CN102874797A - Method for massively preparing high-quality graphene - Google Patents

Method for massively preparing high-quality graphene Download PDF

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Publication number
CN102874797A
CN102874797A CN2012103419893A CN201210341989A CN102874797A CN 102874797 A CN102874797 A CN 102874797A CN 2012103419893 A CN2012103419893 A CN 2012103419893A CN 201210341989 A CN201210341989 A CN 201210341989A CN 102874797 A CN102874797 A CN 102874797A
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graphene
quality graphene
ammonium
preparing high
salt
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CN2012103419893A
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郭向云
王云伟
童希立
靳国强
郭晓宁
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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Abstract

The invention discloses a method for massively preparing high-quality graphene. The method comprises the following steps of mixing a stripping agent and water, preparing a stripping agent solution of which the concentration is 0.2 to 50 weight percent; dispersing expanded graphene into the stripping agent solution in a mass ratio of the expanded graphene to the stripping agent solution of (0.1-10):100, stirring and dipping for 1 to 10h; and performing ultrasonic treatment for 5 to 300 minutes, filtering, washing and drying to obtain the graphene. The method has the advantages that the method is mild in preparation condition and easy to operate, and massive production is easily realized.

Description

A kind of extensive method for preparing high-quality graphene
Technical field
The invention belongs to a kind of technology of preparing of Graphene, particularly a kind of normal temperature or cryochemistry reaction Aided Physical dissociates and prepares on a large scale the method for high-quality graphene.
Background technology
Graphene is the flake graphite material with one or several carbon atomic layer thickness that British scientist was found in 2004.Graphene has high electric transmission speed because of its unique two dimensional crystal structure, and is the known the highest material of physical strength, has very excellent electricity, mechanics, and calorifics and magnetic performance are very widely novel materials of a kind of purposes.Owing to have potential application prospect in various fields, so the basis of Graphene has become the focus that the various countries scientist studies with applied research.
Since Graphene was found, the preparation of Graphene was the focus that people study always.Present preparation method mainly comprises the mechanically peel method, epitaxial growth method, chemical Vapor deposition process, chemistry redox method, the chemistry method etc. of dissociating.It is the most perfect but because the limitation of stripping means, it is not suitable for heavy industrialization and prepares Graphene that the mechanically peel method obtains Graphene.Epitaxial growth method needs the severe condition of high vacuum owing to use monocrystal SiC as substrate, also is difficult to large-scale industrial production.Chemical vapour deposition is that Cu generates Graphene in the substrates such as Ru at monocrystalline or polycrystalline Ni, and the shortcoming of the method is that production cost is too high, is unfavorable for promoting.The standby Graphene of chemistry redox legal system in two steps, at first utilize potassium permanganate, the strong oxidizers such as concentrated nitric acid become graphite oxide (to introduce epoxy at the graphite individual layer graphite oxidation, hydroxyl, the oxygen-containing functional groups such as carbonyl), heating or ultra-sonic dispersion can obtain graphene oxide, then with its reduction, the method is fit to scale operation, but the product defective is more.The chemistry method of dissociating is that graphite oxide is converted into Graphene by the thermal reduction method, and the oxygen-containing functional group of graphite oxide interlayer reacts at a certain temperature, emits rapidly gas so that aluminum oxide/graphite layer when being reduced cleavage open, obtain Graphene.This is a kind of important method for preparing Graphene, and the red grade of the Yang Quan of University Of Tianjin has prepared high-quality Graphene with the dissociate method of graphite oxide of cryochemistry.
