CN103359714A - Preparation method of graphene - Google Patents
Preparation method of graphene Download PDFInfo
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- CN103359714A CN103359714A CN201210093501XA CN201210093501A CN103359714A CN 103359714 A CN103359714 A CN 103359714A CN 201210093501X A CN201210093501X A CN 201210093501XA CN 201210093501 A CN201210093501 A CN 201210093501A CN 103359714 A CN103359714 A CN 103359714A
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Abstract
The invention belongs to the field of graphene, and discloses a preparation method of graphene, which comprises the following steps: preparing chloride intercalated graphite into a chloride intercalated graphite suspension; carrying out heating and ultrasonic treatment on the chloride intercalated graphite suspension to obtain a graphene; filtering the graphene solution, and preparing the filtered graphene and acetone into a graphene suspension; and carrying out ultrasonic and filtration treatment on the graphene suspension at room temperature, and removing chloride to obtain the graphene. By utilizing ultrasonic to strip the chloride intercalated graphite to prepare the graphene, the ultrasonic stripping method disclosed by the invention has the advantages of smaller number of layers of graphene, high yield, simple equipment, and simple and feasible operation, and can easily implement automatic and industrial production; and meanwhile, the graphene prepared by the ultrasonic stripping method has the advantages of fewer defects and complete crystal structure.
Description
Technical field
The present invention relates to the preparation method of Graphene, relate in particular to a kind of ultrasonic method that the muriate intercalated graphite prepares Graphene of peeling off of utilizing.
Background technology
Intercalated graphite just by extensively and profoundly its performance of research and application, possesses again some unique performances because it has kept the good performance of graphite after being found in 1841, can be used for the fields such as conductor, superconductor, battery.Graphene is a kind of Two-dimensional Carbon atomic crystal that the strong K of the peace moral of Univ Manchester UK in 2004 sea nurse (Andre K.Geim) etc. is found; Because structure and the photoelectric property of Graphene uniqueness make it become the study hotspot in the fields such as carbon material, nanotechnology, Condensed Matter Physics and functional materials, have attracted many scientific workers.
At present, the method for preparing Graphene mainly adopts chemical Vapor deposition process, and its prepared Graphene quality is high, but output is few and the poor performance of Graphene.
Summary of the invention
Based on the problems referred to above, problem to be solved by this invention is to provide a kind of preparation method of Graphene.
Technical scheme of the present invention is as follows:
Graphene preparation method provided by the invention is to utilize the muriate intercalated graphite to be raw material, the muriate intercalated graphite is added to the water be made into suspension liquid, utilizes ultrasonic wave that intercalated graphite is peeled off, and through after the cleaning and filtering, just obtains Graphene.Mainly comprise following operation steps:
The muriate intercalated graphite is joined in the beaker, then add deionized water, be made into muriate intercalated graphite suspension liquid under stirring;
Muriate intercalated graphite suspension liquid is heated to 80～90 ℃ carried out ultrasonic 30～60 minutes, obtain graphene solution;
Filtering graphite alkene solution, it is 5～10g/L Graphene suspension liquid that the Graphene after then will filtering again and acetone or alcohol are made into concentration;
Under the room temperature Graphene suspension liquid is filtered after ultrasonic 5～10 minutes, fully peel off intercalated graphite and remove muriate, obtain the Graphene screening; And then with deionized water repeatedly clean, filtering graphite alkene screening, then the Graphene screening after 60 ℃ of lower dry cleanings is 8～12 hours, just obtains Graphene.
The ultrasonic stripping method of the present invention is utilized the ultrasonic method that the muriate intercalated graphite prepares Graphene of peeling off, has the Graphene number of plies few, output is high, equipment is simple, the operation simple and feasible, easily be automated and suitability for industrialized production, simultaneously, ultrasonic stripping method of the present invention makes that the Graphene defective is few and crystalline structure is complete.
Description of drawings
Fig. 1 is preparation technology's schema of preferred embodiment Graphene;
Fig. 2 is the SEM figure of the Graphene that makes of embodiment 1; Wherein, scanning electron microscope adopts the S-3400N-II of Hitachi, and scanning is pressurised into 15kV.
