CN102107869A - Method for preparing graphene by using modifying supercritical peeling technology - Google Patents
Method for preparing graphene by using modifying supercritical peeling technology Download PDFInfo
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Abstract
The invention provides a method for preparing graphene. The method comprises the following steps of: purifying a graphite raw material; guiding ions to a graphite intercalation by a chemical intercalation method to form a graphite intercalation compound, and performing graphite intercalation modularization; further making supercritical fluid (such as CO2, H2O, methane/ ethane/ propane, ethylene/ propylene, methanol/ ethanol, or ammonia or the like) act on the modularized graphite raw material by a modifying supercritical technology, wherein the supercritical fluid enters the graphite intercalation; and implementing effective peeling of a graphite layer by optimizing physical and chemical parameters (such as catalyst concentration, temperature, pressure and the like). According to the method, the peeling of the graphite layer is implemented by the modifying supercritical technology, and the graphene can be produced in batch.
Description
[technical field]
The present invention relates to field of material preparation, particularly about the improvement of preparation method of graphene.
[background technology]
2010, the An Deliegaimu of Univ Manchester UK and Constantine doctor Nuo Woxiaoluofu were because of having shared Nobel Prize in physics in the brilliance research aspect the Graphene.Based on Graphene, carbon-60, the development of novel carbon back functional materials such as carbon nanotube, scientific circles generally believe: " 20th century were centuries of silicon (Si), and 21 century will be the century of carbon (C) ".
Graphene has good electromechanical properties, and for example: electron motion is the fastest: the electronic movement velocity of Graphene has reached 1/300 of the light velocity, considerably beyond the movement velocity of electronics in general conductor.The thinnest, the hardest material: people's recent findings such as the James Hone of Columbia Univ USA, the hardness ratio diamond of Graphene is also high, taller last 100 times of the best in the world iron and steel of strength ratio.High-specific surface area: specific surface area 〉=2650m
2/ g.Be easy to modification and scale operation etc.
Estimate that the Graphene project will guide the industrial chain that is worth the many trillion dollar, bring the huge effect of scale economy.Its Application Areas comprises: lithium cell, ultracapacitor, and the high energy electrode materials of other energy storage device; The ultra light aircraft material that approaches as the scraps of paper; Super tough and tensile flak jackets; " space elevator " needed tough cable.The Graphene transistor, unicircuit, and supercomputer; High frequency circuit; The Graphene photodetector; The Graphene solar cell; The Graphene liquid crystal display, Organic Light Emitting Diode (OLED); High performance terahertz light laser apparatus; Chemical sensor, medical imaging apparatus etc.
The batch process that realizes Graphene is the foundation stone of whole industry chain development.The technology of preparing of being developed at present comprises mechanical preparation technology, the epitaxy method, and Pintsch process takes off the Si method, chemical Vapor deposition process, oxidation reduction process, chemical cleavage method, chemical stripping method or the like.But perhaps there are problems such as safety and environmental pollution in current existing technological method or be difficult to realize volume production, and and then causes the Graphene cost value high.
Therefore, be necessary to provide a kind of new preparation method of graphene, improve the aforementioned disadvantages of prior art.
[summary of the invention]
The object of the present invention is to provide a kind of can the scale production Graphene and the graphene preparation method of environmental protection.
For reaching aforementioned purpose, a kind of preparation method of graphene of the present invention, it comprises:
At first graphite raw material is carried out purification process;
With the iontophoresis graphite layers, form compound between graphite layers by interpolation between chemical layer, make the graphite layers modularization;
By the modification supercritical technology, utilize supercutical fluid to act on modular graphite material, make supercutical fluid enter graphite layers, optimize the physical-chemical parameters, realize effectively peeling off of graphite linings.
Further, describedly graphite raw material is carried out purification process comprise ultrasonic cleaning, remove dephasign material and impurity element.
Further, the ion of interpolation insertion graphite layers comprises organic ion and mineral ion between described chemical layer.
Further, described modification supercutical fluid is that temperature and pressure all are in the above liquid of stagnation point.
Further, described supercutical fluid comprises CO
2, H
2O, methane/ethane/propane, ethylene/propene, methanol/ethanol, or ammonia or the like.
Further, in described supercutical fluid, be added with catalyzer.
