CN106672949A - Method for preparing graphene by assisting in stripping graphite based on gas solubilization - Google Patents
Method for preparing graphene by assisting in stripping graphite based on gas solubilization Download PDFInfo
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- CN106672949A CN106672949A CN201611070936.7A CN201611070936A CN106672949A CN 106672949 A CN106672949 A CN 106672949A CN 201611070936 A CN201611070936 A CN 201611070936A CN 106672949 A CN106672949 A CN 106672949A
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- gas
- stripping
- method based
- solubilising
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
Abstract
The invention discloses a method for preparing graphene by assisting in stripping graphite based on gas solubilization. The method comprises the steps: 1) adding natural flake graphite, a stripping agent and a solvent into a container; 2) closing the container, introducing gas until the pressure is 1 atm to 10 atm and maintaining for 1 hour to 48 hours to realize gas solubilization in the solvent; 3) performing ultrasonic treatment on suspension liquid after gas solubilization at the ultrasonic powder of 100 to 800 W for 5 to 100 hours; 4) performing centrifugal separation on the solution after ultrasonic treatment to obtain a solid substance, namely the graphene. According to the preparation method provided by the invention, efficient stripping of the graphite is realized ultrasonically by taking the high-pressure solubilized gas as an auxiliary stirrping agent and taking the natural graphite as the raw material to prepare the graphene which can be dispersed in an organic solvent with high concentration.
Description
Technical field
The invention belongs to Graphene functional material preparing technical field, and in particular to one kind is based on gas solubilising up-stripping
The method of preparing graphite alkene.
Technical background
Graphene be by the two-dimensional atomic crystal material of single layer of carbon atom close-packed arrays, its have excellent electricity,
Calorifics and mechanical property, widely should so as to have in fields such as flexible electronic device, sensor, composite, energy storage, hydrogen storages
Use prospect.
At present, the preparation method on Graphene mainly has two kinds：Mechanical means and chemical method.Mechanical means includes micro-
The method of mechanical phonograph recorder separation, epitaxy method and heating SiC；Chemical method is chemical dispersion method.
Compared to chemical method, the Graphene crystal formation that Mechanical Method is obtained is more perfect, is readily obtained high-quality graphene, so that
More conducively play every excellent properties of Graphene.Found by the retrieval to prior art, Novoselov et al. uses microcomputer
The come off method of graphite of tool prepares single crystal graphene film, it is possible to the stable existence under external environment, and with metallicity
(Two-dimensional gas of massless dirac fermions in graphene,Nature,2005,438:
197-200.).However, this method is the graphene platelet that individual layer is filtered out using the thin slice of the graphite surface acquisition that rubs, its chi
It is very little whard to control, it is impossible to the reliably graphite flake sample of factory length foot supply.
With native graphite as raw material, using ultrasonic stripping method, it is expected to produce several layer graphenes in enormous quantities, this is conducive to reality
The batch production of the Graphene of existing high-crystallinity.However, at present in the method for report, the graphene dispersion degree that stripping is obtained is not
Height, charge stripping efficiency is also very low, and this significantly limits penetration and promotion of the method in industrial quarters.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided one kind is based on gas solubilising up-stripping graphite system
The method of standby Graphene.Preparation method of the invention is using the gas of high pressure solubilising as up-stripping agent, native graphite conduct
Raw material, ultrasound realizes the efficient stripping of graphite, and preparing can the scattered Graphene of high concentration in organic solvent.
The purpose of the present invention is achieved through the following technical solutions：
It is an object of the invention to provide a kind of method based on gas solubilising up-stripping preparing graphite alkene, bag
Include：
1) by natural flake graphite, remover and solvent addition container；Wherein, the quality of natural flake graphite and solvent
Than being 1：10000~1：10；Natural flake graphite is 1 with the mass ratio of remover：0.5~1：100；
2) closed container is passed through gas to pressure 1atm~10atm and keeps 1h~48h, realizes gas increasing in a solvent
It is molten；
3) ultrasonically treated, 100~800W of ultrasonic power, 5~100h of ultrasonic time are carried out to the suspension after gas solubilising；
4) solution after ultrasonically treated is centrifuged (first low-speed centrifugal again high speed centrifugation), isolated solids
As Graphene.
