CN103922325A - Graphene preparation method - Google Patents
Graphene preparation method Download PDFInfo
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- CN103922325A CN103922325A CN201410153109.9A CN201410153109A CN103922325A CN 103922325 A CN103922325 A CN 103922325A CN 201410153109 A CN201410153109 A CN 201410153109A CN 103922325 A CN103922325 A CN 103922325A
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Abstract
The invention provides a graphene preparation method. The graphene preparation method comprises the following steps: step one, mixing an organic solvent and graphite powder according to the condition that the mass ratio of the organic solvent to the graphite powder is (100-10000): 1, stirring for 0.5-2 hours, freezing at the temperature of minus 30 DEG C to 0 DEG C for 0.5-4 hours, rapidly heating to 100 DEG C-200 DEG C, and reacting for 0.5-4 hours; cooling, centrifuging, and taking out liquid, the upper layer of which contains graphene; step two, continuously adding the organic solvent to lower liquid, and repeating the operation of the step one till solid residues disappear; step three, combining graphene-containing liquid, filtering, washing by using ethyl alcohol, and drying at the temperature of 80 DEG C for 12 hours, thus obtaining the graphene. The graphene preparation method provided by the invention has the advantages that the common graphite powder is used as a raw material, the technology is simple and convenient, equipment is simple, the production cost and the pollution are low, and the product quality is high.
Description
Technical field
That the present invention relates to is a kind of preparation method of Graphene.
Background technology
Its unique mechanics of Graphene, calorifics, electrical and optical properties, become at present a focus of research in the world.Preparing on a large scale individual layer or few layer graphene material becomes the major issue of the widespread use of current restriction Graphene and suitability for industrialized production.The preparation method of Graphene mainly contains following a few class at present: mechanically peel method, epitaxial growth method, and chemical Vapor deposition process, chemical synthesis, graphene oxide reduction method, and longitudinally cut carbon Guan Fa etc.
Mechanically peel method: 2004, Geim and Novoselov utilized this method by pyrolytic graphite adhesive tape tear-off repeatedly, and then Separation and Recovery, obtains large stretch of layer graphene.But this method wastes time and energy, productive rate and individual layer rate are all extremely low, inapplicable scale operation Graphene.Epitaxial growth method: with monocrystal SiC sheet, utilize high temperature distillation to remove Siliciumatom, obtain epitaxially grown Graphene.But the standby graphene film number of this legal system differs, substrate doping easily affects the chemical property of Graphene.Chemical Vapor deposition process: this method refers to that under high temperature, cracking carbon source is deposited the method depositing at the end at solid.Graphene quality that this method obtains is high, productive rate is high.But what generally obtain is multi-layer graphene film or inhomogenous graphene film; Graphene oxide reduction method: utilize graphene oxide precursor to be reduced into Graphene, the method is current most popular graphene preparation method.With respect to this method abundant raw material of additive method, operating process is simple, and equipment is easy to get, and product workability is good, but the integrity of product need to improve.
The prior art approaching the most with the present invention in prior art prepared by Graphene is: a kind of simple high quality, solution-stabilized graphene preparation method (Chinese Patent Application No.: 201110455631.9), first this research mix expanded graphite with ferrocene, after microwave heating expansion, process with HCl, dry, add the ultrasonic 75min of 1-Methyl-2-Pyrrolidone, centrifugal, remove big particle agglomerate, after filtering, wash, being dried, obtain Graphene.The weak point of the method: what the method adopted is the expanded graphite specifically with inflatable performance, has strict restriction for reaction raw materials; In preparation process, apply microwave, ultrasonic technique, increased equipment cost in production process; In preparation process, except the use of organic solvent, also use ferrocene, HCl, not only increased preparation cost, improved the environmental protection treatment cost in production process simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of simple process, production cost is low, and environmental pollution is little, the preparation method of the Graphene that quality product is high.
The object of the present invention is achieved like this:
Step 1, the ratio that is 100～10000:1 in mass ratio by organic solvent and Graphite Powder 99 is mixed, and stirs 0.5～2 hour, under-30 DEG C～0 DEG C condition freezing 0.5～4 hour, is rapidly heated to 100 DEG C～200 DEG C reactions 0.5～4 hour; Cooling, centrifugal, the liquid of taking-up upper strata graphene-containing;
Step 2, lower floor's solid continues to add organic solvent, and the operation of repeating step one disappears to solid residue;
Step 3, the liquid of merging graphene-containing, filters, and by washing with alcohol, 80 DEG C are dried 12 hours, obtain Graphene.
The present invention can also comprise:
1, organic solvent Distillation recovery, recycles.
2, described organic solvent is N-Methyl pyrrolidone, methane amide or dipropylene glycol dme.