Further, aforementioned optimization the physical-chemical parameters comprises the optimization catalyst concn, adjusts treatment temp and pressure.
Compared with prior art, method of the present invention utilizes between chemical layer insertion technology and modification supercritical technology to optimize integration, and the double requirements of scale production and environmental protection is satisfied in the Graphene production more than the preparation technology who is developed can reach tonne.
[description of drawings]
Fig. 1 is the schema of graphene preparation method of the present invention.
Fig. 2 is the graphite layers model synoptic diagram of Graphene preparation process of the present invention.
[embodiment]
Alleged herein " embodiment " or " embodiment " are meant special characteristic, structure or the characteristic that can be contained at least one implementation of the present invention.Different in this manual local " in one embodiment " that occur not are all to refer to same embodiment, neither be independent or optionally mutually exclusive with other embodiment embodiment.
See also shown in Figure 1ly, it shows the schema of preparation method of graphene of the present invention.Graphene preparation method of the present invention as shown in the figure, it comprises the steps:
Step S1: at first graphite raw material is carried out purification process.For example graphite raw material can be put into ultrasonic cleaning device and carry out ultrasonic cleaning, remove the impurity in the graphite raw material, can get rid of dephasign material and impurity element in the graphite raw material by chemical treatment or other modes then.
Step S2: utilize insertion method between chemical layer, ion 21 (comprising inorganic and organic ion) is imported between the aforementioned graphite linings 22 through the graphite raw material behind the purifying, make the graphite layers modularization.See also shown in Figure 2ly, graphite has interlayer structure, with the carbon atom and the SP of one deck
2The hybridized orbital electronics forms covalent linkage, each carbon atom again with 2P
zOrbital electron forms metallic bond, forms the firm netted plane of hexagonal carbon-coating, layer with layer between then combine with faint Van der Waals force, a little less than the bonding force between the carbon-coating, spacing is bigger, causes the number of chemical material can insert bedding void, forms compound between graphite layers.Worked out hundreds of kind intercalation compound at present, no longer enumerated in detail one by one about the method the present invention who inserts between chemical layer.
Step S3: utilize supercutical fluid (as CO
2, H
2O, methane/ethane/propane, ethylene/propene, methanol/ethanol, or ammonia or the like.) act on the aforementioned insertion method of utilizing between chemical layer and import the modular graphite material of ionic, make supercutical fluid enter graphite layers, (for example in supercutical fluid, add catalyzer by optimizing the physical-chemical parameters, and optimization catalyst concn, perhaps regulate temperature and pressure in the treating processes or the like), realize effectively peeling off of graphite linings, thereby mass-produce grapheme material.
Pure material will be according to the difference of temperature and pressure, present change of state such as liquid, gas, solid, if raising temperature and pressure, come the variation of observation state, can find so, if reach specific temperature, pressure, this point of phenomenon that the disappearance of liquid and gas interface can occur is called as stagnation point.Supercutical fluid refers to the fluid that is under the above temperature and pressure of the stagnation point zone, near stagnation point, all fluidic rerum naturas such as fluidic density, viscosity, solubleness, thermal capacity, specific inductivity can occur phenomenon jumpy takes place.
Supercutical fluid has very unique physicochemical property, and its density approaches liquid, and viscosity approaches gas, and spread coefficient is big, viscosity is little, specific inductivity is big.Separating effect is better, is good solvent.Supercritical technology has had various application at present, and for example supercritical fluid extraction, supercutical fluid spraying, supercutical fluid foaming, supercutical fluid clean, supercutical fluid prepares ultrafine particulate, supercutical fluid polymerization or the like.
Method of the present invention utilizes supercutical fluid to enter graphite layers, can realize effectively peeling off of graphite linings by optimizing the physical-chemical parameters then.The rate of peeling off can reach more than 90%.
Method of the present invention, earlier graphite is carried out purification process, then graphite layers is carried out iontophoresis, re-use supercutical fluid and act on graphite, make supercutical fluid enter graphite layers, Graphene is peeled off from graphite by adding catalyzer and adjusting parameters such as optimizing temperature, pressure.Method of the present invention utilizes between chemical layer insertion technology and modification supercritical technology to optimize integration, and the double requirements of scale production and environmental protection is satisfied in the Graphene production more than the preparation technology who is developed can reach tonne.