Relevant Graphene technology of preparing, existing a large amount of patent reports.Chinese patent (application number: 201010514807.9) proposed a kind of technology of preparing of Graphene, it is characterized in that comprising the steps: 1. graphite being placed the mixing solutions that is consisted of by oxygenant and intercalator, by dipping, mechanical stirring or supersound process, obtain the first insert layer compound; 2. above-mentioned first insert layer compound is processed in air, intercalation reagent fast decoupled is realized peeling off first of graphite intercalation compound, obtains first overburden; 3. above-mentioned first overburden is carried out secondary intercalation or mild oxidation, obtain the secondary intercalation thing; 4. the secondary intercalation thing needs to process in air, obtains the secondary overburden; 5. use liquid phase supersound process, solid phase mechanical mill and ball milling to realize thoroughly peeling off of graphite, obtain the product Graphene.Chinese patent (application number: 201110282370.5) proposed a kind of method for preparing Graphene, the graphite intercalation compound of its feature take halogen or metal halide as intercalator be as raw material, expand in oxalic acid or the superoxol and solvent in the ultrasonic preparation high-quality graphene that combines of peeling off.At first the graphite intercalation compound powder is joined in the oxalic acid or superoxol of concentration more than 15wt%, then under 0~100 ℃ condition, process and carried out expansion process in 0.5~24 hour, obtain the quasiflake graphite alkene aggregate of high level expansion.And then, with gained quasiflake graphite alkene aggregate after the expansion process in the aqueous solution or organic solvent solution of organic solvent or various tensio-active agents, ultrasonic oscillation was processed 1 minute~5 hours, realized peeling off, and Graphene is dispersed in forms graphene solution in the solvent.After utilizing spraying drying or cryodesiccated method to remove organic solvent or various tensio-active agent, can obtain graphene powder.Chinese patent (application number: the 200910191895.0) preparation method of a kind of multi-layer graphene of proposition, its feature is take expanded graphite as raw material, it is dispersed in water or the organic solvent, after ultra-sonic dispersion, solid-liquid separation and drying, prepares the multi-layer graphene that thickness is 1-10nm.
Existing Graphene technology of preparing process is complicated, and graphite is after oxidation, contain more oxygen-containing functional group, can not thoroughly remove oxygen-containing functional group when restoring, also can destroy the two-dimentional physical structure of graphite flake layer, make its mechanical property and conductivity variation, or product thickness (greater than 1nm) more than three carbon atomic layer thickness.
Summary of the invention
It is simple, with low cost to the purpose of this invention is to provide a kind of liquid method, the method for preparing high-quality graphene of accomplishing scale production easily.
The present invention is take expanded graphite as raw material, peels off through the chemical reaction Aided Physical, expanded graphite be impregnated in the solution that contains stripper, and after ultrasonic, filtration, washing and drying treatment, it is few to make defective, the high-quality graphene that electroconductibility is good.
Concrete preparation method of the present invention is as follows:
(1) stripper is mixed with water, preparation concentration is the stripper solution of 0.2%-50wt%;
(2) be 0.1-10:100 by expanded graphite and stripper solution mass ratio, expanded graphite is scattered in the stripper solution stirs dipping, stir and dipping time is 1-10 hour, then by ultrasonic 5-300 minute, after filtration, washing, drying makes Graphene.
Aforesaid stripper is one or more of soluble carbonate salt, supercarbonate, ammonium salt, ammonia, urea, azo-compound or sulfonyl hydrazines compound.
Aforesaid soluble carbonate salt comprises yellow soda ash, salt of wormwood or volatile salt.
Aforesaid supercarbonate comprises sodium bicarbonate, saleratus, bicarbonate of ammonia or Calcium hydrogen carbonate.
Aforesaid ammonium salt comprises ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium chloride or ammonium chlorate.
Aforesaid azo-compound comprises Cellmic C 121, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or N'-dinitrosopentamethlyene tetramine.
Aforesaid sulfonyl hydrazines compound comprises p-toluene sulfonyl hydrazide, benzol sulfohydrazide or 4,4'-OBSH.
The Graphene product thickness of the present invention's preparation is little, and the Graphene number of plies is the 1-3 layer, and thickness is less than 1nm; Oxygen level 0.1-6%(massfraction).
Advantage of the present invention is:
Preparation condition is gentle, peels off expanded graphite by chemical reaction and obtains high-quality Graphene, can at utmost reduce the destruction to the Graphene two-dirnentional structure, and the Graphene product thickness of preparation is little, and the Graphene number of plies is the 1-3 layer, and thickness is less than 1nm; Oxygen level 0.1-6%(massfraction).A kind of method that can be used for the scale operation high-quality graphene simultaneously.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the Graphene product for preparing of the present invention.
Embodiment