Embodiment
A kind of graphene preparation method that the present embodiment provides as shown in Figure 1, comprises the steps:
S1, the muriate intercalated graphite is joined beaker, then add deionized water, stir the lower muriate intercalated graphite suspension liquid that concentration is 5～10g/L that is made into;
S2, muriate intercalated graphite suspension liquid is heated to 80～90 ℃, and ultrasonic 30～60 minutes, graphene solution obtained;
S3, graphene solution is filtered, Graphene and acetone or alcohol after then will filtering are made into the Graphene suspension liquid that concentration is 5～10g/L again; Preferred acetone;
Under S4, the room temperature Graphene suspension liquid is filtered after ultrasonic 5～10 minutes, obtains the Graphene screening, then with deionized water repeatedly clean, filtering graphite alkene screening, then the Graphene screening after 60 ℃ of lower dry cleanings is 8～12 hours, obtains Graphene.
In the above-mentioned method for preparing Graphene, preferred:
Among the step S1, muriate is at least a in iron(ic) chloride, nickelous chloride, cupric chloride, cobalt chloride, Repone K, lead chloride and the zinc chloride;
Among the step S2, the type of heating of described intercalated graphite suspension liquid adopts heating in water bath, and heating in water bath is to carry out in the ultrasonic cleaning instrument, and this ultrasonic cleaning instrument power is selected 150～400W;
Among the step S4, also comprise the detecting step to chlorion: after using washed with de-ionized water, filtering graphite alkene screening, in the solution detection filtrate with silver ion whether chlorion is arranged at every turn, if have, then continue with washed with de-ionized water, filtering graphite alkene screening, otherwise, stop to clean; Wherein, the preferred silver nitrate solution of silver ion.
In the above-mentioned method for preparing Graphene, the muriate intercalated graphite adopts following method to make:
Take by weighing mass ratio and be 1: 0.8～1.2 graphite and muriate intercalation thing and insert in the silica tube, sealed silica envelope heats up after 460～500 ℃, insulation, and reaction continues 2-6 hour, and reaction is cooled to room temperature after finishing, and namely gets the muriate intercalated graphite.
The ultrasonic stripping method of the present invention is utilized the ultrasonic method that the muriate intercalated graphite prepares Graphene of peeling off, has the Graphene number of plies few, output is high, equipment is simple, the operation simple and feasible, easily be automated and suitability for industrialized production, simultaneously, ultrasonic stripping method of the present invention makes that the Graphene defective is few and crystalline structure is complete.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
1. take by weighing 15g graphite and 12g iron(ic) chloride intercalation thing is inserted in the silica tube, sealed silica envelope heats up after 460 ℃, insulation, and reaction continues 6 hours, and reaction is cooled to room temperature after finishing, and namely gets the iron(ic) chloride intercalated graphite;
2, get 10g iron(ic) chloride intercalated graphite and join beaker, then add the 2L deionized water, stir the lower iron(ic) chloride intercalated graphite suspension liquid that concentration is 5g/L that is made into;
3. beaker is put in the 150W ultrasonic cleaning instrument, and is heated to 90 ℃ and carried out ultrasonic 30 minutes, obtain graphene solution;
4. graphene solution is filtered, then itself and acetone are made into into the suspension liquid that concentration is 5g/L again, room temperature is filtered after ultrasonic 5 minutes again, gets the Graphene screening;
With deionized water repeatedly clean, filtering graphite alkene screening, and detect in the filtrate without chlorion with AgNO3,60 ℃ of lower dry Graphene screenings 12 hours, just obtain Graphene subsequently.
Fig. 1 is the Graphene SEM picture of embodiment 1 preparation.As can be seen from Figure 1, the thickness of the Graphene of sheet is about 1～2nm, and namely approximately 3～6 layers, meet the thickness range of Graphene, be Graphene.