Above-mentioned explanation has fully disclosed the specific embodiment of the present invention.It is pointed out that and be familiar with the scope that any change that the person skilled in art does the specific embodiment of the present invention does not all break away from claims of the present invention.Correspondingly, the scope of claim of the present invention also is not limited only to previous embodiment.
Claims (7)
1. preparation method of graphene, it comprises:
At first graphite raw material is carried out purification process;
With the iontophoresis graphite layers, form compound between graphite layers by interpolation between chemical layer, make the graphite layers modularization;
By the modification supercritical technology, utilize supercutical fluid to act on modular graphite material, make supercutical fluid enter graphite layers, optimize the physical-chemical parameters, realize effectively peeling off of graphite linings.
2. the method for claim 1 is characterized in that: describedly graphite raw material is carried out purification process comprise ultrasonic cleaning, remove dephasign material and impurity element.
3. the method for claim 1 is characterized in that: the ion that interpolation is inserted graphite layers between described chemical layer comprises organic ion and mineral ion.
4. the method for claim 1 is characterized in that: described modification supercutical fluid is that temperature and pressure all are in the above liquid of stagnation point.
5. method as claimed in claim 4 is characterized in that: described supercutical fluid comprises CO
2, H
2O, methane/ethane/propane, ethylene/propene, methanol/ethanol or ammonia.
6. the method for claim 1 is characterized in that: be added with catalyzer in described supercutical fluid.
7. as claim 1 or 6 described methods, it is characterized in that: aforementioned optimization the physical-chemical parameters comprises optimizes catalyst concn, adjustment treatment temp and pressure.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491313A (en) * | 2011-11-24 | 2012-06-13 | 中国科学院化学研究所 | Preparation device for graphene |
| CN102491314A (en) * | 2011-11-24 | 2012-06-13 | 中国科学院化学研究所 | Method for preparing graphene |
| CN102502607A (en) * | 2011-11-10 | 2012-06-20 | 郑州大学 | Method for preparing graphene solution based on supercritical carbon dioxide and pyrenyl polymers |
| CN102515154A (en) * | 2011-12-31 | 2012-06-27 | 常州大学 | Graphene preparation method |
| CN102583326A (en) * | 2012-01-11 | 2012-07-18 | 上海交通大学 | Method for preparing graphite by compressing CO2 fluid under ultrasonic assistance |
| CN103435030A (en) * | 2013-07-11 | 2013-12-11 | 中国石油大学(北京) | Preparation apparatus and preparation method for graphene |
| CN103771401A (en) * | 2013-12-26 | 2014-05-07 | 中国石油大学(北京) | Preparation method for single-layered graphene |
| CN103896258A (en) * | 2012-12-26 | 2014-07-02 | 海洋王照明科技股份有限公司 | Preparation method for boron-doped graphene |
| CN105399090A (en) * | 2015-12-22 | 2016-03-16 | 成都新柯力化工科技有限公司 | Graphene preparation method by using graphene quantum point mechanical stripping |
| CN104240964B (en) * | 2014-09-18 | 2017-02-15 | 上海交通大学 | Method for achieving in situ composition of graphene and activated carbon through supercutical fluid |
| CN106832500A (en) * | 2017-01-24 | 2017-06-13 | 南京科孚纳米技术有限公司 | A kind of preparation method of Graphene toughness reinforcing latex composite |
| CN108314012A (en) * | 2017-01-16 | 2018-07-24 | 山东恒华新材料有限公司 | Ammonia heat method batch prepares the production technology of graphene |
| CN108609613A (en) * | 2018-07-27 | 2018-10-02 | 郑州大学 | A kind of preparation method of zero defect graphene |
| CN109052380A (en) * | 2018-09-10 | 2018-12-21 | 成都紫苑华光新材料科技有限公司 | The method that full liquid water phase physics removing prepares graphene |
| CN110668433A (en) * | 2019-11-25 | 2020-01-10 | 陕西师范大学 | Method for preparing graphite/graphene composite material by supercritical carbon dioxide fluid and application |
