CN106744887A - A kind of preparation method of Graphene - Google Patents
A kind of preparation method of Graphene Download PDFInfo
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- CN106744887A CN106744887A CN201710032657.XA CN201710032657A CN106744887A CN 106744887 A CN106744887 A CN 106744887A CN 201710032657 A CN201710032657 A CN 201710032657A CN 106744887 A CN106744887 A CN 106744887A
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- graphite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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Abstract
The invention discloses a kind of preparation method of Graphene, by graphite under the buffer existence conditions such as high molecular polymer, inorganic salts compound and aromatic hydrocarbons micromolecular compound, rubbed by mechanical presses and realize peeling off, obtain Graphene；The method has the advantages that can large-scale, green, low cost.
Description
Technical field
The present invention relates to graphene preparation method, and in particular to one kind based on graphite stripping off device realize extensive, green,
The method that low cost prepares Graphene；Belong to technical field of graphene preparation.
Background technology
Since Graphene is found, due to its excellent machinery, electronics and thermal stability, its application is subject to people wide
General attention, as current international popular research field.The application of Graphene is with low cost, high yield, the system of high-quality graphene
Premised on standby.The preparation method of current Graphene mainly has mechanical stripping method, epitaxial growth method, chemical vapour deposition technique and solution
Processing method etc..Epitaxial growth method is that single-crystal silicon carbide is pyrolyzed generation graphene sheet layer under high temperature, high vacuum condition, is obtained
Graphene quality is high, but size is smaller, and needs expensive material and facility；Chemical vapour deposition technique is that organic molecule exists
Cracked under high temperature, high vacuum condition, to be carbonized generate graphene sheet layer in transition metal substrate surface, same apparatus expensive is unfavorable
In large-scale application；Solution processing method is first to aoxidize graphite powder, peel off into graphene oxide, then using chemical reagent as being hydrated
The redox graphenes such as hydrazine, sodium borohydride are into Graphene, and this method is with low cost, can be mass Graphene, but graphite
Oxy radical in alkene plane can not thoroughly reduce removing, and this fault of construction causes the electronic transmission performance of Graphene to be subject to shadow
Ring, and hydrazine hydrate is toxic compounds.Current mechanical stripping method is to peel off hydrolysis graphite with adhesive tape, be can obtain most high-quality
The Graphene of amount, but yield poorly, be not suitable for large-scale application.
The content of the invention
For prior art exist defect, it is an object of the invention to provide a kind of process is simple, it is easy to operate, to ring
Border is friendly, and the yield method for preparing Graphene high, the method green, safety, low cost, is adapted to large-scale application.
In order to realize above-mentioned technical purpose, the invention provides a kind of preparation method of Graphene, the method is that graphite exists
Under buffer existence condition, rubbed by mechanical presses and realize peeling off, obtain Graphene；The buffer includes high molecular polymerization
At least one of thing, inorganic salts compound and aromatic hydrocarbons micromolecular compound.
Technical scheme be it is critical only that and employ suitable buffer, and graphite is acted on by mechanical friction, easily
Because rubbing and overcrushing repeatedly, it is impossible to obtain the Graphene of structural integrity, and the present invention by using buffer, can be effective
Dispersed graphite peels off the Graphene of generation, under graphite outer layer graphene platelet under the friction effect repeatedly is in layer peeled off
Come, and disperseed in time, Graphene can be prevented effectively from because rubbing and overcrushing repeatedly.
Preferred scheme, the high molecular polymer includes polyacrylic compounds, polyvinyl alcohol compound, polyphenyl
At least one of ethylene compounds.More preferably scheme, including polyvinyl alcohol, polyacrylic acid, polymethylacrylic acid, polypropylene
At least one of sour methyl esters, polyethyl acrylate, polymethyl methacrylate, polystyrene.
More preferably scheme, the molecular weight of the high molecular polymer is 0.5 ten thousand~100,000.
Preferred scheme, the inorganic salts compound includes alkaline metal salt compound；Preferred scheme, including chlorine
Change at least one of potassium, sodium chloride, potassium hydroxide, NaOH, sodium sulphate, potassium sulfate.
Preferred scheme, the aromatic hydrocarbons micromolecular compound organic matter includes naphthalene, phenanthrene, anthracene, pyrene, BaP, phenol, benzene
Formic acid,At least one of.
Preferred scheme, buffer is (1~50) with the weight ratio of graphite:1；More elect as (1~10):1.
More preferably scheme, the graphite includes graphite powder and/or graphite flake.
Preferred scheme, the mechanical presses friction process of graphite is realized by graphite stripping off device；The graphite peels off dress
Putting main body includes base and the arcuate movement clamping plate supporting with arc groove containing arc groove；Outside the arcuate movement clamping plate
Cambered surface is evenly distributed with arc bump, and the intrados centre of arcuate movement clamping plate is fixed with clamping plate axle.The device it is only
It is in place of special：Intrados design can make the abundant stress of sample, and edge dead angle is not stayed；Charge stripping efficiency is high, and graphene film is difficult
It is broken；Regulation ambulatory splint shaft length, can easily regulate and control pressure.
