CN105712322A - Method for producing bulky graphene - Google Patents
Method for producing bulky graphene Download PDFInfo
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- CN105712322A CN105712322A CN201410705233.1A CN201410705233A CN105712322A CN 105712322 A CN105712322 A CN 105712322A CN 201410705233 A CN201410705233 A CN 201410705233A CN 105712322 A CN105712322 A CN 105712322A
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Abstract
The invention discloses a method for producing bulky grapheme. The method comprises the following steps: S1) injecting graphite flakes and a stripper in a ball milling jar, wherein the stripper comprises the following components: 100 parts of water, 30-100 parts of an alcohols solvent, 50-80 parts of a polyacrylate or polyacrylate derivative, 1-30 parts of flaky metal powder, and 0.5-5 parts of water-soluble salt; S2) performing ball milling on the components for 4-48 hours, wherein a rotating speed of a bowl mill is more than 2000 rpm/min; S3) stopping a reaction and discharging a fluid suspension for standing; S4) conveying the graphene fluid suspension to a centrifuge for centrifugation, after centrifugation, an upper level clear liquid is taken for vacuum-filtering to obtain a filter cake; and S5) washing the filter cake, performing freeze drying on the filter cake. The method is capable of stripping bulky graphene with high efficiency.
Description
Technical field
The present invention relates to Graphene production technical field, be specifically related to the physics stripping type production method of a kind of large stretch of Graphene.
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 method producing large stretch of Graphene, 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 producing large stretch of 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,
Flake metal powder 1～30 part,
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.
Preferred technical scheme is, in step sl, described flake metal powder is one or more in zinc powder, nikel powder, argentum powder.
It is preferred that technical scheme be that in step sl, described flake metal powder is of a size of 3～10 microns.
Prior art is compared, Graphene stripping type production method of the present invention is by adopting special 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 and shear and peeling effect；Coordinate flake metal powder, it is possible to the peeling force that graphite is produced along lamella direction；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 large stretch of 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 producing large stretch of 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: 100 parts of water, ethanol 60 parts by weight, polyacrylate 50 parts by weight, zinc flake 1 parts by weight, lithium fluoride 0.5 parts by weight.Wherein, the number-average molecular weight of polyacrylate is more than 100000；Zinc flake is of a size of 3～10 microns.The weight ratio of graphite flakes and stripper is 1:4.
S2. ball milling 4h, the rotating speed of ball mill is 8000rpm/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 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.
Embodiment 2
The present invention is a kind of method producing large stretch of 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: 100 parts of water, ethanol 15 parts by weight, normal propyl alcohol 15 parts by weight, polyurethane-modified polyacrylate 80 parts by weight, Nickel Powder 30 parts by weight, sodium fluoride 2 parts by weight.Wherein, the number-average molecular weight of polyurethane-modified polyacrylate is more than 100000；Nickel Powder is of a size of 3～10 microns.The weight ratio of graphite flakes and stripper is 1:3.
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 2000rpm/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 3
The present invention is a kind of method producing large stretch of 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: 100 parts of water, n-butyl alcohol 30 parts by weight, propylene glycol 50 parts by weight, polyurethane-modified polyacrylate 60 parts by weight, flake silver powder 20 parts by weight, sodium chloride 4 parts by weight.Wherein, the number-average molecular weight of polyurethane-modified polyacrylate is more than 100000；Flake silver powder is of a size of 3～10 microns.The weight ratio of graphite flakes and stripper is 1:5.
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 4000rpm/min, and centrifugation time 20min 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 producing large stretch of 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: 100 parts of water, terpineol 100 parts by weight, polyacrylate 70 parts by weight, zinc flake 10 parts by weight, Nickel Powder 10 parts by weight, lithium chloride 5 parts by weight.Wherein, the number-average molecular weight of polyacrylate is more than 100000；Nickel Powder and zinc powder are of a size of 3～10 microns.The weight ratio of graphite flakes and stripper is 1:2.
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 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 (6)
1. the method producing large stretch of 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,
Flake metal powder 1～30 part,
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 producing large stretch of Graphene as claimed in claim 1, 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 producing large stretch of Graphene as claimed in claim 1, 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 producing large stretch of Graphene as claimed in claim 1, 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.
5. the method producing large stretch of Graphene as claimed in claim 1, it is characterised in that in described step S1, described flake metal powder is one or more in zinc powder, nikel powder, argentum powder.
6. the method producing large stretch of Graphene as claimed in claim 5, it is characterised in that in described step S1, described flake metal powder is of a size of 3～10 microns.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410705233.1A CN105712322A (en) | 2014-12-01 | 2014-12-01 | Method for producing bulky graphene |
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| CN201410705233.1A CN105712322A (en) | 2014-12-01 | 2014-12-01 | Method for producing bulky graphene |
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| CN105712322A true CN105712322A (en) | 2016-06-29 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107043105A (en) * | 2017-05-25 | 2017-08-15 | 拜永孝 | A kind of method of continuous prepare with scale high-quality graphene |
| CN110405207A (en) * | 2019-08-14 | 2019-11-05 | 哈尔滨工业大学 | A kind of method that the SPS sintering of PE-CVD auxiliary prepares graphene enhancing titanium composite material |
-
2014
- 2014-12-01 CN CN201410705233.1A patent/CN105712322A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107043105A (en) * | 2017-05-25 | 2017-08-15 | 拜永孝 | A kind of method of continuous prepare with scale high-quality graphene |
| CN110405207A (en) * | 2019-08-14 | 2019-11-05 | 哈尔滨工业大学 | A kind of method that the SPS sintering of PE-CVD auxiliary prepares graphene enhancing titanium composite material |
| CN110405207B (en) * | 2019-08-14 | 2021-07-20 | 哈尔滨工业大学 | Method for preparing graphene reinforced titanium-based composite material by PE-CVD assisted SPS sintering |
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