CN103922325B - A kind of preparation method of Graphene - Google Patents
A kind of preparation method of Graphene Download PDFInfo
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- CN103922325B CN103922325B CN201410153109.9A CN201410153109A CN103922325B CN 103922325 B CN103922325 B CN 103922325B CN 201410153109 A CN201410153109 A CN 201410153109A CN 103922325 B CN103922325 B CN 103922325B
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Abstract
The present invention is to provide a kind of preparation method of Graphene.Step one, the ratio being 100 ~ 10000:1 in mass ratio by organic solvent and Graphite Powder 99 mixes, 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, take out the liquid of upper strata graphene-containing; Step 2, lower floor's solid continues to add organic solvent, the operation of repeating step one, disappears to solid residue; Step 3, merges the liquid of graphene-containing, filters, and by washing with alcohol, 80 DEG C of dryings 12 hours, obtain Graphene.The invention provides a kind of with common Graphite Powder 99 for raw material, simple process, equipment is simple, production cost is low, less contamination, the graphene preparation method that quality product is high.
Description
Technical field
That the present invention relates to is a kind of preparation method of Graphene.
Background technology
The mechanics of its uniqueness of Graphene, calorifics, electrical and optical properties, become the focus studied in the world at present.Prepare individual layer on a large scale or lack the major issue that layer graphene material becomes restriction Graphene widespread use and suitability for industrialized production at present.The preparation method of current Graphene mainly contains following a few class: mechanically peel method, epitaxial growth method, chemical Vapor deposition process, chemical synthesis, graphene oxide reduction method, and longitudinally cuts carbon tube method etc.
Mechanically peel method: 2004, Geim and Novoselov utilizes 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 all extremely low, inapplicable scale operation Graphene.Epitaxial growth method: with monocrystal SiC sheet, utilizes high temperature to distil and removes 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: under this method refers to high temperature, cracking carbon source deposits the method that the end deposits at solid.The 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.Relative 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.
Prior art the most close 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 expanded graphite mixes with ferrocene by this research, with HCl process after microwave heating expansion, dry, add the ultrasonic 75min of 1-Methyl-2-Pyrrolidone, centrifugal, remove big particle agglomerate, after filtration, washing, drying, 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, add equipment cost in production process; In preparation process except the use of organic solvent, also use ferrocene, HCl, not only add preparation cost, improve 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 one, the ratio being 100 ~ 10000:1 in mass ratio by organic solvent and Graphite Powder 99 mixes, 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, take out the liquid of upper strata graphene-containing;
Step 2, lower floor's solid continues to add organic solvent, the operation of repeating step one, disappears to solid residue;
Step 3, merges the liquid of graphene-containing, filters, and by washing with alcohol, 80 DEG C of dryings 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 dimethyl ether.
3, the preferred N-Methyl pyrrolidone of described organic solvent.
4, being rapidly heated described in 100 DEG C ~ 200 DEG C is in 3 ~ 5 minutes, be warming up to 100 DEG C ~ 200 DEG C.
The invention provides a kind of with common Graphite Powder 99 for 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 dispersion is bad and preparation process is loaded down with trivial details, the present invention take Graphite Powder 99 as raw material, machine solvent (N-Methyl pyrrolidone) is stripping liquid, the simplest cold and hot expansion two-step approach is only utilized just to achieve the stripping of Graphite Powder 99, obtain high-performance, in a liquid dispersed splendid grapheme material.In reaction process, utilize principle of expanding with heat and contracting with cold, by special adsorption macromolecular in stripping liquid, realize the expansion of Graphite Powder 99 molecular layer spacing, interlaminar action power dies down or disappears, and finally obtains single-layer graphene nanometer sheet.
Technique effect of the present invention is mainly reflected in:
1 in raw material: the present invention with common Graphite Powder 99 for raw material, applied range, raw materials cost is low;
2 in production unit: equipment is simple, and without particular requirement, be easy to suitability for industrialized production, equipment cost is low;
3 in production technique: technique is simple, can realize, be easy to suitability for industrialized production by means of only furnishing temperature of reaction;
4 in energy-conserving and environment-protective: all organic solvent Distillation recoveries, recycle, and can realize pollutent 0 and discharge.
5 in product: graphene dispersion is stable, productive rate is high, thickness is thin.
Accompanying drawing explanation
Fig. 1 is before peeling off and peels off the XRD figure of after product: a is Graphite Powder 99; B is Graphene.
Embodiment
Illustrate below and the present invention is described in more detail.
Embodiment 1:
Methane amide is (100 ~ 10000) with the mass ratio of Graphite Powder 99: 1 mixes, and stirs 0.5 ~ 2 hour, under-30 DEG C ~ 0 DEG C condition freezing 0.5 ~ 4 hour; Be warming up to 100 DEG C ~ 200 DEG C reactions 0.5 ~ 4 hour.Cooling, centrifugal, take out the liquid of 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 reaction 1 hour.
Embodiment 5:
Embodiment 4 is changed into :-10 DEG C freezing 1 hour; Be rapidly heated at 180 DEG C reaction 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 and the mass ratio of Graphite Powder 99 are that 500-2000:1 mixes.
Embodiment 8:
Embodiment 3 is changed into: N-Methyl pyrrolidone and the mass ratio of Graphite Powder 99 are that 1000:1 mixes.
Embodiment 9:
Embodiment 4 is changed into: N-Methyl pyrrolidone and the mass ratio of Graphite Powder 99 are that 1000:1 mixes.
Embodiment 10:
Embodiment 5 is changed into: N-Methyl pyrrolidone and the mass ratio of Graphite Powder 99 are that 1000:1 mixes.
Embodiment 11:
Embodiment 1 is changed into: dimethyl ether is (100 ~ 10000) with the mass ratio of Graphite Powder 99: 1 mixes.
Embodiment 12:
Embodiment 2 is changed into: dimethyl ether and the mass ratio of Graphite Powder 99 are that 500-2000:1 mixes.
Embodiment 13:
Embodiment 3 is changed into: dimethyl ether and the mass ratio of Graphite Powder 99 are that 1000:1 mixes.
Embodiment 14:
Embodiment 4 is changed into: dimethyl ether and the mass ratio of Graphite Powder 99 are that 1000:1 mixes.
Embodiment 15:
Embodiment 5 is changed into: dimethyl ether and the mass ratio of Graphite Powder 99 are that 1000:1 mixes.
Claims (2)
1. a preparation method for Graphene, is characterized in that:
Step one, the ratio being 100 ~ 10000:1 in mass ratio by methane amide and Graphite Powder 99 mixes, and stirs 0.5 ~ 2 hour, under-30 DEG C ~ 0 DEG C condition freezing 0.5 ~ 4 hour, is warming up to 100 DEG C ~ 200 DEG C reactions 0.5 ~ 4 hour in 3 ~ 5 minutes; Cooling, centrifugal, take out the liquid of upper strata graphene-containing;
Step 2, lower floor's solid continues to add methane amide, the operation of repeating step one, disappears to solid residue;
Step 3, merges the liquid of graphene-containing, filters, and by washing with alcohol, 80 DEG C of dryings 12 hours, obtain Graphene.
2. the preparation method of a kind of Graphene according to claim 1, is characterized in that: methane amide Distillation recovery, recycles.
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| CN201410153109.9A CN103922325B (en) | 2014-04-17 | 2014-04-17 | A kind of preparation method of Graphene |
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| CN103922325A CN103922325A (en) | 2014-07-16 |
| CN103922325B true CN103922325B (en) | 2015-12-09 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
Citations (5)
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| 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 |
| 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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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| 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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