CN102372268B - Preparation method of graphene material - Google Patents
Preparation method of graphene material Download PDFInfo
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- CN102372268B CN102372268B CN 201110315932 CN201110315932A CN102372268B CN 102372268 B CN102372268 B CN 102372268B CN 201110315932 CN201110315932 CN 201110315932 CN 201110315932 A CN201110315932 A CN 201110315932A CN 102372268 B CN102372268 B CN 102372268B
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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 preparation method of carbon material Graphene, particularly with electrochemical method metallic lithium is embedded graphite, then adopt chemical process to produce volumetric expansion at graphite layers formation compound and cause graphite linings to separate the method for preparing Graphene.
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, consists of laminate structure, has complete stratiform cleavage characteristic.Be separated by between layers in the graphite crystal larger, combine with Van der Waals force, cleavage surface is take molecular linkage as main, 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 take molecular linkage as main, can embed lithium atom, therefore also be negative material commonly used in the lithium ion battery.Following electrochemical redox reaction occurs 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 peel off out from graphite material, carbon atom arrangement have cellular or the regular hexagon structure, is the two-dirnentional structure that carbon atom consists of.The thickness of this graphite crystal film only has 0.335nm, thickness only be 200,000 of hairline/, be the elementary cell that makes up other dimension carbonaceous materials (such as zero dimension soccerballene, one dimension carbon nanotube, three-dimensional graphite), have fabulous crystallinity and electric property.2004, the people such as the Novoselov of Univ Manchester UK and Geim utilized the method for mechanically peel successfully to prepare single-layer graphene for the first time in the laboratory, and the Graphene that obtains not only quality is high, and can stable existence in external environment.The successful preparation of Graphene and excellent rigid structure thereof, good electroconductibility brings a revolution will for the fields such as physics, materialogy, electrocatalysis and bio-sensing.
The preparation method of Graphene has multiple, but comparatively ripe synthetic method mainly contains micromechanics stripping method, epitaxial growth method, vapour deposition process and reduction-oxidation graphite method.
The micromechanics stripping method is by a kind of method of mechanical force from the sur-face peeling graphene sheet layer of fresh graphite crystal.After utilizing ionic fluid at first etching to be carried out on the thick high orientation pyrolytic graphite surface of 1mm, sample is attached on the glass substrate, carries out repeatedly tear-off with the method that micromechanics is peeled off with scotch tape.Then, glass substrate is ultrasonic with acetone, prepared the grapheme material with monolithic layer distribution.At high vacuum (1.33x10
-10Pa), under high temperature (1300 ℃) environment, can utilize epitaxial growth method to go out one deck graphene film in the SiC surface growth.At C
2H
4Under the atmosphere, can utilize vapour deposition process to deposit a layer graphene at polycrystalline Ni substrate surface.Similarly at SiO
2Modify the layer of Ni film in the/Si substrate, at Ar and H
2After carrying out roasting pretreatment in the gas mixture, using CH
4And H
2Can grow a layer graphene under the atmosphere.Reduction-oxidation graphite method is so that the suitability for industrialized production Graphene becomes possibility.This method is that graphite is generated graphite oxide through peroxidation, with ultra-sonic dispersion method in the 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 could form after the long-time reaction under strong acid condition usually.
It is generally acknowledged, the graphite oxide two-dimensional layer space structure that is as the criterion, with the strong covalent bond combination, interlayer contains a large amount of oxygen-containing functional groups and is connected with weak hydrogen bond in the layer.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, easily disperses to form stable colloidal sol in polar solvent.In addition, after graphite was oxidized to hydrophilic graphite oxide by strong oxidizer, its interlamellar spacing increased, and increased to 0.7-1.2nm after the oxidation by the 0.335nm before the oxidation.Apply certain external force, graphene oxide can be dissociated out from the constraint of the Van der Waals force of graphite oxide forms graphene oxide sheet.
Summary of the invention
The technical problem to be solved in the present invention is, provide a kind of pollution-free, fast, graphene preparation method easily, be particularly related to electrochemical method metallic lithium is embedded graphite, then adopt chemical process to produce volumetric expansion at graphite layers formation compound and cause graphite linings to separate the method for preparing Graphene.
