CN105480965A - Preparation method of graphene - Google Patents
Preparation method of graphene Download PDFInfo
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- CN105480965A CN105480965A CN201510838230.XA CN201510838230A CN105480965A CN 105480965 A CN105480965 A CN 105480965A CN 201510838230 A CN201510838230 A CN 201510838230A CN 105480965 A CN105480965 A CN 105480965A
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- graphene
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- expanded graphite
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Abstract
The invention discloses a preparation method of graphene. Expandable graphite is stood and immersed in an auxiliary agent aqueous solution and the solution is subjected to ultrasonic peeling in an organic solvent and then is dried so that the solvent is removed and graphene is obtained. The expandable graphite has a wide raw material source and the auxiliary agent is a common industrial product so that a cost is low. The solvent can be recovered and recycled. The preparation method has simple processes and has large scale preparation feasibility.
Description
Technical field
The present invention relates to a kind of graphene preparation method, be specially expanded graphite and auxiliary agent in the solution ultrasonic stripping prepare the method for Graphene, belong to field of graphene.
Background technology
Graphene is a kind of novel Two-dimensional Carbon nano material, forms with negative electrode active material the performance that matrix material can improve battery device, and Graphene can reduce or limit side effect and increase electronic conduction in positive active material charge and discharge process.
Method conventional is at present mostly oxidation reduction process, but graphene-structured defect prepared by this method is many, technology controlling and process is complicated, use acid with strong oxidizing property in a large number, and cost is higher.Therefore, a kind of low cost of exploitation, extensive, the technique method for Graphene easy to control is needed badly.Application publication number is that the Chinese patent of CN102431999A discloses a kind of method preparing high-quality graphene, the graphite intercalation compound being intercalator with halogen or metal halide is for raw material, oxalic acid or superoxol is used to expand, then ultrasonic preparation Graphene in the solution.Application publication number is the preparation method that the Chinese patent of CN102452649A discloses a kind of Graphene, by graphite as in the mixing solutions be made up of oxygenant and intercalator, by dipping, mechanical stirring or supersound process, obtain first insert layer compound, in air, fast pyrogenation obtains first overburden; Then carry out secondary stripping, obtain Graphene.Application publication number is that the Chinese patent of CN102431998A discloses a kind of chemical method intercalation and peels off graphite and prepare the method for high-quality graphene in a large number, with chemical method, the reagent such as Glacial acetic acid, iron trichloride, ammonium nitrate, Potcrate are inserted into graphite layers, microwave treatment, ultrasonic stripping, prepares Graphene.Application publication number is a kind of method that the Chinese patent of CN102757042A discloses liquid phase chemical Preparative TLC Graphene, graphite and superoxide and vitriol oil hybrid reaction make sulfuric acid intercalated graphite, through microwave treatment, form quasiflake graphite alkene aggregate, carry out ultrasonic again, obtain thin layer graphite; Then react with metal chloride, obtain the thin layer graphite of metal chloride intercalation; Mix with nonvolatile strong acid again, through supersound process, obtain Graphene.The Chinese patent of application publication number CN102583351A discloses the method for the few layer graphene of a kind of liquid phase intercalation combine with technique Microwave Radiation in Manufacturing preparation, and first graphite put into and replaced quaternary ammonium cation and OH containing tetraalkyl by the method
-solution in carry out supersound process, make tetraalkyl replace quaternary ammonium cation be inserted into graphite layers formed intercalation, cause graphite layers apart from increase; Then the graphite after process is carried out microwave exposure, graphite intercalation is decomposed, produces a large amount of gas, increase graphite layers distance further; Then the graphite dispersion after process is carried out supersound process in low polar organic solvent, make graphite occur to peel off generation Graphene; Finally carry out centrifugal treating, take out supernatant liquid after process and be few layer graphene dispersion liquid.The few layer graphene number of plies prepared, below 10 layers, has the advantage that defect is few, oxy radical is few, specific conductivity is high.Application publication number is that the Chinese patent of CN102874797A discloses a kind of method preparing high-quality graphene on a large scale, is mixed by stripper with water, and preparation concentration is the stripper solution of 0.2 ~ 50wt%; Be 0.1 ~ 10:100 according to expanded graphite and stripper solution mass ratio, be scattered in by expanded graphite in stripper solution to stir and infiltrate, then ultrasonic, after filtration, washing, drying obtain Graphene.Application publication number is that the Chinese patent of CN102874798 discloses a kind of method preparing Graphene, configuration soluble carbonate salt, supercarbonate, ammonium salt, urea, azo-compound, sulfonyl hydrazines compound solution are as whipping agent, expanded graphite is soaked wherein, then add heat extraction solvent, add thermal dissociation and prepare Graphene.As seen through the above analysis, intercalation plavini is the effective ways preparing high-quality graphene.
