/min continuously produces until no hydrogen, and the expression reaction finishes.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102583356A (en) * | 2012-03-20 | 2012-07-18 | 无锡第六元素高科技发展有限公司 | Method for transferring and washing graphene film |
| CN102923697A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Method for preparing graphene energy storing material through electrochemical cathodic disbonding |
| CN103326002A (en) * | 2013-06-26 | 2013-09-25 | 冯林杰 | Preparation method of graphene and ferrous disulfide composite positive electrode material |
| CN103332684A (en) * | 2013-07-12 | 2013-10-02 | 海南光宇生物科技有限公司 | A kind of preparation method of graphene |
| CN103794756A (en) * | 2012-11-02 | 2014-05-14 | 海洋王照明科技股份有限公司 | Lithium-pre-embedded graphene pole piece, preparation method thereof and applications thereof |
| CN104058395A (en) * | 2014-07-11 | 2014-09-24 | 武汉理工大学 | Method for preparing graphene by carrying out ultrasonic treatment on lithium intercalated graphite |
| CN104860311A (en) * | 2015-05-26 | 2015-08-26 | 广东烛光新能源科技有限公司 | Preparation method of graphene |
| CN104909360A (en) * | 2015-05-26 | 2015-09-16 | 广东烛光新能源科技有限公司 | Preparation method for graphene |
| CN105097293A (en) * | 2015-08-24 | 2015-11-25 | 中国科学院电工研究所 | Lithium pre-embedding method of negative electrode of lithium ion capacitor |
| WO2017100968A1 (en) * | 2015-12-14 | 2017-06-22 | Baoshan Iron & Steel Co., Ltd. | Graphene oxide and method of production thereof |
| CN111252757A (en) * | 2019-10-10 | 2020-06-09 | 中国科学院生态环境研究中心 | Method for preparing graphene by using waste lithium ion power battery |
| CN112573511A (en) * | 2020-12-03 | 2021-03-30 | 铜仁学院 | Simple preparation method of graphene |
| CN113816368A (en) * | 2021-10-26 | 2021-12-21 | 深圳烯材科技有限公司 | Method for preparing graphene oxide by electrolyzing muddy graphite interlayer compound |
| CN114555520A (en) * | 2019-11-15 | 2022-05-27 | 株式会社Lg新能源 | Preparation method of graphene nanosheet |
| CN115650223A (en) * | 2022-08-30 | 2023-01-31 | 福建华峰新材料有限公司 | Fractal-aggregated graphene oxide nanoparticles and preparation and application thereof |
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| CN102583356A (en) * | 2012-03-20 | 2012-07-18 | 无锡第六元素高科技发展有限公司 | Method for transferring and washing graphene film |
| CN103794756A (en) * | 2012-11-02 | 2014-05-14 | 海洋王照明科技股份有限公司 | Lithium-pre-embedded graphene pole piece, preparation method thereof and applications thereof |
| CN102923697A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Method for preparing graphene energy storing material through electrochemical cathodic disbonding |
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| CN103332684A (en) * | 2013-07-12 | 2013-10-02 | 海南光宇生物科技有限公司 | A kind of preparation method of graphene |
| CN104058395A (en) * | 2014-07-11 | 2014-09-24 | 武汉理工大学 | Method for preparing graphene by carrying out ultrasonic treatment on lithium intercalated graphite |
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| CN108602678A (en) * | 2015-12-14 | 2018-09-28 | 宝山钢铁股份有限公司 | Graphene oxide and its production method |
| KR20180122320A (en) * | 2015-12-14 | 2018-11-12 | 바오샨 아이론 앤 스틸 유한공사 | Graphene oxide, its preparation method and product |
| KR102505202B1 (en) | 2015-12-14 | 2023-03-02 | 바오샨 아이론 앤 스틸 유한공사 | Graphene oxide, manufacturing method and product thereof |
| CN111252757A (en) * | 2019-10-10 | 2020-06-09 | 中国科学院生态环境研究中心 | Method for preparing graphene by using waste lithium ion power battery |
| CN114555520A (en) * | 2019-11-15 | 2022-05-27 | 株式会社Lg新能源 | Preparation method of graphene nanosheet |
| CN114555520B (en) * | 2019-11-15 | 2024-01-02 | 株式会社Lg新能源 | Preparation method of graphene nanosheets |
| CN112573511A (en) * | 2020-12-03 | 2021-03-30 | 铜仁学院 | Simple preparation method of graphene |
| CN113816368A (en) * | 2021-10-26 | 2021-12-21 | 深圳烯材科技有限公司 | Method for preparing graphene oxide by electrolyzing muddy graphite interlayer compound |
| CN115650223A (en) * | 2022-08-30 | 2023-01-31 | 福建华峰新材料有限公司 | Fractal-aggregated graphene oxide nanoparticles and preparation and application thereof |
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