CN102874798A - Method for preparing graphene - Google Patents
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- CN102874798A CN102874798A CN2012103421569A CN201210342156A CN102874798A CN 102874798 A CN102874798 A CN 102874798A CN 2012103421569 A CN2012103421569 A CN 2012103421569A CN 201210342156 A CN201210342156 A CN 201210342156A CN 102874798 A CN102874798 A CN 102874798A
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Abstract
The invention discloses a method for preparing graphene. The method comprises the following steps of: preparing a foaming agent solution of which the concentration is 0.2 to 20 weight percent; soaking expanded graphene into the foaming agent solution at the concentration of 0.1 to 10 weight percent; stirring for 0.1 to 5h; heating to the temperature of 50 to 100 DEG C under the stirring condition, drying to remove a solvent so as to obtain the expanded graphene filled with the foaming agent; and keeping the expanded graphene filled with the foaming agent at the temperature of 100 to 500 DEG C for 5 to 60 minutes to obtain the graphene with high performance. The method has the advantages that the method is easy to operate, and large-scale production is easily realized.
Description
Technical field
The invention belongs to a kind of technology of preparing of Graphene, particularly a kind of cryochemistry reaction Aided Physical dissociates and prepares the method for Graphene.
Background technology
Graphene has high electric transmission speed because of its unique two dimensional crystal structure, and very excellent electricity, mechanics, calorifics and magnetic performance, is very widely novel material of a kind of purposes.Graphene has potential application prospect at numerous areas, and therefore relevant fundamental research and applied research have become the focus of various countries scientist research.
Since Graphene was found, the preparation of Graphene was the focus that people study always.Present preparation method mainly contains the mechanically peel method, epitaxial growth method, chemical vapour deposition and chemical reduction method.Wherein the chemical preparation Graphene is to be known as at present the method that might realize scale operation, but this method also comes with some shortcomings.The method production cost is higher on the one hand, and the method has been destroyed the Two-dimensional electron structure of graphite in process of production on the other hand, and its excellent chemical physics performance is had a greatly reduced quality.
The technology of preparing of relevant Graphene, existing a large amount of patent literatures.Such as Chinese patent (application number: 201010627679.1) proposed a kind of cryochem process for preparing Graphene, this law technology feature is that graphene oxide take chemical oxidation preparation is as raw material, take sodium borohydride as reductive agent, by assisting of catalyzer, reduction to graphene oxide, oxygen-containing functional group on the graphene oxide (epoxy, hydroxyl, carboxyl and carbonyl) is removed, made Graphene.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, the intercalator fast decoupled is realized peeling off first of graphite intercalation compound, obtains first overburden; 3. above-mentioned first overburden is adopted secondary intercalation method or mild oxidation method, 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 high-quality graphene, it is characterized in that using with halogen or metal halide as the graphite intercalation compound of intercalator as raw material, ultrasonic peeling off combines in expansion and the solvent in oxalic acid or superoxol, the preparation Graphene.At first the graphite intercalation compound powder is joined concentration more than 15wt% oxalic acid or superoxol in carry out expansion process, obtain the quasiflake graphite alkene aggregate of high level expansion.Then, in the aqueous solution or organic solution of organic solvent or various tensio-active agents, ultra-sonic oscillation were processed 1 minute～5 hours, realized peeling off, and Graphene is dispersed in forms graphene solution in the solvent with this quasiflake graphite alkene aggregate.Utilize spraying drying or cryodesiccated method, behind removal organic solvent or the various tensio-active agent, can obtain graphene powder.
Existing Graphene technology of preparing process more complicated, graphite linings carbon can participate in chemical reaction in the preparation process, thereby can be more residual in the gained Graphene be difficult to remove peel off auxiliary agent.In addition, strong oxidizing reaction makes that oxygen-containing functional group increases in the graphite flake layer, also be difficult to thorough removal when restoring, and redox reaction also can be destroyed the two-dirnentional structure of carbon atomic layer.
