CN105712326A - Method for producing graphene - Google Patents
Method for producing graphene Download PDFInfo
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- CN105712326A CN105712326A CN201410706292.0A CN201410706292A CN105712326A CN 105712326 A CN105712326 A CN 105712326A CN 201410706292 A CN201410706292 A CN 201410706292A CN 105712326 A CN105712326 A CN 105712326A
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Abstract
The invention discloses a method for producing graphene. The method comprises the following steps: S1) injecting the graphite flakes and a stripper in a kettle, turning on a motor of the kettle for stirring the materials, uniformly mixing the materials, wherein the stripper comprises the following components in parts by weight: 100 parts of an alcohols solvent, 50-80 parts of polyacrylate or a polyacrylate derivative, 0.5-4 parts of silica/poly(methyl methacrylate-styrene)double-shell composite microspheres, and 0.5-5 parts of water-soluble salt; S2) heating the kettle, keeping the temperature of the kettle at 50-80 DEG C, wherein the pressure is 1-3 atm, the rotating speed of a mixer shaft is 1000-2000 rpm/min, and the reaction time is 3-6 hours; S3) stopping the reaction, discharging an upper level fluid suspension, and standing; S4) centrifuging a graphene fluid suspension, after centrifugation is carried out, taking an upper level clear liquid for performing vacuum-filtering to obtain a filter cake; and S5) washing the filter cake, and performing freeze drying on the filter cake. The method used for stripping graphene has the advantages of no corrosion on equipment, and no damage on a structure of graphene.
Description
Technical field
The present invention relates to Graphene production technical field, be specifically related to a kind of Graphene 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 Graphene production method, 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 Graphene production method, 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 the kettle with agitator according to the weight ratio of 1:2～5, and the motor starting kettle is stirred, and makes mixing of materials uniform, wherein the consisting of of stripper:
Alcohols solvent 100 parts,
Polyacrylate or polyacrylate derivatives 50～80 parts,
Silicon dioxide/polymer composite microsphere 0.5～10 part,
Water soluble salt 0.5～5 part；
Wherein, each component is in its parts by weight；
S2. heating kettle, keeping still body temperature is 50 DEG C ~ 80 DEG C, and pressure is 1～3atm, and agitator shaft speed is 1000 ~ 2000rpm/min, response time 3 ~ 6h；
S3. by discharging opening, upper strata 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 S1, the particle diameter of described silicon dioxide/polymer composite microsphere is below 20 microns, and the particle diameter of described silicon dioxide is more than 50 nanometers, and described polymer layer of thickness is more than 10 nanometers.
Preferred technical scheme is, in step S1, described silicon dioxide/polymer composite microsphere is silicon dioxide/poly-(methyl methacrylate～styrene) bivalve layer complex microsphere.
Preferred technical scheme is, in step S1, 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 S1, the number-average molecular weight of described polyacrylate or polyacrylate derivatives is more than 100000.
Preferred technical scheme is, in step S1, described water soluble salt is the one in lithium fluoride, sodium fluoride, sodium chloride, lithium chloride.
Prior art is compared, Graphene production method of the present invention is by adopting special stripper for the stripping of Graphene, this stripper is added with the polyacrylate with glue viscosity or polyacrylate derivatives, use this stripper to coordinate to grind or stirring, the requirement to grinding or mixing speed can be reduced, it is not necessary to graphite flake layer ultra high shear can be realized the stripping to Graphene；Coordinating silicon dioxide/polymer composite microsphere, the core of silicon dioxide/polymer composite microsphere is stone, it is possible to graphite produces big release effect and shell deformable, non-friable functionalized graphene；The water soluble salt additionally added in system can improve the electric conductivity of system, avoid the Graphene peeled off because electrostatic is superimposed together again, particularly eliminate the electrostatic on silicon dioxide/polymer composite microsphere surface, make the Graphene after stripping keep the dispersity after peeling off.This Graphene production method is being peeled off while Graphene, and not etching apparatus does not damage graphene-structured.
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 Graphene production method, and the method comprises the following steps:
S1. by purity more than 98%, particle diameter is in 30 ~ 500 μm of graphite flakes and the stripper injection kettle with agitator, the motor starting kettle is stirred, make mixing of materials uniform, wherein the consisting of of stripper: ethanol 100 parts by weight, polyacrylate 50 parts by weight, silicon dioxide/poly-(methyl methacrylate～styrene) bivalve layer complex microsphere 0.5 parts by weight, lithium fluoride 2 parts by weight.Wherein, the particle diameter of silicon dioxide/poly-(methyl methacrylate～styrene) bivalve layer complex microsphere is below 20 microns, and the particle diameter of silica core is more than 50 nanometers, and the thickness of shell is more than 10 nanometers；The number-average molecular weight of polyacrylate is more than 100000.The weight ratio of graphite flakes and stripper is 1:2.
S2. heating kettle, keeping still body temperature is 80 DEG C, and pressure is 3atm, and agitator shaft speed is 1000rpm/min, response time 3h.