Embodiment 2
1. take by weighing 15g graphite and 15g cupric chloride intercalation thing is inserted in the silica tube, sealed silica envelope heats up after 480 ℃, insulation, and reaction continues 4 hours, and reaction is cooled to room temperature after finishing, and namely gets the cupric chloride intercalated graphite;
2, get 10g cupric chloride intercalated graphite and join beaker, then add the 1L deionized water, stir the lower cupric chloride intercalated graphite suspension liquid that concentration is 10g/L that is made into;
3. beaker is put in the 150W ultrasonic cleaning instrument, and is heated to 80 ℃ and carried out ultrasonic 60 minutes, obtain graphene solution;
4. graphene solution is filtered, then again itself and acetone are made into the suspension liquid that concentration is 10g/L, room temperature is filtered after ultrasonic 10 minutes again, gets the Graphene screening;
With deionized water repeatedly clean, filtering graphite alkene screening, and detect in the filtrate without chlorion with AgNO3,60 ℃ of lower dry Graphene screenings 8 hours, just obtain Graphene subsequently.
Embodiment 3
1. take by weighing 10g graphite and 12g Repone K intercalation thing is inserted in the silica tube, sealed silica envelope heats up after 500 ℃, insulation, and reaction continues 2 hours, and reaction is cooled to room temperature after finishing, and namely gets the Repone K intercalated graphite;
2, get 8g Repone K intercalated graphite and join beaker, then add the 1L deionized water, stir the lower Repone K intercalated graphite suspension liquid that concentration is 8g/L that is made into;
3. beaker is put in the 150W ultrasonic cleaning instrument, and is heated to 85 ℃ and carried out ultrasonic 50 minutes, obtain graphene solution;
4. graphene solution is filtered, then again itself and acetone are made into the suspension liquid that concentration is 8g/L, room temperature is filtered after ultrasonic 8 minutes again, gets the Graphene screening;
With deionized water repeatedly clean, filtering graphite alkene screening, and detect in the filtrate without chlorion with AgNO3, subsequently 60 ℃ lower dry 10 hours, just obtain Graphene.
Embodiment 4
1. take by weighing 10g graphite and 8g cobalt chloride intercalation thing is inserted in the silica tube, sealed silica envelope heats up after 470 ℃, insulation, and reaction continues 5 hours, and reaction is cooled to room temperature after finishing, and namely gets the cobalt chloride intercalated graphite;
2, get 6g cobalt chloride intercalated graphite and join beaker, then add the 1L deionized water, stir the lower cobalt chloride intercalated graphite suspension liquid that concentration is 6g/L that is made into;
3. beaker is put in the 150W ultrasonic cleaning instrument, and is heated to 90 ℃ and carried out ultrasonic 40 minutes, obtain graphene solution;
4. graphene solution is filtered, then again itself and acetone are made into the suspension liquid that concentration is 6g/L, room temperature is filtered after ultrasonic 5 minutes again, gets the Graphene screening;
With deionized water repeatedly clean, filtering graphite alkene screening, and detect in the filtrate without chlorion with AgNO3, subsequently 60 ℃ lower dry 9 hours, just obtain Graphene.
Embodiment 5
1. take by weighing 10g graphite and 10g nickelous chloride intercalation thing is inserted in the silica tube, sealed silica envelope heats up after 480 ℃, insulation, and reaction continues 3 hours, and reaction is cooled to room temperature after finishing, and namely gets the nickelous chloride intercalated graphite;
2, get 8g nickelous chloride intercalated graphite and join beaker, then add the 1L deionized water, stir the lower nickelous chloride intercalated graphite suspension liquid that concentration is 8g/L that is made into;
3. beaker is put in the 150W ultrasonic cleaning instrument, and is heated to 80 ℃ and carried out ultrasonic 60 minutes, obtain graphene solution;
4. graphene solution is filtered, then again itself and ethanol are made into the suspension liquid that concentration is 8g/L, room temperature is filtered after ultrasonic 7 minutes again, gets the Graphene screening;
With deionized water repeatedly clean, filtering graphite alkene screening, and detect in the filtrate without chlorion with AgNO3, subsequently 60 ℃ lower dry 12 hours, just obtain Graphene.