| CN111020613A (en) * | 2019-12-18 | 2020-04-17 | 武汉低维材料研究院有限公司 | Preparation method of ultrathin graphene powder and product prepared by preparation method |
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| US20040034151A1 (en) * | 2002-08-15 | 2004-02-19 | Graftech Inc. | Graphite composites and methods of making such composites |
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2011
- 2011-03-21 CN CN2011100675431A patent/CN102107869A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20040034151A1 (en) * | 2002-08-15 | 2004-02-19 | Graftech Inc. | Graphite composites and methods of making such composites |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502607A (en) * | 2011-11-10 | 2012-06-20 | 郑州大学 | Method for preparing graphene solution based on supercritical carbon dioxide and pyrenyl polymers |
| CN102502607B (en) * | 2011-11-10 | 2013-07-31 | 郑州大学 | Method for preparing graphene solution based on supercritical carbon dioxide and pyrenyl polymers |
| CN102491314A (en) * | 2011-11-24 | 2012-06-13 | 中国科学院化学研究所 | Method for preparing graphene |
| CN102491313A (en) * | 2011-11-24 | 2012-06-13 | 中国科学院化学研究所 | Preparation device for graphene |
| CN102515154A (en) * | 2011-12-31 | 2012-06-27 | 常州大学 | Graphene preparation method |
| CN102515154B (en) * | 2011-12-31 | 2013-12-18 | 常州大学 | Graphene preparation method |
| CN102583326A (en) * | 2012-01-11 | 2012-07-18 | 上海交通大学 | Method for preparing graphite by compressing CO2 fluid under ultrasonic assistance |
| CN102583326B (en) * | 2012-01-11 | 2014-02-19 | 上海交通大学 | Method for preparing graphite by compressing CO2 fluid under ultrasonic assistance |
| CN103896258A (en) * | 2012-12-26 | 2014-07-02 | 海洋王照明科技股份有限公司 | Preparation method for boron-doped graphene |
| CN103896258B (en) * | 2012-12-26 | 2016-01-27 | 海洋王照明科技股份有限公司 | A kind of preparation method of boron doped graphene |
| CN103435030B (en) * | 2013-07-11 | 2015-08-19 | 中国石油大学(北京) | A kind of preparation facilities of Graphene and method |
| CN103435030A (en) * | 2013-07-11 | 2013-12-11 | 中国石油大学(北京) | Preparation apparatus and preparation method for graphene |
| CN103771401A (en) * | 2013-12-26 | 2014-05-07 | 中国石油大学(北京) | Preparation method for single-layered graphene |
| CN103771401B (en) * | 2013-12-26 | 2015-09-09 | 中国石油大学(北京) | A kind of preparation method of few layer graphene and device |
| WO2015096317A1 (en) * | 2013-12-26 | 2015-07-02 | 中国石油大学(北京) | Method for preparing single-layered graphene |
| CN104240964B (en) * | 2014-09-18 | 2017-02-15 | 上海交通大学 | Method for achieving in situ composition of graphene and activated carbon through supercutical fluid |
| CN105399090A (en) * | 2015-12-22 | 2016-03-16 | 成都新柯力化工科技有限公司 | Graphene preparation method by using graphene quantum point mechanical stripping |
| CN108314012A (en) * | 2017-01-16 | 2018-07-24 | 山东恒华新材料有限公司 | Ammonia heat method batch prepares the production technology of graphene |
| CN106832500A (en) * | 2017-01-24 | 2017-06-13 | 南京科孚纳米技术有限公司 | A kind of preparation method of Graphene toughness reinforcing latex composite |
| CN108609613A (en) * | 2018-07-27 | 2018-10-02 | 郑州大学 | A kind of preparation method of zero defect graphene |
| CN108609613B (en) * | 2018-07-27 | 2021-09-17 | 郑州大学 | Preparation method of defect-free graphene |
| CN109052380A (en) * | 2018-09-10 | 2018-12-21 | 成都紫苑华光新材料科技有限公司 | The method that full liquid water phase physics removing prepares graphene |
| CN110668433A (en) * | 2019-11-25 | 2020-01-10 | 陕西师范大学 | Method for preparing graphite/graphene composite material by supercritical carbon dioxide fluid and application |
| CN111020613A (en) * | 2019-12-18 | 2020-04-17 | 武汉低维材料研究院有限公司 | Preparation method of ultrathin graphene powder and product prepared by preparation method |
| CN111020613B (en) * | 2019-12-18 | 2021-05-21 | 武汉低维材料研究院有限公司 | Preparation method of ultrathin graphene powder and product prepared by preparation method |
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