3, the preferred N-Methyl pyrrolidone of described organic solvent.
4, described in, being rapidly heated to 100 DEG C～200 DEG C is in 3～5 minutes, to be warming up to 100 DEG C～200 DEG C.
The invention provides a kind of taking common Graphite Powder 99 as raw material, simple process, equipment is simple, production cost is low, less contamination, the graphene preparation method that quality product is high.
Technical characteristics of the present invention is: prepare for forefathers the defect that Graphene dispersiveness is bad and preparation process is loaded down with trivial details, the present invention is taking Graphite Powder 99 as raw material, machine solvent (N-Methyl pyrrolidone) is stripping liquid, only utilize the simplest cold and hot expansion two-step approach just to realize peeling off of Graphite Powder 99, obtain high-performance, dispersed splendid grapheme material in liquid.In reaction process, utilize principle of expanding with heat and contracting with cold, by macromolecular intercalation effect in stripping liquid, realize the expansion of Graphite Powder 99 molecular layer spacing, interlaminar action power dies down or disappears, and has finally obtained single-layer graphene nanometer sheet.
Technique effect of the present invention is mainly reflected in:
1 aspect raw material: the present invention is taking common Graphite Powder 99 as raw material, applied range, and raw materials cost is low;
2 aspect production unit: equipment is simple, without particular requirement, is easy to suitability for industrialized production, and equipment cost is low;
3 aspect production technique: technique is simple, only can realize by furnishing temperature of reaction, is easy to suitability for industrialized production;
4 aspect energy-conserving and environment-protective: all organic solvent Distillation recoveries, recycle, and can realize pollutent 0 and discharge.
5 aspect product: Graphene stably dispersing, productive rate are high, thin thickness.
Brief description of the drawings
Fig. 1 is before peeling off and peels off the XRD figure of after product: a is Graphite Powder 99; B is Graphene.
Embodiment
For example the present invention is described in more detail below.
Embodiment 1:
Methane amide is (100～10000) with the mass ratio of Graphite Powder 99: 1 mixes, and stirs under-30 DEG C～0 DEG C condition freezing 0.5～4 hour 0.5～2 hour; Be warming up to 100 DEG C～200 DEG C reactions 0.5～4 hour.Cooling, centrifugal, the liquid of taking-up upper strata graphene-containing, lower floor's solid continues to add organic solvent.Repeat above-mentioned steps 3-5 time, disappear to solid residue.Merge the liquid of graphene-containing, filter, by washing with alcohol, 80 DEG C of dry 12h, obtain Graphene.Organic solvent Distillation recovery, recycles.
Embodiment 2:
Embodiment 1 is changed into: the mass ratio of methane amide and Graphite Powder 99 is 500-2000:1, stir 0.5-1.5 hour ,-20～-10 DEG C of freezing 1-3 hour; Be rapidly heated at 180～200 DEG C and react 1-3 hour.
Embodiment 3:
Embodiment 2 is changed into: the mass ratio of methane amide and Graphite Powder 99 is 1000:1, stir 1 hour.
Embodiment 4:
Embodiment 3 is changed into :-20～-10 DEG C freezing 1 hour; Be rapidly heated at 180～200 DEG C and react 1 hour.
Embodiment 5:
Embodiment 4 is changed into :-10 DEG C freezing 1 hour; Be rapidly heated at 180 DEG C and react 1 hour.
Embodiment 6:
Embodiment 1 is changed into: N-Methyl pyrrolidone is (100～10000) with the mass ratio of Graphite Powder 99: 1 mixes.
Embodiment 7:
Embodiment 2 is changed into: N-Methyl pyrrolidone is that 500-2000:1 mixes with the mass ratio of Graphite Powder 99.
Embodiment 8:
Embodiment 3 is changed into: N-Methyl pyrrolidone is that 1000:1 mixes with the mass ratio of Graphite Powder 99.
Embodiment 9:
Embodiment 4 is changed into: N-Methyl pyrrolidone is that 1000:1 mixes with the mass ratio of Graphite Powder 99.
Embodiment 10:
Embodiment 5 is changed into: N-Methyl pyrrolidone is that 1000:1 mixes with the mass ratio of Graphite Powder 99.
Embodiment 11:
Embodiment 1 is changed into: dipropylene glycol dme is (100～10000) with the mass ratio of Graphite Powder 99: 1 mixes.
Embodiment 12:
Embodiment 2 is changed into: dipropylene glycol dme is that 500-2000:1 mixes with the mass ratio of Graphite Powder 99.
Embodiment 13:
Embodiment 3 is changed into: dipropylene glycol dme is that 1000:1 mixes with the mass ratio of Graphite Powder 99.
Embodiment 14:
Embodiment 4 is changed into: dipropylene glycol dme is that 1000:1 mixes with the mass ratio of Graphite Powder 99.