Embodiment 6
1. take by weighing 10g graphite and 8g lead chloride intercalation thing is inserted in the silica tube, sealed silica envelope heats up after 460 ℃, insulation, and reaction continues 5 hours, and reaction is cooled to room temperature after finishing, and namely gets the lead chloride intercalated graphite;
2, get 7g lead chloride intercalated graphite and join beaker, then add the 1L deionized water, stir the lower zinc chloride intercalated graphite suspension liquid that concentration is 7g/L that is made into;
3. beaker is put in the 150W ultrasonic cleaning instrument, and is heated to 85 ℃ and carried out ultrasonic 50 minutes, obtain graphene solution;
4. graphene solution is filtered, then again itself and ethanol are made into the suspension liquid that concentration is 7g/L, room temperature is filtered after ultrasonic 9 minutes again, gets the Graphene screening;
With deionized water repeatedly clean, filtering graphite alkene screening, and detect in the filtrate without chlorion with AgNO3, subsequently 60 ℃ lower dry 9 hours, just obtain Graphene.
Embodiment 7
1. take by weighing 12g graphite and 11g zinc chloride intercalation thing is inserted in the silica tube, sealed silica envelope heats up after 490 ℃, insulation, and reaction continues 3 hours, and reaction is cooled to room temperature after finishing, and namely gets the zinc chloride intercalated graphite;
2, get 9g zinc chloride intercalated graphite and join beaker, then add the 1L deionized water, stir the lower zinc chloride intercalated graphite suspension liquid that concentration is 9g/L that is made into;
3. beaker is put in the 150W ultrasonic cleaning instrument, and is heated to 90 ℃ and carried out ultrasonic 40 minutes, obtain graphene solution;
4. graphene solution is filtered, then again itself and ethanol are made into the suspension liquid that concentration is 9g/L, room temperature is filtered after ultrasonic 10 minutes again, gets the Graphene screening;
With deionized water repeatedly clean, filtering graphite alkene screening, and detect in the filtrate without chlorion with AgNO3, subsequently 60 ℃ lower dry 10 hours, just obtain Graphene.
Should be understood that, above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (5)
1. the preparation method of a Graphene is characterized in that, comprises the steps:
S1, the muriate intercalated graphite is joined beaker, then add deionized water, stir the lower muriate intercalated graphite suspension liquid that concentration is 5～10g/L that is made into;
S2, muriate intercalated graphite suspension liquid is heated to 80～90 ℃, and ultrasonic 30～60 minutes, graphene solution obtained;
S3, graphene solution is filtered, Graphene and acetone or alcohol after then will filtering are made into the Graphene suspension liquid that concentration is 5～10g/L again;
Under S4, the room temperature Graphene suspension liquid is filtered after ultrasonic 5～10 minutes, obtains the Graphene screening, then with deionized water repeatedly clean, filtering graphite alkene screening, then the Graphene screening after 60 ℃ of lower dry cleanings is 8～12 hours, obtains Graphene.
2. the preparation method of Graphene according to claim 1 is characterized in that, among the step S1, described muriate is at least a in iron(ic) chloride, nickelous chloride, cupric chloride, cobalt chloride, Repone K, lead chloride and the zinc chloride.
3. the preparation method of Graphene according to claim 1 is characterized in that, among the step S2, the type of heating of described intercalated graphite suspension liquid adopts heating in water bath.
4. the preparation method of Graphene according to claim 3 is characterized in that, among the step S2, described heating in water bath is to carry out in the ultrasonic cleaning instrument.