Summary of the invention
The purpose of this invention is to provide a kind of simple to operate, the graphene preparation method of easily accomplishing scale production.
The present invention prepares Graphene take expanded graphite as raw material by the chemical reaction up-stripping.By flooding in the solution that expanded graphite is added whipping agent, residue is under 100-500 ℃ condition rapid thermal process 5-60 minute after the solvent evaporated, makes Graphene.
The concrete preparation method of the present invention is as follows:
(1) compound concentration is the foaming agent solution of 0.2-20wt%, and expanded graphite is immersed in the foaming agent solution by 0.1-10wt% concentration, stirs 0.1-5 hour, and is last, under agitation condition, is heated to 50-100
oThe C solvent evaporated has obtained filling the expanded graphite of whipping agent;
(2) with the expanded graphite that contains whipping agent of step (1) preparation under 100-500 ℃, constant temperature 5-60 minute, can make the Graphene of excellent performance.
Aforesaid whipping agent comprises one or more of soluble carbonate salt, supercarbonate, ammonium salt, urea, azo-compound, sulfonyl hydrazines compound and nitroso compound.
Aforesaid soluble carbonate salt is yellow soda ash, salt of wormwood or volatile salt.
Aforesaid supercarbonate is sodium bicarbonate, saleratus or Calcium hydrogen carbonate;
Aforesaid ammonium salt is ammonium nitrate, ammonium sulfate, ammonium phosphate, chlorination or ammonium chlorate;
Aforesaid azo-compound is Cellmic C 121 or Diisopropyl azodicarboxylate;
Aforesaid sulfonyl hydrazines compound is toluene sulfonyl hydrazide, benzol sulfohydrazide or 4,4'-OBSH;
Aforesaid take nitroso compound as N'-dinitrosopentamethlyene tetramine.
The present invention compared with prior art has following advantage:
Graphene preparation method simple to operate, as easily to accomplish scale production.
1, the Graphene physical and chemical performance of present method preparation is close to the Graphene of mechanically peel, and with low cost, easily is applied to scale operation.
2, simple to operate, and the graphene-structured defective of preparation graphene sheet layer mean thickness few and preparation is the 0.02-5%(massfraction less than 1nm, oxygen level).
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 below 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.What be necessary to illustrate is for the member of ordinary skill in the art, and 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 aqueous sodium carbonate 200ml of preparation 20wt% is scattered in 20 gram expanded graphites in the mentioned solution under agitation condition, stirs 30 minutes, then 60
oSolvent evaporated under the C condition is collected product.In 150 ℃ of lower maintenances 5 minutes, the graphene sheet layer mean thickness 0.54nm, the oxygen level that obtain are the 3.42%(massfraction with the evaporate to dryness product).
Embodiment 2
The ammonium carbonate solution 200ml of preparation 5wt% is scattered in 1 gram expanded graphite in the mentioned solution under agitation condition, stirs 6 minutes.Then solvent evaporated under 50 ℃ of conditions is collected product.With the evaporate to dryness product in 100 ℃ of lower maintenances 10 minutes, obtain lamella mean thickness 0.94nm, oxygen level is the 3.71%(massfraction) Graphene.
Embodiment 3
The aqueous ammonium nitrate solution 200ml of preparation 15wt% is scattered in 10 gram expanded graphites in the mentioned solution under agitation condition, stirs 180 minutes, then 90
oSolvent evaporated under the C condition is collected product.With the evaporate to dryness product in 300 ℃ of lower maintenances 5 minutes, obtain lamella mean thickness 0.65nm, oxygen level is the 0.12%(massfraction) Graphene.