More preferably scheme, by graphite and buffer be placed in graphite stripping off device arc groove and arcuate movement clamping plate it
Between, lower active force is applied with to clamping plate axle, move up and down arcuate movement clamping plate, repeatedly extrusion friction, graphite peels off into graphite
Alkene.
Further preferred scheme, amount of force between 0.5~0.8MPa, the speed that arcuate movement clamping plate is moved up and down
Degree is in 80~200m/s.Optimal amount of force up and down between 0.6~0.75MPa, arcuate movement clamping plate optimum travel rate degree
In 120~180m/s.Pressure is too small or the too small stripping for being difficult to graphite of speed, and excessive velocities or pressure are excessive, easily
Graphene is caused to crush.
It is relative to be directed to prior art, the Advantageous Effects that technical scheme is brought：
1) technical scheme can effectively prevent Graphene by using buffer in the stripping process of Graphene
The overcrushing during rubbing repeatedly, obtains the Graphene of structural integrity, improves the yield of Graphene.
2) technical scheme can make the abundant stress of graphite by designing graphite stripping off device, not stay edge dead
Angle, improves charge stripping efficiency, and graphene film is non-breakable, improve production efficiency, is suitable for large-scale production.
3) technical scheme is produced in graphite stripping process without any excitant and corrosivity hydrogen chloride gas,
It is that a kind of pure physics is peeled off, is conducive to environmental protection.
4) technical scheme process is simple, easy to operate, low cost, are adapted to large-scale application.
Brief description of the drawings
【Fig. 1】It is graphite stripping off device structural section figure of the invention；
【Fig. 2】It is graphite stripping off device structure top view of the invention；
【Fig. 3】It is Graphene product morphology in the embodiment of the present invention 1；
【Fig. 4】It is Graphene product morphology in the embodiment of the present invention 2；
【Fig. 5】It is Graphene product morphology in the embodiment of the present invention 3；
【Fig. 6】It is Graphene product morphology in comparative example of the present invention 1；
【Fig. 7】It is Graphene product morphology in comparative example of the present invention 2；
【Fig. 8】It is Graphene product morphology in comparative example of the present invention 3；
In Fig. 1 and Fig. 2,1 is clamping plate axle, and 2 is arc bump, and 3 is arcuate movement clamping plate, and 4 is graphite sample, and 5 is base.
Specific embodiment
Following examples are intended to illustrate present invention, are further limited rather than to the scope that the claims in the present invention are protected
It is fixed.
The Graphene stripping off device used in following examples is as depicted in figs. 1 and 2.Graphene stripping off device main body includes
Base and the arcuate movement clamping plate supporting with arc groove containing arc groove；Arcuate movement clamping plate size is recessed with the arc of base
Groove is matched, and the arc radius size than arc groove is slightly smaller, and the extrados of the arcuate movement clamping plate is evenly distributed with small arc
Projection, arc bump is used to increase stress and the friction of graphite, and this is the art it should be understood that arcuate movement clamping plate
Intrados centre is fixed with clamping plate axle, and clamping plate axle is mainly used in applying external force.
Embodiment 1
L () 1 kilogram of graphite flake and 5 kilograms of polyvinyl alcohol (molecular weight 80,000) stir.
(2) graphite flake and polyvinyl alcohol mixture are placed between base arc groove and arcuate movement clamping plate, and clamping plate is upper and lower
Apply active force extruding friction, in 0.7MPa, arcuate movement clamping plate translational speed is in 120m/s for upper and lower amount of force.Until stone
Ink sheet becomes straticulation (regular sampling Detection).
(3) step 2 gained solid is placed in 50 DEG C of hot-water soak washings, and sieving separating obtains Graphene, kept dry.Graphite
The yield of alkene is 87%.Product pattern is as shown in Figure 3.
Embodiment 2
L () 1 kilogram of graphite flake and 10 kilograms of naphthalenes stir.
(2) graphite flake and naphthalene mixtures are placed between base arc groove and arcuate movement clamping plate, and clamping plate applies to make up and down
Firmly extruding friction, in 0.65MPa, arcuate movement clamping plate translational speed is in 160m/s for upper and lower amount of force.
(3) step 2 gained solid is placed in acetic acid washing by soaking, and sieving separating obtains Graphene, kept dry.Graphene
Yield is 95%.Product pattern is as shown in Figure 4.
Embodiment 3
L () 1 kilogram of graphite flake and 2 kilograms of sodium chloride stir.
(2) graphite flake and sodium chloride mixture are placed between base arc groove and arcuate movement clamping plate, and clamping plate is squeezed up and down
Pressure friction, until graphite flake becomes straticulation (regular sampling Detection).Apply active force extruding friction, upper and lower amount of force exists
0.6MPa, arcuate movement clamping plate translational speed is in 180m/s.
(3) step 2 gained solid is placed in water washing by soaking, and sieving separating obtains Graphene, kept dry.The product of Graphene
Rate is 84%.Product pattern is as shown in Figure 5.
Comparative example 1
L () 1 kilogram of graphite flake and 2 kilograms of calcium carbonate stir.