Preferably, the step 1) in natural flake graphite size be 50~10000 mesh.
Preferably, the step 1) in the mass ratio of natural flake graphite and solvent be 1：5000~1：100；Natural squama
Piece graphite is 1 with the mass ratio of remover：0.5~1：10.
Preferably, the step 1) in remover be selected from stearic acid, neopelex, quaternary ammonium compound, lecithin
The surface-actives such as fat, amino acid, glycine betaine, fatty glyceride, fatty acid sorbitan, polysorbate, polyoxyethylene, polyalcohol
The one or more combination of agent.
Preferably, the step 1) in solvent be selected from water, ethanol, methyl alcohol, acetone, propyl alcohol, butanol, acetic acid, acetic acid second
Ester, N methyl pyrrolidones, DMF, DMA, dimethyl sulfoxide (DMSO), hexane, toluene, benzene second
The one or more combination of alkene, perchloroethylene, trichloro ethylene, ethylene glycol ether and triethanolamine etc..
Preferably, the step 2) in gas be selected from air, nitrogen, oxygen, argon gas, hydrogen, carbon dioxide, formaldehyde,
The one or more combination of acetylene, methane, helium, hydrogen sulfide, sulfur dioxide, propane etc..
Preferably, the step 2) in pressure be 5atm~8atm.
Preferably, the step 2) in pressure hold time be 18h~36h.
Preferably, the step 3) in ultrasonic power be 500~700W, ultrasonic time be 5~24h.
Preferably, the step 4) in centrifugal treating include two stages of low-speed centrifugal and high speed centrifugation；Wherein, low speed
To remove big graphite particle, low-speed centrifugal speed is 200~2000rpm, and the total time of low-speed centrifugal is 20~180min for centrifugation；
To collect Graphene, ultracentrifugal speed is 8000~12000rpm to high speed centrifugation, the ultracentrifugal time for every time 10~
60min。
Compared with prior art, the positive effect of the present invention is as follows：
(1) preparation method of the invention is using graphite as raw material, and cheap low cost is more easily peelable into graphite
Alkene, and it is greatly improved yield；
(2) it is auxiliary remover using solubilized gas, the gas of solubilising is centered around around graphite flake, was peeled off in ultrasound
Cheng Zhong, between graphite flake layer together with remover, ultrasonic energy causes the gas of solubilising in lamella to expand rapidly, with remover
The rapid stripping of graphite flake layer is realized together, therefore the technique can greatly improved the charge stripping efficiency of graphite, safer, environmental protection
And it is environment-friendly；
(3) preparation method is simple to equipment requirement, easy to operate, and production stage is few, is suitable for large-scale production.
(4) the graphene-structured defect for being obtained using preparation method of the invention is few, and the number of plies is few, and concentration is high, and well
Remain the excellent properties of Graphene.
Brief description of the drawings
Fig. 1 is Graphene transmission electron microscope image prepared by the embodiment of the present invention 1.
Specific embodiment
Embodiments of the invention are elaborated below, the present embodiment is carried out under premised on technical solution of the present invention
Implement, give detailed implementation method and specific operating process, but protection scope of the present invention is not limited to following implementations
Example.
Embodiment 1
1) by the mesh natural flake graphites of 5mg 500 (Qingdao Tianyuan graphite Co., Ltd), 5mg neopelexes and
10mL water is added in closed container；
2) carbon dioxide is passed through in closed container, is 5atm to pressure, and keep 24h, realize the solubilising of carbon dioxide；
3) after pressure release, ultrasonically treated 5h is carried out in power 100W to the suspension containing solubilized gas；
4) to the solution after ultrasonically treated in 500rpm low-speed centrifugals 40min；Again through 10000rpm high speed centrifugations 3 times, often
Secondary centrifugation 10min, isolated solid matter is lamella two-dimensional graphene.