Embodiment 4
Preparation 0.2wt% Diisopropyl azodicarboxylate ethanolic soln 200ml is scattered in 0.2 gram expanded graphite in the mentioned solution under agitation condition, stirs 240 minutes, then 60
oSolvent evaporated under the C condition is collected product.With the evaporate to dryness product in 270 ℃ of lower maintenances 9 minutes, obtain lamella mean thickness 0.84nm, oxygen level is the 0.78%(massfraction) Graphene.
Embodiment 5
The N' of preparation 2wt%-dinitrosopentamethlyene tetramine ethanolic soln 200ml,, 1 gram expanded graphite is scattered in the mentioned solution under agitation condition, stirred 300 minutes, then 80
oSolvent evaporated under the C condition is collected product.With the evaporate to dryness product in 200 ℃ of lower maintenances 50 minutes, obtain lamella mean thickness 0.89nm, oxygen level is the 1.62%(massfraction) Graphene.
Embodiment 6
The Cellmic C 121 hydrothermal solution 200ml of preparation 10wt%,, 1 gram expanded graphite is scattered in the mentioned solution under agitation condition, stirred 150 minutes, then 100
oSolvent evaporated under the C condition is collected product.With the evaporate to dryness product in 500 ℃ of lower maintenances 30 minutes, obtain lamella mean thickness 0.56nm, oxygen level is the 0.05%(massfraction) Graphene.
Embodiment 7
Preparation contains the ammonium nitrate of 15wt% and the ammonium carbonate solution 200ml of 5wt%, and 10 gram expanded graphites are scattered in the mentioned solution under agitation condition, stirs 180 minutes, then 90
oSolvent evaporated under the C condition is collected product.With the evaporate to dryness product in 300 ℃ of lower maintenances 25 minutes, obtain lamella mean thickness 0.59nm, oxygen level is the 1.32%(massfraction) Graphene.
Embodiment 8
Preparation contains the ammonium nitrate of 15wt% and the sodium bicarbonate aqueous solution 200ml of 5wt%, and 10 gram expanded graphites are scattered in the mentioned solution under agitation condition, stirs 180 minutes, then 90
oSolvent evaporated under the C condition is collected product.With the evaporate to dryness product in 300 ℃ of lower maintenances 50 minutes, obtain lamella mean thickness 0.50nm, oxygen level is the 1.96%(massfraction) Graphene.
Embodiment 9
The benzol sulfohydrazide ethanolic soln 50ml of 2wt% is prepared in preparation, contains the sodium bicarbonate aqueous solution 100ml of 5wt%, contains the aqueous sodium carbonate 50ml of 1wt%, mix three kinds of solution and form mixed solution, 10 gram expanded graphites are scattered in the mentioned solution under agitation condition, stirred 180 minutes, then 90
oSolvent evaporated under the C condition is collected product.With the evaporate to dryness product in 300 ℃ of lower maintenances 40 minutes, obtain lamella mean thickness 0.84nm, oxygen level is the 2.01%(massfraction) Graphene.
Embodiment 10
The benzol sulfohydrazide ethanolic soln 50ml of preparation preparation 1wt%, 0.1wt% Diisopropyl azodicarboxylate ethanolic soln 100ml, the aqueous sodium carbonate 50ml that contains 1wt%, mix three kinds of solution and form mixed solution, 10 gram expanded graphites are scattered in the mentioned solution under agitation condition, stirred 180 minutes, then 90
oSolvent evaporated under the C condition is collected product.With the evaporate to dryness product in 300 ℃ of lower maintenances 60 minutes, obtain lamella mean thickness 0.99nm, oxygen level is the 1.93%(massfraction) Graphene.
Claims (8)
1. a method for preparing Graphene is characterized in that comprising the steps:
(1) compound concentration is the foaming agent solution of 0.2-20wt%, and expanded graphite is immersed in the foaming agent solution by 0.1-10wt% concentration, stirs 0.1-5 hour, and is last, under agitation condition, is heated to 50-100
oThe C solvent evaporated has obtained filling the expanded graphite of whipping agent;
(2) with the expanded graphite that contains whipping agent of step (1) preparation under 100-500 ℃, constant temperature 5-60 minute, can make the Graphene of excellent performance.
