CN105712330A - Viscous physical stripping method for graphene - Google Patents
Viscous physical stripping method for graphene Download PDFInfo
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- CN105712330A CN105712330A CN201410708363.0A CN201410708363A CN105712330A CN 105712330 A CN105712330 A CN 105712330A CN 201410708363 A CN201410708363 A CN 201410708363A CN 105712330 A CN105712330 A CN 105712330A
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Abstract
The invention discloses a viscous physical stripping method for graphene. The method comprises the steps of: S1. injecting flake graphite and a stripping solution into a ball milling tank, wherein the stripping solution is composed of 100 parts of water, 30-100 parts of an alcohol solvent, 50-80 parts of polyacrylic ester or a polyacrylic ester derivative, and 0.5-5 parts of a water-soluble salt; S2. conducting ball milling for 4-48h, and controlling the rotation speed of the ball mill above 2000rpm/min; S3. at the end of reaction, discharging a suspension solution to a storage tank and performing standing; S4. conveying the graphene suspension solution into a centrifuge to conduct centrifugation, then taking the supernatant and performing vacuum filtration to obtain a filter cake; and S5. washing the filter cake and conducting freeze drying. The stripping method can efficiently strip graphene.
Description
Technical field
The present invention relates to Graphene production technical field, be specifically related to a kind of Graphene physics stripping type production method.
Background technology
Graphene is a kind of two-dimensional material with good flexibility, electrical property.You need to add is that, stricti jurise is said, Graphene is the lamellar of a kind of monolayer；But due to the preparation difficulty of single-layer graphene, generally also the form the few-layer graphene alkene with similar performance is also ranged in the category of Graphene.
At present, the method that prepared by Graphene mainly has: chemically grown method and physics stripping method.Low compared to efficiency, be not suitable for the chemically grown method of industrialized mass production; it is raw material that physics stripping method mainly adopts cheap graphite; make graphite layers peeling-off by graphite crystal is applied mechanical force; break the Van der Waals force of graphite layers; forming monolithic graphite alkene or form the few-layer graphene alkene, this physical separation methods has more industrial prospect and applicable large-scale production.
In Graphene stripping means, it is necessary to add some auxiliary agents to increase the interlayer distance of graphite or so-called intercalation, so that graphite is peeled off better.As adopted nitric acid, potassium permanganate, chromic acid or hydrogen peroxide as oxidant, concentrated sulphuric acid, as intercalator, introduces the oxy radicals such as hydroxyl, epoxide group and carboxyl at graphite layers or edge, increase graphite layers from, be beneficial to follow-up graphite layers and peel off.But this chemical substance intercalated technique acid consumption is big, production process has the pollution of the harmful gass such as SOx, NOx or heavy metal ion, product there is sulfur remain, the Graphene finally given is easily generated defect, and in the application equipment there is is corrosion, reduce the service life of equipment, add production cost.
Summary of the invention
It is an object of the invention to overcome the defect existed in prior art, it is provided that a kind of plastic state physics peels off the method for Graphene, and the method can be efficiently peeled off graphite, and the structural deterioration of Graphene is little.
For realizing the purpose of the present invention, the technical scheme is that a kind of method that plastic state physics peels off Graphene, the method comprises the following steps:
S1. by purity more than 98%, particle diameter is that 30 ~ 500 μm of graphite flakes and stripper inject in ball grinder according to the weight ratio of 1:2～5, wherein the consisting of of stripper:
100 parts of water,
Alcohols solvent 30～100 parts,
Polyacrylate or polyacrylate derivatives 50～80 parts,
Water soluble salt 0.5～5 part；
Wherein, each component is in its parts by weight.
S2. ball milling 4～48h, the rotating speed of ball mill is more than 2000rpm/min；
S3. by discharging opening, suspension is expelled in storage tank after stopped reaction, stands 24h head product derived above；
S4. the graphene suspension in the storage tank obtained by step S3 is delivered in centrifuge, and centrifuge speed is 1000～6000rpm/min, and centrifugation time 10min～2h takes the supernatant, and in vacuum apparatus, vacuum is filtrated to get filter cake；
S5. filter cake step S4 obtained with appropriate distilled water wash, filter cake more than lyophilization 3h in freeze drying plant, namely obtain graphene product.