Summary of the invention
The object of the present invention is to provide a kind of graphene preparation method, dissociating of expanded graphite is realized by promoter effect, avoiding the complex process of oxidation reduction process and restive, save graphite intercalation and strong oxidizing property is dissociated, is a kind of method of Graphene of low cost, preparation in macroscopic quantity structural integrity.
Technical scheme of the present invention: a kind of graphene preparation method, is characterized by and comprise the steps:
(1) get auxiliary agent to add in deionized water and make pasty state, the volume mass of water and auxiliary agent is than being 10 ~ 50:1 for (ml/g);
(2) be added to by expanded graphite in step (1), fully disperse, leave standstill infiltration 8 ~ 36h, auxiliary agent is 2 ~ 10 times of expanded graphite quality;
(3) join in nitrogenous organic solvent by the mixture of step (2), nitrogenous organic solvent is 200 ~ 600:1 with the volume mass ratio (ml/g) of expanded graphite; Ultrasonic stripping carries out solution stirring simultaneously, 0.5 ~ 3h, except desolventizing, dry, obtains graphene powder.
In the present invention, described auxiliary agent is oxalic acid, volatile salt, bicarbonate of ammonia, and the content of water not only enters between graphite flake layer auxiliary agent and has a significant impact, and also can have an impact to dissociating in follow-up organic solvent, therefore needs the amount controlling water; Described nitrogenous organic solvent is DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone.
Positively effect of the present invention just adopts expanded graphite to be prepared as known maturation method, and raw material sources are extensive, with low cost; Auxiliary agent is common industrial product, very easily removes, and introduces impurity can not to follow-up use; In ultrasonic stripping process, auxiliary agent is auxiliary destroys graphite layers Van der Waals force, can the integrity of more complete holding structure, the equal recoverable of solvent for use; Technological process is simple, and equipment used is common general-purpose equipment, is easy to preparation in macroscopic quantity.
accompanying drawing illustrates:
Fig. 1 photo being dehydrated into block Graphene of the present invention.
The stereoscan photograph of Fig. 2 Graphene of the present invention.
The Raman spectrogram of Fig. 3 Graphene of the present invention.
The infrared spectrum of Fig. 4 Graphene of the present invention.
Embodiment
Just do further specific descriptions to the present invention below in conjunction with embodiment, claim includes but not limited to described embodiment content.
Embodiment 1
(1) get 7g oxalic acid to add in 70ml deionized water and make pasty state, it is even to add 3.5g expanded graphite dispersed with stirring, leaves standstill and infiltrates 12h.
(2) mixture that (1) obtains is joined in the DMF of 500ml, stirring, ultrasonic 0.5h, then add the DMF of 200ml, continue stirring, ultrasonic 1h; Stop stirring, continue ultrasonic 0.5h, pull the unreacted expanded graphite swimming in liquid level out.
(3) repeatedly wash with ethanol, removing DMF and oxalic acid, dry, obtain graphene powder, yield is 77%.
Embodiment 2
(1) get 7g volatile salt to add in 70ml deionized water and make pasty state, it is even to add 3.5g expanded graphite dispersed with stirring, leaves standstill and infiltrates 8h.
(2) mixture that (1) obtains is joined in the DMF of 700ml, stirring, ultrasonic 0.5h; Stop stirring, continue ultrasonic 0.5h, pull the unreacted expanded graphite swimming in liquid level out.
(3) repeatedly wash with ethanol, removing DMF, obtains half-dried graphene powder, adds the freezing 12h of 50ml deionized water, thaw, repeatedly wash with large water gaging, and dry, obtain graphene powder, yield is 72%.
Embodiment 3
(1) get 2g volatile salt to add in 20ml deionized water and make pasty state, it is even to add 0.2g expanded graphite dispersed with stirring, leaves standstill and infiltrates 36h.
(2) mixture that (1) obtains is joined in the N,N-dimethylacetamide of 40ml, stirring, ultrasonic 1h; Stop stirring, continue ultrasonic 0.5h, pull the unreacted expanded graphite swimming in liquid level out.