Further illustrate characteristics of the present invention in conjunction with example, but be not limited to example.The following stated embodiment has only expressed concentrated embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Be necessary to illustrate be for this area the member of ordinary skill, without departing from the inventive concept of the premise, the improvement that can also make and distortion all belong to protection scope of the present invention.Therefore, claim of the present invention should be as the criterion with claims.
Embodiment 1
The Cellmic C 121 hydrothermal solution 200ml of preparation 10wt%, the 5g expanded graphite is scattered in the mentioned solution, stir and flood 150 minutes ultrasonic 5 minutes, remove unreacted expanded graphite, washing, drying obtain Graphene, lamella mean thickness 0.98nm, oxygen level 2.13%(massfraction).
Embodiment 2
The Diisopropyl azodicarboxylate ethanolic soln 200ml of preparation 15wt%, the 8g expanded graphite is scattered in the mentioned solution, stirring was also flooded 180 minutes, ultrasonic 30 minutes, remove unreacted expanded graphite, washing, dry Graphene, lamella mean thickness 0.75nm, the oxygen level 2.81%(massfraction of getting).
Embodiment 3
The 2,2'-Azobis(2,4-dimethylvaleronitrile) methanol solution 200ml of preparation 12wt%, the 6g expanded graphite is scattered in the mentioned solution, stir and flood 600 minutes ultrasonic 60 minutes, remove unreacted expanded graphite, washing, drying obtain Graphene, lamella mean thickness 0.82 nm, oxygen level 2.63%(massfraction).
Embodiment 4
The ammonium bicarbonate aqueous solution 200ml of preparation 20wt%, the 20g expanded graphite is scattered in the mentioned solution, stir and flood 60 minutes ultrasonic 100 minutes, remove unreacted expanded graphite, washing, drying mainly are Graphenes, lamella mean thickness 0.48 nm, oxygen level 4.94%(massfraction).
Embodiment 5
The ammonium carbonate solution 200ml of preparation 50wt%(, the 20g expanded graphite is scattered in the mentioned solution, stir and flood 120 minutes ultrasonic 30 minutes, remove unreacted expanded graphite, washing, drying mainly are Graphenes, lamella mean thickness 0.92nm, oxygen level 4.36%(massfraction).
Embodiment 6
The N' of preparation 0.2wt%-dinitrosopentamethlyene tetramine ethanolic soln 200ml, the 0.2g expanded graphite is scattered in the mentioned solution, stir and flood 400 minutes ultrasonic 100 minutes, remove unreacted expanded graphite, washing, drying obtain Graphene, lamella mean thickness 0.78nm, oxygen level 0.27%(massfraction).
Embodiment 7
Preparation contains bicarbonate of ammonia and the 45wt% ammonium carbonate solution 200ml of 5wt%, the 20g expanded graphite is scattered in the mentioned solution, stir and flood 250 minutes ultrasonic 240 minutes, remove unreacted expanded graphite, washing, drying obtain Graphene, lamella mean thickness 0.53 nm, oxygen level 5.41%(massfraction).
Embodiment 8
Preparation contains the benzol sulfohydrazide of 8wt% and the N' of 0.2wt%-dinitrosopentamethlyene tetramine ethanolic soln 200ml, the 4g expanded graphite is scattered in the mentioned solution, stir and flood 300 minutes ultrasonic 120 minutes, remove unreacted expanded graphite, washing, drying obtain Graphene, lamella mean thickness 0.98nm, oxygen level 1.13%(massfraction).
Embodiment 9
The preparation 8wt% benzol sulfohydrazide ethanolic soln 200ml, the 4g expanded graphite is scattered in the mentioned solution, stir and flood 300 minutes ultrasonic 120 minutes, remove unreacted expanded graphite, washing, drying obtain Graphene, lamella mean thickness 0.94nm, oxygen level 1.22%(massfraction).
Embodiment 10
The benzol sulfohydrazide ethanolic soln 50ml of preparation 1wt%, the ammonium bicarbonate aqueous solution 150ml that contains wt5%, mix two kinds of solution, the 4g expanded graphite is scattered in the above-mentioned mixing solutions, stirring was also flooded 300 minutes ultrasonic 300 minutes, removed unreacted expanded graphite, and washing, drying obtain Graphene, lamella mean thickness 0.90nm, oxygen level 2.00%(massfraction).
Embodiment 11
The benzol sulfohydrazide ethanolic soln 50ml of preparation 2wt%, the ammonium bicarbonate aqueous solution 100ml that contains 5wt%, the aqueous sodium carbonate 50ml that contains 1wt%, mix three kinds of solution and form mixed solutions, the 4g expanded graphite is scattered in the mentioned solution, stir and flood 300 minutes ultrasonic 180 minutes, remove unreacted expanded graphite, washing, drying obtain Graphene, lamella mean thickness 0.89nm, oxygen level 2.45%(massfraction).
Embodiment 12
Preparation contains the benzol sulfohydrazide ethanolic soln 50ml of 2wt%, the 2,2'-Azobis(2,4-dimethylvaleronitrile) methanol solution 100ml of 6wt%, the ammonium bicarbonate aqueous solution 50ml of 2 wt% mixes three kinds of solution and forms mixed solution, the 4g expanded graphite is scattered in the mentioned solution, stirring was also flooded 300 minutes ultrasonic 240 minutes, removed unreacted expanded graphite, and washing, drying obtain Graphene, lamella mean thickness 0.93nm, oxygen level 2.33%(massfraction).