Preferred technical scheme is, in step sl, described alcohols solvent is one or more in ethanol, normal propyl alcohol, n-butyl alcohol, propylene glycol and terpineol.
Preferred technical scheme is, in step sl, the number-average molecular weight of described polyacrylate or polyacrylate derivatives is more than 100000.
Preferred technical scheme is, in step sl, described water soluble salt is the one in lithium fluoride, sodium fluoride, sodium chloride, lithium chloride.
Prior art is compared, plastic state physics of the present invention peels off the method for Graphene by adopting special plastic state stripper for the stripping of Graphene, this stripper adds polyacrylate or the polyacrylate derivatives with glue viscosity, this stripper is used to coordinate ball milling, the requirement to ball milling speed can be reduced, improve shear effect, it is not necessary to graphite flake layer ultra high shear can be realized the stripping to Graphene；It addition, the water soluble salt added in system can improve the electric conductivity of system, it is to avoid the Graphene of stripping, because electrostatic is superimposed together again, keeps the dispersity after peeling off.This stripping means can separate Graphene efficiently.
Detailed description of the invention
Below in conjunction with embodiment, the specific embodiment of the present invention is further described.Following example are only for clearly illustrating technical scheme, and can not limit the scope of the invention with this.
Embodiment 1
The present invention is a kind of method that plastic state physics peels off Graphene, and the method comprises the following steps:
S1. by purity more than 98%, particle diameter is that 30 ~ 500 μm of graphite flakes and stripper inject in ball grinder, wherein the consisting of of stripper: water 100 parts by weight, ethanol 30 parts by weight, polyacrylate 50 parts by weight, lithium fluoride 0.5 parts by weight.Wherein, the number-average molecular weight of polyacrylate is more than 100000.The weight ratio of graphite flakes and stripper is 1:2.
S2. ball milling 4h, the rotating speed of ball mill is 6000rpm/min.
S3. by discharging opening, suspension is expelled in storage tank after stopped reaction, stands 24h head product derived above.
S4. the graphene suspension in the storage tank obtained by step S3 is delivered in centrifuge, and centrifuge speed is 1000rpm/min, and centrifugation time 10min takes the supernatant, and in vacuum apparatus, vacuum is filtrated to get filter cake.
S5. filter cake step S4 obtained with appropriate distilled water wash, filter cake more than lyophilization 3h in freeze drying plant, namely obtain graphene product.
Embodiment 2
The present invention is a kind of method that plastic state physics peels off Graphene, and the method comprises the following steps:
S1. by purity more than 98%, particle diameter is that 30 ~ 500 μm of graphite flakes and stripper inject in ball grinder, wherein the consisting of of stripper: water 100 parts by weight, ethanol 40 parts by weight, normal propyl alcohol 20 parts by weight, polyurethane-modified polyacrylate 80 parts by weight, sodium fluoride 2 parts by weight.Wherein, the number-average molecular weight of polyurethane-modified polyacrylate is more than 100000.The weight ratio of graphite flakes and stripper is 1:3.
S2. ball milling 8h, the rotating speed of ball mill is 4000rpm/min.
S3. by discharging opening, suspension is expelled in storage tank after stopped reaction, stands 24h head product derived above.
S4. the graphene suspension in the storage tank obtained by step S3 is delivered in centrifuge, and centrifuge speed is 3000rpm/min, and centrifugation time 30min takes the supernatant, and in vacuum apparatus, vacuum is filtrated to get filter cake.
S5. filter cake step S4 obtained with appropriate distilled water wash, filter cake more than lyophilization 3h in freeze drying plant, namely obtain graphene product.
Embodiment 3
The present invention is a kind of method that plastic state physics peels off Graphene, and the method comprises the following steps:
S1. by purity more than 98%, particle diameter is that 30 ~ 500 μm of graphite flakes and stripper inject in ball grinder, wherein the consisting of of stripper: water 100 parts by weight, n-butyl alcohol 40 parts by weight, propylene glycol 40 parts by weight, polyurethane-modified polyacrylate 60 parts by weight, sodium chloride 4 parts by weight.Wherein, the number-average molecular weight of polyurethane-modified polyacrylate is more than 100000.The weight ratio of graphite flakes and stripper is 1:4.
S2. ball milling 24h, the rotating speed of ball mill is 3000rpm/min.
S3. by discharging opening, suspension is expelled in storage tank after stopped reaction, stands 24h head product derived above.