(3) pour in 400ml deionized water by (2) solution, heat release, leave standstill 2h, remove clear liquid, repeatedly add water standing, remove clear liquid, freezing 12h, thaws, and repeatedly washs with ethanol, and dry, obtain graphene powder, yield is 81%.
Embodiment 4
(1) get 2g bicarbonate of ammonia to add in 20ml deionized water and make pasty state, it is even to add 0.2g expanded graphite dispersed with stirring, leaves standstill and infiltrates 8h.
(2) mixture that (1) obtains is joined in the DMF of 40ml, stirring, ultrasonic 1h; Stop stirring, continue ultrasonic 0.5h, pull the unreacted expanded graphite swimming in liquid level out.
(3) leave standstill 2h, repeatedly wash with ethanol, dry, obtain graphene powder, yield is 75%.
Embodiment 5
(1) get 1g volatile salt and 1g bicarbonate of ammonia to add in 20ml deionized water and make pasty state, it is even to add 0.2g expanded graphite dispersed with stirring, leaves standstill and infiltrates 12h.
(2) mixture that (1) obtains is joined in the N-Methyl pyrrolidone of 40ml, stirring, ultrasonic 2h; Stop stirring, continue ultrasonic 0.5h, pull the unreacted expanded graphite swimming in liquid level out.
(3) remove N-Methyl pyrrolidone, obtain half-dried graphene powder, add the freezing 12h of 50ml deionized water, thaw, repeatedly wash with large water gaging, dry, obtain graphene powder, yield is 73%.
Claims (3)
1. a graphene preparation method, is characterized in that, gets auxiliary agent and adds in deionized water and make mashed prod, and the volume mass of water and auxiliary agent is than being 10 ~ 50:1 for (ml/g); Expanded graphite is added in mashed prod, fully disperses, leave standstill infiltration 8 ~ 36h, obtain expanded graphite mixture; Joined by mixture in nitrogenous organic solvent, nitrogenous organic solvent is 200 ~ 600:1 with the volume mass ratio (ml/g) of expanded graphite, and ultrasonic stripping carries out solution stirring simultaneously, time 0.5 ~ 3h, except desolventizing, dry, obtains graphene powder.
2. a kind of graphene preparation method according to claim 1, is characterized in that, described auxiliary agent is oxalic acid, volatile salt, bicarbonate of ammonia, and auxiliary agent is 2 ~ 10 times of expanded graphite quality.
3. a kind of graphene preparation method according to claim 1, is characterized in that, described nitrogenous organic solvent is DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone.
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| CN201510838230.XA CN105480965A (en) | 2015-11-26 | 2015-11-26 | Preparation method of graphene |
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| CN201510838230.XA CN105480965A (en) | 2015-11-26 | 2015-11-26 | Preparation method of graphene |
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| CN105480965A true CN105480965A (en) | 2016-04-13 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106825591A (en) * | 2017-03-23 | 2017-06-13 | 厦门圣之岛金属科技有限公司 | A kind of tin alkene raw powder's production technology |
| CN109817382A (en) * | 2017-11-21 | 2019-05-28 | 山东欧铂新材料有限公司 | A kind of preparation method of high-stability graphene electrocondution slurry |
| CN109911912A (en) * | 2019-05-06 | 2019-06-21 | 南京工业大学 | A kind of method that ice crystal stripping method prepares boron-based compounds nanometer sheet |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102874797A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Method for massively preparing high-quality graphene |
| CN103058176A (en) * | 2012-12-29 | 2013-04-24 | 华侨大学 | Method for preparing graphene efficiently |
-
2015
- 2015-11-26 CN CN201510838230.XA patent/CN105480965A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102874797A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Method for massively preparing high-quality graphene |
| CN103058176A (en) * | 2012-12-29 | 2013-04-24 | 华侨大学 | Method for preparing graphene efficiently |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106825591A (en) * | 2017-03-23 | 2017-06-13 | 厦门圣之岛金属科技有限公司 | A kind of tin alkene raw powder's production technology |
| CN109817382A (en) * | 2017-11-21 | 2019-05-28 | 山东欧铂新材料有限公司 | A kind of preparation method of high-stability graphene electrocondution slurry |
| CN109817382B (en) * | 2017-11-21 | 2020-09-29 | 山东欧铂新材料有限公司 | Preparation method of high-stability graphene conductive paste |
| CN109911912A (en) * | 2019-05-06 | 2019-06-21 | 南京工业大学 | A kind of method that ice crystal stripping method prepares boron-based compounds nanometer sheet |
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Application publication date: 20160413 |
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