2. a kind of method for preparing Graphene as claimed in claim 1 is characterized in that described whipping agent is one or more of soluble carbonate salt, supercarbonate, ammonium salt, urea, azo-compound, sulfonyl hydrazines compound and nitroso compound.
3. a kind of method for preparing 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 method for preparing Graphene as claimed in claim 2 is characterized in that described supercarbonate is sodium bicarbonate, saleratus or Calcium hydrogen carbonate.
5. a kind of method for preparing Graphene as claimed in claim 2 is characterized in that described ammonium salt is ammonium nitrate, ammonium sulfate, ammonium phosphate, chlorination or ammonium chlorate.
6. a kind of method for preparing Graphene as claimed in claim 2 is characterized in that described azo-compound is Cellmic C 121 or Diisopropyl azodicarboxylate.
7. a kind of method for preparing Graphene as claimed in claim 2 is characterized in that described sulfonyl hydrazines compound is toluene sulfonyl hydrazide, benzol sulfohydrazide or 4,4'-OBSH.
8. a kind of method for preparing Graphene as claimed in claim 2 is characterized in that described nitroso compound is N'-dinitrosopentamethlyene tetramine.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103303911A (en) * | 2013-06-27 | 2013-09-18 | 哈尔滨工业大学 | Method for preparing graphene by foaming expansion method |
| CN103435059A (en) * | 2013-08-15 | 2013-12-11 | 汕头保税区三宝光晶云母科技有限公司 | Method for bulking artificially synthesized fluorophlogopite sheet |
| CN103950928A (en) * | 2014-05-22 | 2014-07-30 | 苏州斯迪克新材料科技股份有限公司 | Preparation method of graphene |
| CN103950927A (en) * | 2014-05-21 | 2014-07-30 | 苏州斯迪克新材料科技股份有限公司 | 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 |
| 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 |
| CN110775966A (en) * | 2019-11-21 | 2020-02-11 | 秦皇岛中科瀚祺科技有限公司 | Flexible graphene film and application thereof |
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| CN101746755A (en) * | 2009-12-14 | 2010-06-23 | 重庆大学 | Method for preparing multi-layer graphene |
| CN101774574A (en) * | 2010-01-22 | 2010-07-14 | 湘潭大学 | Preparation method of graphene inorganic nanocomposite |
| CN102431999A (en) * | 2011-09-22 | 2012-05-02 | 中国科学院金属研究所 | Method for preparing high-quality graphene |
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| CN101746755A (en) * | 2009-12-14 | 2010-06-23 | 重庆大学 | Method for preparing multi-layer graphene |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103303911A (en) * | 2013-06-27 | 2013-09-18 | 哈尔滨工业大学 | Method for preparing graphene by foaming expansion method |
| CN103435059A (en) * | 2013-08-15 | 2013-12-11 | 汕头保税区三宝光晶云母科技有限公司 | Method for bulking artificially synthesized fluorophlogopite sheet |
| 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 |
| CN103950927A (en) * | 2014-05-21 | 2014-07-30 | 苏州斯迪克新材料科技股份有限公司 | Preparation method of graphene |
| CN103950927B (en) * | 2014-05-21 | 2016-08-24 | 苏州斯迪克新材料科技股份有限公司 | A kind of preparation method of Graphene |
| CN103950928A (en) * | 2014-05-22 | 2014-07-30 | 苏州斯迪克新材料科技股份有限公司 | 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 |
| CN110775966A (en) * | 2019-11-21 | 2020-02-11 | 秦皇岛中科瀚祺科技有限公司 | Flexible graphene film and application thereof |
| CN110775966B (en) * | 2019-11-21 | 2021-07-27 | 秦皇岛中科瀚祺科技有限公司 | Flexible graphene film and application thereof |
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Application publication date: 20130116 |