5. the preparation method of Graphene according to claim 1, it is characterized in that, among the step S4, also comprise the detecting step to chlorion: after using washed with de-ionized water, filtering graphite alkene screening at every turn, solution with silver ion detects in the filtrate whether chlorion is arranged, if having, then continues with washed with de-ionized water Graphene screening, otherwise, stop to clean.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588195A (en) * | 2013-11-01 | 2014-02-19 | 天津大学 | Preparation method of graphene |
| CN105820514A (en) * | 2016-04-08 | 2016-08-03 | 泰州巨纳新能源有限公司 | Preparation method of high-conductivity graphene-resin composite material |
| CN107934945A (en) * | 2017-12-07 | 2018-04-20 | 西南交通大学 | A kind of method for preparing magnetic graphene using molysite gas phase intercalation and microwave technology |
| CN108640107A (en) * | 2018-07-06 | 2018-10-12 | 广州特种承压设备检测研究院 | A kind of intercalator of quick stripping graphite for high-quality graphene volume production |
| CN108706575A (en) * | 2018-07-06 | 2018-10-26 | 广州特种承压设备检测研究院 | A kind of preparation method of liquid phase ball milling stripping graphene |
| CN109671952A (en) * | 2018-12-21 | 2019-04-23 | 福建翔丰华新能源材料有限公司 | Microcrystalline graphene-based composite conductive slurry for lithium battery and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0311298A2 (en) * | 1987-10-06 | 1989-04-12 | Cabotex Co. Ltd. | Preparing an intercalation compound |
| US5503717A (en) * | 1994-06-13 | 1996-04-02 | Kang; Feiyu | Method of manufacturing flexible graphite |
| US20080206124A1 (en) * | 2007-02-22 | 2008-08-28 | Jang Bor Z | Method of producing nano-scaled graphene and inorganic platelets and their nanocomposites |
| US20110017587A1 (en) * | 2009-07-27 | 2011-01-27 | Aruna Zhamu | Production of chemically functionalized nano graphene materials |
| WO2011081268A1 (en) * | 2009-12-31 | 2011-07-07 | 한국과학기술원 | Method for producing graphenes through the production of a graphite intercalation compound using salts |
-
2012
- 2012-03-31 CN CN201210093501XA patent/CN103359714A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0311298A2 (en) * | 1987-10-06 | 1989-04-12 | Cabotex Co. Ltd. | Preparing an intercalation compound |
| US5503717A (en) * | 1994-06-13 | 1996-04-02 | Kang; Feiyu | Method of manufacturing flexible graphite |
| US20080206124A1 (en) * | 2007-02-22 | 2008-08-28 | Jang Bor Z | Method of producing nano-scaled graphene and inorganic platelets and their nanocomposites |
| US20110017587A1 (en) * | 2009-07-27 | 2011-01-27 | Aruna Zhamu | Production of chemically functionalized nano graphene materials |
| WO2011081268A1 (en) * | 2009-12-31 | 2011-07-07 | 한국과학기술원 | Method for producing graphenes through the production of a graphite intercalation compound using salts |
Non-Patent Citations (2)
| Title |
|---|
| CHIH-JEN SHIH ET AL.: "Bi- and trilayer graphene solutions", 《NATURE NANOTECHNOLOGY》 * |
| M.S. DRESSELHAUS ET AL.: "Intercalation compounds of graphite", 《ADVANCES IN PHYSICS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588195A (en) * | 2013-11-01 | 2014-02-19 | 天津大学 | Preparation method of graphene |
| CN105820514A (en) * | 2016-04-08 | 2016-08-03 | 泰州巨纳新能源有限公司 | Preparation method of high-conductivity graphene-resin composite material |
| CN107934945A (en) * | 2017-12-07 | 2018-04-20 | 西南交通大学 | A kind of method for preparing magnetic graphene using molysite gas phase intercalation and microwave technology |
| CN108640107A (en) * | 2018-07-06 | 2018-10-12 | 广州特种承压设备检测研究院 | A kind of intercalator of quick stripping graphite for high-quality graphene volume production |
| CN108706575A (en) * | 2018-07-06 | 2018-10-26 | 广州特种承压设备检测研究院 | A kind of preparation method of liquid phase ball milling stripping graphene |
| CN109671952A (en) * | 2018-12-21 | 2019-04-23 | 福建翔丰华新能源材料有限公司 | Microcrystalline graphene-based composite conductive slurry for lithium battery and preparation method thereof |
| CN109671952B (en) * | 2018-12-21 | 2022-03-04 | 福建翔丰华新能源材料有限公司 | Microcrystalline graphene-based composite conductive slurry for lithium battery and preparation method thereof |
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Application publication date: 20131023 |