(2) graphite flake and calcium carbonate mixture are placed between base arc groove and arcuate movement clamping plate, and clamping plate is applied up and down
Plus active force extruding friction, in 0.7MPa, arcuate movement clamping plate translational speed is in 140m/s for upper and lower amount of force.
(3) step 2 gained solid is placed in hydrochloric acid washing by soaking, and sieving separating obtains powder, kept dry.The product of Graphene
Rate is 13%, and major part is graphite scrap.Product pattern is as shown in Figure 6.
Comparative example 2
L () 1 kilogram of graphite flake and 2 kilograms of polyethylene (molecular weight 10,000) stir.
(2) graphite flake and polyethylene mixture are placed between base arc groove and arcuate movement clamping plate, and clamping plate is applied up and down
Plus active force extruding friction, in 0.7MPa, arcuate movement clamping plate translational speed is in 140m/s for upper and lower amount of force.
(3) step 2 gained solid is placed in chloroform washing by soaking, and sieving separating obtains powder, kept dry.The product of Graphene
Rate is 24%, and major part is graphite scrap.Product pattern is as shown in Figure 7.
Comparative example 3
L () 1 kilogram of graphite flake and 2 kilograms of ethyl acetate stir.
(2) graphite flake and ethyl acetate mixture are placed between base arc groove and arcuate movement clamping plate, and clamping plate is upper and lower
Apply active force extruding friction, in 0.7MPa, arcuate movement clamping plate translational speed is in 140m/s for upper and lower amount of force.
(3) step 2 gained solid is placed in acetone soak washing, and sieving separating obtains powder, kept dry.The product of Graphene
Rate is 17%, and major part is graphite scrap.Product pattern is as shown in Figure 8.
Claims (10)
1. a kind of preparation method of Graphene, it is characterised in that：Graphite under buffer existence condition, by mechanical presses friction
Realize peeling off, obtain Graphene；The buffer includes high molecular polymer, inorganic salts compound and aromatic hydrocarbons micromolecular
At least one of compound.
2. the preparation method of Graphene according to claim 1, it is characterised in that：The high molecular polymer includes poly- second
Enol, polyacrylic acid, polymethylacrylic acid, PMA, polyethyl acrylate, polymethyl methacrylate, polyphenyl second
At least one of alkene.
3. the preparation method of Graphene according to claim 2, it is characterised in that：The molecular weight of the high molecular polymer
It is 0.5 ten thousand~100,000.
4. the preparation method of Graphene according to claim 1, it is characterised in that：The inorganic salts compound includes chlorine
Change at least one of potassium, sodium chloride, potassium hydroxide, NaOH, sodium sulphate, potassium sulfate.
5. the preparation method of Graphene according to claim 1, it is characterised in that the aromatic hydrocarbons micromolecular compound has
Machine thing include naphthalene, phenanthrene, anthracene, pyrene, BaP, phenol, benzoic acid,At least one of.
6. the preparation method of Graphene according to claims 1 to 5, it is characterised in that：The weight ratio of buffer and graphite
It is (1~50):1.
7. the preparation method of Graphene according to claim 6, it is characterised in that：The graphite include graphite powder and/or
Graphite flake.
8. the preparation method of the Graphene according to any one of claim 1~7, it is characterised in that：The mechanical presses of graphite
Friction process is realized by graphite stripping off device；The graphite stripping off device main body includes base and and arc containing arc groove
The supporting arcuate movement clamping plate of groove；The extrados of the arcuate movement clamping plate is evenly distributed with arc bump, arcuate movement folder
The intrados centre of plate is fixed with clamping plate axle.
9. the preparation method of Graphene according to claim 8, it is characterised in that：Graphite and buffer are placed in graphite stripping
Between the arc groove and arcuate movement clamping plate of device, lower active force is applied with to clamping plate axle, makes arcuate movement clamping plate upper and lower
Move, repeatedly extrusion friction, graphite peels off into Graphene.
10. the preparation method of Graphene according to claim 9, it is characterised in that：Amount of force is in 0.5~0.8MPa
Between, the speed that arcuate movement clamping plate is moved up and down is in 80~200m/s.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103180244A (en) * | 2010-10-28 | 2013-06-26 | 英派尔科技开发有限公司 | Exfoliation of graphene by multilayer coextrusion |
| CN104609413A (en) * | 2015-02-11 | 2015-05-13 | 合肥微晶材料科技有限公司 | Machine-like stripping device for ton-scale production of graphene and production method of machine-like stripping device |
| CN106185884A (en) * | 2016-06-27 | 2016-12-07 | 刘效伟 | A kind of rapid, high volume produces the method for Graphene |
-
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- 2017-01-16 CN CN201710032657.XA patent/CN106744887A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103180244A (en) * | 2010-10-28 | 2013-06-26 | 英派尔科技开发有限公司 | Exfoliation of graphene by multilayer coextrusion |
| CN104609413A (en) * | 2015-02-11 | 2015-05-13 | 合肥微晶材料科技有限公司 | Machine-like stripping device for ton-scale production of graphene and production method of machine-like stripping device |
| CN106185884A (en) * | 2016-06-27 | 2016-12-07 | 刘效伟 | A kind of rapid, high volume produces the method for Graphene |
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