S4. the graphene suspension in the storage tank obtained by step S3 is delivered in centrifuge, and centrifuge speed is 4000rpm/min, and centrifugation time 1h takes the supernatant, and in vacuum apparatus, vacuum is filtrated to get filter cake.
S5. filter cake step S4 obtained with appropriate distilled water wash, filter cake more than lyophilization 3h in freeze drying plant, namely obtain graphene product.
Embodiment 4
The present invention is a kind of method that plastic state physics peels off Graphene, and the method comprises the following steps:
S1. by purity more than 98%, particle diameter is that 30 ~ 500 μm of graphite flakes and stripper inject in ball grinder, wherein the consisting of of stripper: water 100 parts by weight, terpineol 100 parts by weight, polyacrylate 70 parts by weight, lithium chloride 5 parts by weight.Wherein, the number-average molecular weight of polyacrylate is more than 100000.The weight ratio of graphite flakes and stripper is 1:5.
S2. ball milling 48h, the rotating speed of ball mill is 2000rpm/min.
S3. by discharging opening, suspension is expelled in storage tank after stopped reaction, stands 24h head product derived above.
S4. the graphene suspension in the storage tank obtained by step S3 is delivered in centrifuge, and centrifuge speed is 6000rpm/min, and centrifugation time 10min takes the supernatant, and in vacuum apparatus, vacuum is filtrated to get filter cake.
S5. filter cake step S4 obtained with appropriate distilled water wash, filter cake more than lyophilization 3h in freeze drying plant, namely obtain graphene product.
The above is only the preferred embodiment of the present invention; it should be pointed out that, for those skilled in the art, under the premise without departing from the technology of the present invention principle; can also making some improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (4)
1. the method that a plastic state physics peels off Graphene, it is characterised in that the method comprises the following steps:
S1. by purity more than 98%, particle diameter is that 30 ~ 500 μm of graphite flakes and stripper inject in ball grinder according to the weight ratio of 1:2～5, wherein the consisting of of stripper:
100 parts of water,
Alcohols solvent 30～100 parts,
Polyacrylate or polyacrylate derivatives 50～80 parts,
Water soluble salt 0.5～5 part；
Wherein, each component is in its parts by weight；
S2. ball milling 4～48h, the rotating speed of ball mill is more than 2000rpm/min；
S3. by discharging opening, suspension is expelled in storage tank after stopped reaction, stands 24h head product derived above；
S4. the graphene suspension in the storage tank obtained by step S3 is delivered in centrifuge, and centrifuge speed is 1000～6000rpm/min, and centrifugation time 10min～2h takes the supernatant, and in vacuum apparatus, vacuum is filtrated to get filter cake；
S5. filter cake step S4 obtained with appropriate distilled water wash, filter cake more than lyophilization 3h in freeze drying plant, namely obtain graphene product.
2. the method that plastic state physics as claimed in claim 1 peels off Graphene, it is characterised in that in described step S1, described alcohols solvent is one or more in ethanol, normal propyl alcohol, n-butyl alcohol, propylene glycol and terpineol.
3. the method that plastic state physics as claimed in claim 1 peels off Graphene, it is characterised in that in described step S1, the number-average molecular weight of described polyacrylate or polyacrylate derivatives is more than 100000.
4. the method that plastic state physics as claimed in claim 1 peels off Graphene, it is characterised in that in described step S1, described water soluble salt is the one in lithium fluoride, sodium fluoride, sodium chloride, lithium chloride.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410708363.0A CN105712330A (en) | 2014-12-01 | 2014-12-01 | Viscous physical stripping method for graphene |
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| CN201410708363.0A CN105712330A (en) | 2014-12-01 | 2014-12-01 | Viscous physical stripping method for graphene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106283184A (en) * | 2016-08-31 | 2017-01-04 | 无锡东恒新能源科技有限公司 | A kind of monocrystal graphite material preparation facilities |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106283184A (en) * | 2016-08-31 | 2017-01-04 | 无锡东恒新能源科技有限公司 | A kind of monocrystal graphite material preparation facilities |
| CN106283184B (en) * | 2016-08-31 | 2018-09-04 | 无锡东恒新能源科技有限公司 | A kind of monocrystal graphite material preparation facilities |
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Application publication date: 20160629 |