Claims (7)

1. a method for preparing on a large scale high-quality graphene is characterized in that comprising the steps:
(1) stripper is mixed with water, preparation concentration is the stripper solution of 0.2%-50wt%;
(2) be 0.1-10:100 by expanded graphite and stripper solution mass ratio, expanded graphite is scattered in the stripper solution stirs dipping, stir and dipping time is 1-10 hour, then by ultrasonic 5-300 minute, after filtration, washing, drying makes Graphene.
2. a kind of extensive method for preparing high-quality graphene as claimed in claim 1 is characterized in that described stripper is one or more of soluble carbonate salt, supercarbonate, ammonium salt, ammonia, urea, azo-compound or sulfonyl hydrazines compound.
3. a kind of extensive method for preparing high-quality graphene as claimed in claim 2 is characterized in that described soluble carbonate salt is yellow soda ash, salt of wormwood or volatile salt.
4. a kind of extensive method for preparing high-quality graphene as claimed in claim 2 is characterized in that described supercarbonate is sodium bicarbonate, saleratus, bicarbonate of ammonia or Calcium hydrogen carbonate.
5. a kind of extensive method for preparing high-quality graphene as claimed in claim 2 is characterized in that described ammonium salt is ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium chloride or ammonium chlorate.
6. a kind of extensive method for preparing high-quality graphene as claimed in claim 2 is characterized in that aforesaid azo-compound is Cellmic C 121, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or N'-dinitrosopentamethlyene tetramine.
7. a kind of extensive method for preparing high-quality graphene as claimed in claim 2 is characterized in that described sulfonyl hydrazines compound is p-toluene sulfonyl hydrazide, benzol sulfohydrazide or 4,4'-OBSH.
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Cited By (15)

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Publication number Priority date Publication date Assignee Title
CN103964428A (en) * 2014-05-26 2014-08-06 苏州斯迪克新材料科技股份有限公司 Preparation method of graphene
CN103964426A (en) * 2014-05-15 2014-08-06 苏州斯迪克新材料科技股份有限公司 Method for preparing graphene
CN104609395A (en) * 2013-11-04 2015-05-13 嵇天浩 Graphene and preparation method thereof
CN104973593A (en) * 2015-06-18 2015-10-14 湖南大学 Stripping method of stratified materials
WO2016045035A1 (en) * 2014-09-25 2016-03-31 深圳粤网节能技术服务有限公司 Method for preparing graphene
CN105480965A (en) * 2015-11-26 2016-04-13 中国第一汽车股份有限公司 Preparation method of graphene
CN105502357A (en) * 2015-12-22 2016-04-20 成都新柯力化工科技有限公司 Stripping agent special for preparing graphene through mechanical stripping and preparation method
CN105692602A (en) * 2016-03-08 2016-06-22 上海大学 Method for simply and rapidly preparing thin graphene
CN105916807A (en) * 2013-09-24 2016-08-31 康斯乔最高科学研究公司 Exfoliation of graphite with deep eutectic solvents
CN106698397A (en) * 2015-11-17 2017-05-24 上海驭扬投资有限公司 Method for preparing graphene by means of microwave radiation pretreatment
CN107527746A (en) * 2017-08-04 2017-12-29 湖南国盛石墨科技有限公司 A kind of graphene negative electricity pole piece and its preparation method and application
CN108946715A (en) * 2018-09-28 2018-12-07 嘉兴烯成新材料有限公司 Water soluble starter prepares graphene oxide method
CN110092947A (en) * 2018-01-30 2019-08-06 山东省圣泉生物质石墨烯研究院 A kind of micro-nano cellulose compound, and its preparation method and application
CN113563759A (en) * 2021-07-14 2021-10-29 中国科学院山西煤炭化学研究所 Graphene and nano-silver composite material and preparation method thereof
CN115709989A (en) * 2022-11-14 2023-02-24 中国科学院山西煤炭化学研究所 Method for preparing graphene through large-scale self-adaptive electrochemical stripping, graphene and thermal management film