S3. by discharging opening, upper strata 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 Graphene production method, and the method comprises the following steps:
S1. by purity more than 98%, particle diameter is in 30 ~ 500 μm of graphite flakes and the stripper injection kettle with agitator, the motor starting kettle is stirred, make mixing of materials uniform, wherein the consisting of of stripper: ethanol 50 parts by weight, normal propyl alcohol 50 parts by weight, polyurethane-modified polyacrylate 80 parts by weight, silicon dioxide/poly-(methyl methacrylate～styrene) bivalve layer complex microsphere 5 parts by weight, sodium fluoride 5 parts by weight.Wherein, the particle diameter of silicon dioxide/poly-(methyl methacrylate～styrene) bivalve layer complex microsphere is below 20 microns, and the particle diameter of silica core is more than 50 nanometers, and the thickness of shell is more than 10 nanometers；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. heating kettle, keeping still body temperature is 50 DEG C, and pressure is 1atm, and agitator shaft speed is 2000rpm/min, response time 6h.
S3. by discharging opening, upper strata 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 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 Graphene production method, and the method comprises the following steps:
S1. by purity more than 98%, particle diameter is in 30 ~ 500 μm of graphite flakes and the stripper injection kettle with agitator, the motor starting kettle is stirred, make mixing of materials uniform, wherein the consisting of of stripper: n-butyl alcohol 40 parts by weight, propylene glycol 60 parts by weight, polyurethane-modified polyacrylate 60 parts by weight, silicon dioxide/poly-(methyl methacrylate～styrene) bivalve layer complex microsphere 2 parts by weight, sodium chloride 0.5 parts by weight.Wherein, the particle diameter of silicon dioxide/poly-(methyl methacrylate～styrene) bivalve layer complex microsphere is below 20 microns, and the particle diameter of silica core is more than 50 nanometers, and the thickness of shell is more than 10 nanometers；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. heating kettle, keeping still body temperature is 60 DEG C, and pressure is 2atm, and agitator shaft speed is 1500rpm/min, response time 4h.
S3. by discharging opening, upper strata 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 5000rpm/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 Graphene production method, and the method comprises the following steps:
S1. by purity more than 98%, particle diameter is in 30 ~ 500 μm of graphite flakes and the stripper injection kettle with agitator, the motor starting kettle is stirred, make mixing of materials uniform, wherein the consisting of of stripper: terpineol 100 parts by weight, polyacrylate 70 parts by weight, silicon dioxide/poly-(methyl methacrylate～styrene) bivalve layer complex microsphere 10 parts by weight, lithium chloride 3 parts by weight.Wherein, the particle diameter of silicon dioxide/poly-(methyl methacrylate～styrene) bivalve layer complex microsphere is below 20 microns, and the particle diameter of silica core is more than 50 nanometers, and the thickness of shell is more than 10 nanometers；The number-average molecular weight of polyacrylate is more than 100000.The weight ratio of graphite flakes and stripper is 1:5.
S2. heating kettle, keeping still body temperature is 55 DEG C, and pressure is 2atm, and agitator shaft speed is 15000rpm/min, response time 5h.
S3. by discharging opening, upper strata 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. a Graphene production method, 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 the kettle with agitator according to the weight ratio of 1:2～5, and the motor starting kettle is stirred, and makes mixing of materials uniform, wherein the consisting of of stripper:
Alcohols solvent 100 parts,
Polyacrylate or polyacrylate derivatives 50～80 parts,
Silicon dioxide/polymer composite microsphere 0.5～10 part,
Water soluble salt 0.5～5 part；
Wherein, each component is in its parts by weight；
S2. heating kettle, keeping still body temperature is 50 DEG C ~ 80 DEG C, and pressure is 1～3atm, and agitator shaft speed is 1000 ~ 2000rpm/min, response time 3 ~ 6h；
S3. by discharging opening, upper strata 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. Graphene production method as claimed in claim 1, it is characterized in that, in described step S1, the particle diameter of described silicon dioxide/polymer composite microsphere is below 20 microns, the particle diameter of described silicon dioxide is more than 50 nanometers, and described polymer layer of thickness is more than 10 nanometers.
3. Graphene production method as claimed in claim 2, it is characterised in that in described step S1, described silicon dioxide/polymer composite microsphere is silicon dioxide/poly-(methyl methacrylate～styrene) bivalve layer complex microsphere.
4. Graphene production method 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.
5. Graphene production method 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.
6. Graphene production method 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.
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| CN201410706292.0A CN105712326A (en) | 2014-12-01 | 2014-12-01 | Method for producing graphene |
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| CN201410706292.0A CN105712326A (en) | 2014-12-01 | 2014-12-01 | Method for producing graphene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106311581A (en) * | 2016-08-19 | 2017-01-11 | 苏州思创源博电子科技有限公司 | Manufacturing method for efficient composite heat sink for electronic product |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106311581A (en) * | 2016-08-19 | 2017-01-11 | 苏州思创源博电子科技有限公司 | Manufacturing method for efficient composite heat sink for electronic product |
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