Graphene yield of the Graphene productivity ratio without gas solubilization processing for obtaining is processed through this process to improve
200%.Fig. 1 is the Graphene transmission electron microscope image for preparing, it can be seen that two-dimensional slice Graphene is piled into thin transparent
Layer.
Embodiment 2
Step such as embodiment 1,10000 mesh natural flake graphites are changed into by the natural flaky graphite of 500 mesh, other conditions with
Embodiment 1 is identical.Graphene yield of the Graphene productivity ratio without gas solubilization processing for obtaining is processed through this process to improve
400%.
Embodiment 3
Step such as embodiment 1, DMF is changed into by aqueous solvent, and other conditions are same as Example 1.Through this
Graphene yield of the Graphene productivity ratio without gas solubilization processing that process treatment is obtained improves 300%.
Embodiment 4
Step such as embodiment 1, polyoxyethylene, other conditions and embodiment 1 are changed into by remover neopelex
It is identical.Graphene yield of the Graphene productivity ratio without gas solubilization processing for obtaining is processed through this process improve 250%.
Embodiment 5
Step such as embodiment 1, changes gas into acetylene, and other conditions are same as Example 1.Process what is obtained through this process
Graphene yield of the Graphene productivity ratio without gas solubilization processing improves 270%.
Embodiment 6
Step such as embodiment 1,800W is become by ultrasonic power, and other conditions are same as Example 1.Processed through this process
To Graphene yield of the Graphene productivity ratio without gas solubilization processing improve 350%.
General principle of the invention, principal character and advantages of the present invention has been shown and described above.The technology of the industry
Personnel it should be appreciated that the present invention is not limited to the above embodiments, simply explanation described in above-described embodiment and specification this
The principle of invention, various changes and modifications of the present invention are possible without departing from the spirit and scope of the present invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appending claims and its
Equivalent is defined.
Claims (10)
1. a kind of method based on gas solubilising up-stripping preparing graphite alkene, including：
1) by natural flake graphite, remover and solvent addition container；Wherein, natural flake graphite is with the mass ratio of solvent
1：10000~1：10；Natural flake graphite is 1 with the mass ratio of remover：0.5~1：100；
2) closed container is passed through gas to pressure 1atm~10atm and keeps 1h~48h, realizes gas solubilising in a solvent；
3) ultrasonically treated, 100~800W of ultrasonic power, 5~100h of ultrasonic time are carried out to the suspension after gas solubilising；
4) solution after ultrasonically treated is centrifuged, isolated solids is Graphene.
2. a kind of method based on gas solubilising up-stripping preparing graphite alkene according to claim 1, its feature
It is：The step 1) in natural flake graphite size be 50~10000 mesh.
3. a kind of method based on gas solubilising up-stripping preparing graphite alkene according to claim 1, its feature
It is：The step 1) in the mass ratio of natural flake graphite and solvent be 1：5000~1：100；Natural flake graphite and stripping
It is 1 from the mass ratio of agent：0.5~1：10.
4. a kind of method based on gas solubilising up-stripping preparing graphite alkene according to claim 1, its feature
It is：The step 1) in remover be selected from stearic acid, neopelex, quaternary ammonium compound, lecithin, amino acid,
One kind of the surfactants such as glycine betaine, fatty glyceride, fatty acid sorbitan, polysorbate, polyoxyethylene, polyalcohol or
Several combinations.