Embodiment 15:
Embodiment 5 is changed into: dipropylene glycol dme is that 1000:1 mixes with the mass ratio of Graphite Powder 99.
Claims (7)
1. a preparation method for Graphene, is characterized in that:
Step 1, the ratio that is 100～10000:1 in mass ratio by organic solvent and Graphite Powder 99 is mixed, and stirs 0.5～2 hour, under-30 DEG C～0 DEG C condition freezing 0.5～4 hour, is rapidly heated to 100 DEG C～200 DEG C reactions 0.5～4 hour; Cooling, centrifugal, the liquid of taking-up upper strata graphene-containing;
Step 2, lower floor's solid continues to add organic solvent, and the operation of repeating step one disappears to solid residue;
Step 3, the liquid of merging graphene-containing, filters, and by washing with alcohol, 80 DEG C are dried 12 hours, obtain Graphene.
2. the preparation method of a kind of Graphene according to claim 1, is characterized in that: organic solvent Distillation recovery, recycles.
3. the preparation method of a kind of Graphene according to claim 1 and 2, is characterized in that: described organic solvent is N-Methyl pyrrolidone, methane amide or dipropylene glycol dme.
4. the preparation method of a kind of Graphene according to claim 3, is characterized in that: described organic solvent selects N-Methyl pyrrolidone.
5. the preparation method of a kind of Graphene according to claim 1 and 2, is characterized in that: described in to be rapidly heated to 100 DEG C～200 DEG C be in 3～5 minutes, to be warming up to 100 DEG C～200 DEG C.
6. the preparation method of a kind of Graphene according to claim 3, is characterized in that: described in to be rapidly heated to 100 DEG C～200 DEG C be in 3～5 minutes, to be warming up to 100 DEG C～200 DEG C.
7. the preparation method of a kind of Graphene according to claim 4, is characterized in that: described in to be rapidly heated to 100 DEG C～200 DEG C be in 3～5 minutes, to be warming up to 100 DEG C～200 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105523553A (en) * | 2016-02-04 | 2016-04-27 | 成都新柯力化工科技有限公司 | Method for preparing graphene through single cold side frozen single-molecule water expansion |
| CN106315569A (en) * | 2016-11-04 | 2017-01-11 | 河南腾飞高分子复合材料股份有限公司 | Preparation method for graphene |
| CN108359133A (en) * | 2018-01-26 | 2018-08-03 | 新疆磐基实业有限公司 | The additive and its preparation method and application of geotechnological film dynamic performance can be improved |
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| CN102115078A (en) * | 2011-01-19 | 2011-07-06 | 上海交通大学 | Method for preparing graphene by using supercritical fluid |
| US20110311432A1 (en) * | 2010-06-18 | 2011-12-22 | Nen-Wen Pu | Method for manufacturing graphene |
| CN102659096A (en) * | 2012-04-27 | 2012-09-12 | 湖南大学 | Preparation methods of graphene dispersion solution and thin film of graphene |
| CN103723712A (en) * | 2013-11-22 | 2014-04-16 | 盐城纳新天地新材料科技有限公司 | Preparation method of single-layer graphene dimethylformamide solution |
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| US20110311432A1 (en) * | 2010-06-18 | 2011-12-22 | Nen-Wen Pu | Method for manufacturing graphene |
| CN101966988A (en) * | 2010-11-17 | 2011-02-09 | 哈尔滨工业大学 | Method for preparing graphene powder |
| CN102115078A (en) * | 2011-01-19 | 2011-07-06 | 上海交通大学 | Method for preparing graphene by using supercritical fluid |
| CN102659096A (en) * | 2012-04-27 | 2012-09-12 | 湖南大学 | Preparation methods of graphene dispersion solution and thin film of graphene |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105523553A (en) * | 2016-02-04 | 2016-04-27 | 成都新柯力化工科技有限公司 | Method for preparing graphene through single cold side frozen single-molecule water expansion |
| CN105523553B (en) * | 2016-02-04 | 2017-07-04 | 成都新柯力化工科技有限公司 | It is a kind of suddenly to freeze the method that unimolecule water expansion prepares Graphene by single cold end |
| CN106315569A (en) * | 2016-11-04 | 2017-01-11 | 河南腾飞高分子复合材料股份有限公司 | Preparation method for graphene |
| CN106315569B (en) * | 2016-11-04 | 2019-05-21 | 河南腾飞高分子复合材料股份有限公司 | A kind of preparation method of graphene |
| CN108359133A (en) * | 2018-01-26 | 2018-08-03 | 新疆磐基实业有限公司 | The additive and its preparation method and application of geotechnological film dynamic performance can be improved |
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| CN103922325B (en) | 2015-12-09 |
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