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Cited By (20)

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Publication number Priority date Publication date Assignee Title
CN105916807A (en) * 2013-09-24 2016-08-31 康斯乔最高科学研究公司 Exfoliation of graphite with deep eutectic solvents
CN104609395A (en) * 2013-11-04 2015-05-13 嵇天浩 Graphene and preparation method thereof
CN104609395B (en) * 2013-11-04 2017-06-06 北京工商大学 Graphene and preparation method thereof
CN103964426A (en) * 2014-05-15 2014-08-06 苏州斯迪克新材料科技股份有限公司 Method for preparing graphene
CN103964426B (en) * 2014-05-15 2016-08-17 苏州斯迪克新材料科技股份有限公司 A kind of preparation method of Graphene
CN103964428A (en) * 2014-05-26 2014-08-06 苏州斯迪克新材料科技股份有限公司 Preparation method of graphene
WO2016045035A1 (en) * 2014-09-25 2016-03-31 深圳粤网节能技术服务有限公司 Method for preparing graphene
CN104973593A (en) * 2015-06-18 2015-10-14 湖南大学 Stripping method of stratified materials
CN104973593B (en) * 2015-06-18 2018-03-30 湖南大学 A kind of stratified material stripping means
CN106698397A (en) * 2015-11-17 2017-05-24 上海驭扬投资有限公司 Method for preparing graphene by means of microwave radiation pretreatment
CN105480965A (en) * 2015-11-26 2016-04-13 中国第一汽车股份有限公司 Preparation method of graphene
CN105502357A (en) * 2015-12-22 2016-04-20 成都新柯力化工科技有限公司 Stripping agent special for preparing graphene through mechanical stripping and preparation method
CN105692602A (en) * 2016-03-08 2016-06-22 上海大学 Method for simply and rapidly preparing thin graphene
CN107527746A (en) * 2017-08-04 2017-12-29 湖南国盛石墨科技有限公司 A kind of graphene negative electricity pole piece and its preparation method and application
CN110092947A (en) * 2018-01-30 2019-08-06 山东省圣泉生物质石墨烯研究院 A kind of micro-nano cellulose compound, and its preparation method and application
CN108946715A (en) * 2018-09-28 2018-12-07 嘉兴烯成新材料有限公司 Water soluble starter prepares graphene oxide method
CN113563759A (en) * 2021-07-14 2021-10-29 中国科学院山西煤炭化学研究所 Graphene and nano-silver composite material and preparation method thereof
CN113563759B (en) * 2021-07-14 2022-11-25 中国科学院山西煤炭化学研究所 Graphene and nano-silver composite material and preparation method thereof
CN115709989A (en) * 2022-11-14 2023-02-24 中国科学院山西煤炭化学研究所 Method for preparing graphene through large-scale self-adaptive electrochemical stripping, graphene and thermal management film
CN115709989B (en) * 2022-11-14 2023-12-01 中国科学院山西煤炭化学研究所 Method for preparing graphene through large-scale self-adaptive electrochemical stripping, graphene and thermal management film

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Application publication date: 20130116