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 100Kgcm
-2Pressure under compression moulding, obtain negative electrode after the vacuum-drying;
(2) take the lithium sheet as positive electrode, the electrode materials side of negative electrode and anode is fixed in airtight electrolyzer both sides in opposite directions, inject electrolytic solution, consist of embedding lithium electrolyzer;
Electrolytic solution is with LiPF
6Be solute, the mixture take mass ratio as 4: 2: 4 NSC 11801, methyl carbonate and methylcarbonate is as solvent, the LiPF in the electrolytic solution
6Concentration be 1molL-
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;
(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, react described in the step (4) and in nitrogen protection atmosphere, carry out.
Among the present invention, react described in the step (4) and realize in the following way: with carbon lithium intercalation compound LiC
6Change in the container, at the uniform velocity continue to drip pure water direct with the speed less than 1ml/min and produce to the no hydrogen bubble, the expression reaction finishes.
Among the present invention, react described in the step (4) and realize in the following way: with carbon lithium intercalation compound LiC
6Change in the container, this container places 100 ℃ of constant temperature oil baths; Feed continuously 100 ℃ water vapour until no hydrogen produces with the speed less than 1ml/min, the expression reaction finishes.
Among the present invention, with metallic lithium atom indentation graphite layers, can generate with the water reaction principle of lithium hydroxide and hydrogen in the mode of Electrochemical lithiation according to metallic lithium, produce 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 that remains on the graphite linings can be avoided forming graphite-structure again forming molecular linkage between the monolithic graphite after the release hydrogen again.But ultrasonic cleaning and subsequently filtration wash-out lithium hydroxide 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 Electrochemical lithiation, 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 Electrochemical lithiation uses can recycle.Compare with the standby Graphene of reduction-oxidation graphite legal system, the present invention prepares in the process of Graphene and need not strong acid, lithium can be embedded graphite layers within the relatively short time, forming graphite oxide then needs to use strong acid and graphite to react for a long time, is difficult to control the level of response of graphite oxide.Electrochemical lithiation then can form according to the charge volume accurate calculation amount of carbon lithium intercalation compound, thereby more is conducive to the control of reacting and carries 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
-2Pressure under compression moulding, obtained graphite cathode in 3 hours 120 ℃ of lower vacuum-dryings.
Embodiment two: graphite embedding lithium
Take the lithium sheet as positive electrode, the electrode materials side of negative electrode and anode is fixed in airtight electrolyzer both sides in opposite directions, inject electrolytic solution, consist of embedding lithium electrolyzer, as shown in Figure 1.The length of negative electrode and anode and widely be respectively 5 and 2 centimetres.Cathode coverage crystalline flake graphite 0.5 gram, electrolytic solution is with LiPF
6Be solute, the mixture of NSC 11801, methyl carbonate and methylcarbonate is solvent, NSC 11801: methyl carbonate: the mass ratio of methylcarbonate is 4: 2: 4, the LiPF in the electrolytic solution
6Concentration be 1molL-
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, is filled with high pure nitrogen (purity 99.999%), makes to be full of nitrogen atmosphere in the flask, then drips pure water in round-bottomed flask with the speed less than 1ml/min.This moment LiC
6Give birth to reaction with steeping in water for reconstitution and produce hydrogen.Continue to drip pure water extremely again without Bubble formation.Flask is moved to ultrasonic sink carry out ultrasonic cleaning, pass through suction filtration, clean again suction filtration again, obtain filter cake.High purity graphite alkene will be obtained, as shown in Figure 2 behind the filtration cakes torrefaction.
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
-2Pressure under compression moulding, obtained graphite cathode in 5 hours 120 ℃ of lower vacuum-dryings.
Take the lithium sheet as positive electrode, the electrode materials side of negative electrode and anode is fixed in airtight electrolyzer both sides in opposite directions, inject electrolytic solution, consist of embedding lithium electrolyzer.The length of negative electrode and anode and widely be respectively 5 and 2 centimetres.Cathode coverage crystalline flake graphite 0.5 gram, electrolytic solution is with LiPF
6Be solute, the mixture of NSC 11801, methyl carbonate and methylcarbonate is solvent, NSC 11801: methyl carbonate: the mass ratio of methylcarbonate is 4: 2: 4, the LiPF in the electrolytic solution
6Concentration be 1molL-
1
Anode and cathode voltage is set as 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, be filled with high pure nitrogen (purity 99.999%), make to be full of nitrogen atmosphere in the flask, then with the water vapour less than 100 ℃ of the continuous infeeds of the speed of 1ml/min.Round-bottomed flask places constant temperature oil bath, and the control temperature of reaction 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 ultrasonic sink carry out ultrasonic cleaning, pass through suction filtration, clean again suction filtration again, obtain filter cake.High purity graphite alkene will be obtained behind the filtration cakes torrefaction.