5. a kind of method based on gas solubilising up-stripping preparing graphite alkene according to claim 1, its feature
It is：The step 1) in solvent be selected from water, ethanol, methyl alcohol, acetone, propyl alcohol, butanol, acetic acid, ethyl acetate, N methyl pyrroles
Pyrrolidone, DMF, DMA, dimethyl sulfoxide (DMSO), hexane, toluene, styrene, perchloro- second
The one or more combination of alkene, trichloro ethylene, ethylene glycol ether and triethanolamine etc..
6. a kind of method based on gas solubilising up-stripping preparing graphite alkene according to claim 1, its feature
It is：The step 2) in gas be selected from air, nitrogen, oxygen, argon gas, hydrogen, carbon dioxide, formaldehyde, acetylene, methane,
The one or more combination of helium, hydrogen sulfide, sulfur dioxide, propane etc..
7. a kind of method based on gas solubilising up-stripping preparing graphite alkene according to claim 1, its feature
It is：The step 2) in pressure be 5atm~8atm.
8. a kind of method based on gas solubilising up-stripping preparing graphite alkene according to claim 1, its feature
It is：The step 2) in pressure hold time be 18h~36h.
9. a kind of method based on gas solubilising up-stripping preparing graphite alkene according to claim 1, its feature
It is：The step 3) in ultrasonic power be 500~700W, ultrasonic time be 5~24h.
10. a kind of method based on gas solubilising up-stripping preparing graphite alkene according to claim 1, its feature
It is：The step 4) in centrifugal treating include two stages of low-speed centrifugal and high speed centrifugation；Wherein, low-speed centrifugal speed is
200~2000rpm, the total time of low-speed centrifugal is 20~180min；Ultracentrifugal speed is 8000~12000rpm, at a high speed
The time of centrifugation is every time 10~60min.
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| CN201611070936.7A CN106672949A (en) | 2016-11-29 | 2016-11-29 | Method for preparing graphene by assisting in stripping graphite based on gas solubilization |
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| CN201611070936.7A CN106672949A (en) | 2016-11-29 | 2016-11-29 | Method for preparing graphene by assisting in stripping graphite based on gas solubilization |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107628610A (en) * | 2017-10-30 | 2018-01-26 | 北京万源工业有限公司 | A kind of method that mechanical stripping method prepares graphene and graphene conductive liquid |
| CN109796012A (en) * | 2019-04-10 | 2019-05-24 | 任国峰 | A kind of graphene and preparation method thereof prepared by electrochemical process |
| CN110143586A (en) * | 2019-03-26 | 2019-08-20 | 上海烯望材料科技有限公司 | A kind of preparation method of the graphene of single layer or few layer |
| RU2787431C1 (en) * | 2021-10-29 | 2023-01-09 | Валерий Юлдашевич Ахмедов | Method for producing layered graphite and multilayer graphene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104843688A (en) * | 2015-04-20 | 2015-08-19 | 德阳烯碳科技有限公司 | Graphene preparation method |
-
2016
- 2016-11-29 CN CN201611070936.7A patent/CN106672949A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104843688A (en) * | 2015-04-20 | 2015-08-19 | 德阳烯碳科技有限公司 | Graphene preparation method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107628610A (en) * | 2017-10-30 | 2018-01-26 | 北京万源工业有限公司 | A kind of method that mechanical stripping method prepares graphene and graphene conductive liquid |
| CN110143586A (en) * | 2019-03-26 | 2019-08-20 | 上海烯望材料科技有限公司 | A kind of preparation method of the graphene of single layer or few layer |
| CN110143586B (en) * | 2019-03-26 | 2021-04-02 | 中科悦达(上海)材料科技有限公司 | Preparation method of single-layer or few-layer graphene |
| CN109796012A (en) * | 2019-04-10 | 2019-05-24 | 任国峰 | A kind of graphene and preparation method thereof prepared by electrochemical process |
| RU2787431C1 (en) * | 2021-10-29 | 2023-01-09 | Валерий Юлдашевич Ахмедов | Method for producing layered graphite and multilayer graphene |
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