At last, above announcement only is specific embodiments of the 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 5 wt % 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 100 Kg cm
-2Pressure under compression moulding, obtain negative electrode after the vacuum-drying;
(2) take the lithium sheet as positive electrode, the electrode materials side of negative electrode and anode is fixed in airtight electrolyzer both sides in opposite directions, inject electrolytic solution, consist of embedding lithium electrolyzer;
Electrolytic solution is with LiPF
6Be solute, the mixture take mass ratio as 4: 2: 4 NSC 11801, methyl carbonate and methylcarbonate is as solvent, the LiPF in the electrolytic solution
6Concentration be 1 mol 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;
(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, reacts described in the step (4) and carries out in nitrogen protection atmosphere.
3. the preparation method of grapheme material according to claim 1 is characterized in that, reacts described in the step (4) and realizes in the following way: with carbon lithium intercalation compound LiC
6Change in the container, at the uniform velocity continue to drip pure water direct with the speed less than 1 ml/min and produce to the no hydrogen bubble, the expression reaction finishes.
4. the preparation method of grapheme material according to claim 1 is characterized in that, reacts described in the step (4) and realizes in the following way: with carbon lithium intercalation compound LiC
6Change in the container, this container places 100 ℃ of constant temperature oil baths; Feed continuously 100 ℃ water vapour until no hydrogen produces with the speed less than 1 ml/min, the expression reaction finishes.
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| CN 201110315932 CN102372268B (en) | 2011-10-18 | 2011-10-18 | Preparation method of graphene material |
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|---|---|---|---|
| CN 201110315932 CN102372268B (en) | 2011-10-18 | 2011-10-18 | Preparation method of graphene material |
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| CN102372268B true CN102372268B (en) | 2013-04-03 |
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583356B (en) * | 2012-03-20 | 2015-01-21 | 无锡格菲电子薄膜科技有限公司 | 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 |
| CN102923697B (en) * | 2012-11-19 | 2014-10-01 | 中南大学 | Method for preparing graphene energy storing material through electrochemical cathodic disbonding |
| CN103326002B (en) * | 2013-06-26 | 2015-11-04 | 国网浙江嵊州市供电公司 | The preparation method of a kind of Graphene-ferrous disulfide composite positive pole |
| CN103332684B (en) * | 2013-07-12 | 2015-05-06 | 海南光宇生物科技有限公司 | 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 |
| CN104860311B (en) * | 2015-05-26 | 2017-01-25 | 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 |
| CN108602678A (en) * | 2015-12-14 | 2018-09-28 | 宝山钢铁股份有限公司 | Graphene oxide and its production method |
| 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 |
| KR20210059387A (en) * | 2019-11-15 | 2021-05-25 | 주식회사 엘지화학 | Method for manufacturing graphene nano-sheet |
| CN112573511A (en) * | 2020-12-03 | 2021-03-30 | 铜仁学院 | Simple preparation method of graphene |
| CN113816368B (en) * | 2021-10-26 | 2023-04-07 | 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693534A (en) * | 2009-10-09 | 2010-04-14 | 天津大学 | Preparation method of single-layer graphene |
| US20110014111A1 (en) * | 2007-08-01 | 2011-01-20 | Mary Anne Leugers | Highly efficient process for manufacture of exfoliated graphene |
| CN102173414A (en) * | 2011-03-18 | 2011-09-07 | 中国地质大学（武汉） | Method for preparing graphene oxide by chemical peeling |
-
2011
- 2011-10-18 CN CN 201110315932 patent/CN102372268B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110014111A1 (en) * | 2007-08-01 | 2011-01-20 | Mary Anne Leugers | Highly efficient process for manufacture of exfoliated graphene |
| CN101693534A (en) * | 2009-10-09 | 2010-04-14 | 天津大学 | Preparation method of single-layer graphene |
| CN102173414A (en) * | 2011-03-18 | 2011-09-07 | 中国地质大学（武汉） | Method for preparing graphene oxide by chemical peeling |
Non-Patent Citations (2)
| Title |
|---|
| 冯颖等.石墨烯片的制备与表征.《新型炭材料》.2011,第26卷(第1期),26-30. |
| 石墨烯片的制备与表征;冯颖等;《新型炭材料》;20110228;第26卷(第1期);26-30 * |
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