CN106672951B - A kind of environmental-friendly high efficiency can prepare with scale graphene method - Google Patents
A kind of environmental-friendly high efficiency can prepare with scale graphene method Download PDFInfo
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- CN106672951B CN106672951B CN201611153179.XA CN201611153179A CN106672951B CN 106672951 B CN106672951 B CN 106672951B CN 201611153179 A CN201611153179 A CN 201611153179A CN 106672951 B CN106672951 B CN 106672951B
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- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- 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
Abstract
A kind of environmental-friendly high efficiency can prepare with scale graphene method, belong to technical field of graphene preparation.By will be in the aqueous dispersion liquid of graphite dispersion to graphite derivative, it is removed in conventional shearing equipment, obtaining lamella size is 1-10 microns, and the number of plies is 1-5 layers, it is initially 2-7mg/mL aqueous dispersion liquid rich in graphene concentration, obtains graphene after the processing such as being fired.This method has many advantages, such as that charge stripping efficiency is high, at low cost, environmentally protective, has industrial applications prospect.
Description
Technical field
The invention belongs to technical field of graphene preparation, also belong to act on using graphite derivative as dispersing agent in shear stress
The application of lower removing preparation field of graphene.More particularly to using graphite as raw material, by stock dispersion with cutting in graphite derivative
Stress prepares high concentration graphene method.
Background technique
As a kind of novel nano material, the preparation and application research of graphene becomes the hot spot of Material Field.Graphite
Alkene is one kind by SP2The carbon atom of hydridization bonding in the form of hexagon grid forms the two-dimensional surface single layer structure of carbon.Graphite
Alkene is the basic unit for constructing other dimension carbon materials.There is graphene good electricity-optics performance, mechanical property, heat to pass
Performance and high charge carrier mobility are led, while there are also outstanding mechanical strengths and flexibility.Graphene these
Property allows it to have become a hot topic of research.The graphene and its derivative handled by chemical modification is even more to have specific function
Material can be used for transistor, liquid-crystal apparatus, electrochemica biological sensor, supercapacitor, fuel cell, solar battery etc.
Deng.Although the extensive high quality of production of graphene is still a difficult point currently, having prepared high-quality graphene, because
This solves this difficult point as the focus of attention and research.
Currently, people usually use mechanical stripping method, chemical vapour deposition technique, epitaxial growth method, oxidation-reduction method, liquid phase stripping
Graphene is prepared from method etc..But every kind of method has shortcoming.For example, mechanical stripping method can prepare high-quality graphene,
But limits throughput.Though and vapour deposition process can be used for preparing large-area graphene, its production technology complexity, preparation condition
The separation of harsh, high production cost and graphene film and shifting process have very high difficulty.Oxidation-reduction method is current energy
The method of large-scale industrial production, but the graphene prepared existing defects on the Nomenclature Composition and Structure of Complexes, leverage graphite
The chemical property of alkene.Liquid phase stripping method prepares graphene simple process and low cost, but yield is small etc., and removing used is set
Standby usually supersonic generator, causes product defects more, and area is small, using limited, scale amplification difficulty.Liquid phase removes legal system
Standby graphene is a kind of method for being expected to realize high-quality graphene mass production.So high-performance can largely be prepared by developing one kind
The new method of graphene is critically important.The existing release system that liquid phase method prepares graphene specifically include that organic solvent and auxiliary agent,
Water/surfactant, ionic liquid etc..There are some disadvantages when organic solvent is as stripping media, and if toxicity is big, price is high
It is expensive, hardly possible separates, and biocompatibility is bad etc..Water is good solvent and nontoxicity, but the surface tension of water can not be with stone
Black alkene matches, it is necessary to surfactant is added to reduce the surface tension of water, to help to remove graphite.Different surfaces is living
Property agent is due to the difference of its structural property, and the effect for removing graphene is also different, moreover, added by same surfactant
Amount it is different, the peeling effect of graphite is also different.Common surfactant has, neopelex, polyethylene pyrrole
Pyridine alkanone, sodium taurocholate, cow-bezoar NaTDC etc..This brings two main problems again simultaneously, first is that increased costs, second is that absorption
Surfactant be difficult to remove, it is difficult to recycle.
Under the action of shear stress, raw graphite is shelled using the graphite derivative for being easily dispersed in water as dispersing agent by the present invention
From graphene is prepared, had using the advantages of this dispersing agent: (1) charge stripping efficiency is high, has industrial application value；(2) do not draw
Enter exogenous impurity, the graphite derivative being added while being stripped into two-dimension nano materials, it can be by the means such as being centrifuged and standing
It separates, is reused as dispersing agent or as product with graphene；Stone can also be converted by the means such as restoring and calcining
Black alkene.Using water as dispersing agent, removing carries out the system used at normal temperatures and pressures, green, environmental protection, safety.More it is essential that
Shearing equipment of the present invention is all industrial commonly used equipment, easy scale amplification.
Summary of the invention
The present invention provides a kind of novel method for preparing graphene with shearing equipment.Using the derivative of graphite as dispersion
Agent is removed with shearing equipment in water, obtains graphene.This method is simple and easy, and obtained nanometer tablet quality is high, and size can
Control, high efficiency, low cost are suitble to large-scale production, are with a wide range of applications.
The invention discloses a kind of methods for preparing graphene with shearing equipment removing, it is characterised in that has mistake below
Journey and step:
Using graphite derivative as dispersing agent, different graphite raw materials is distributed to the aqueous dispersion liquid of graphite derivative
In, in shearing equipment, under the regular hour, carries out removing and processing obtains graphene.Mixed liquor after above-mentioned removing into
Row is stood or centrifugation, and supernatant is pure graphene solution.Or the suspension rich in graphene after shearing dispersion is calcined
Obtain graphene.
Graphite raw material includes but is not limited to: expansible graphite, natural flake graphite, synthetic graphite etc..
Graphite derivative includes but is not limited to: graphite oxide, edge graphite oxide, sulfonated graphite, carboxyl graphite etc..
The shearing equipment used includes and is not limited to: ball mill, high-speed shearing machine, high-speed mixer etc..
It stands or is centrifugated；The purifying graphenes such as high-temperature roasting, calcination temperature is between 300-1050 DEG C, and the time is in 3-
Between 3600s.
Using water as medium, the mass ratio of graphite derivative and graphite raw material is between 1:1-1:30.It is shelled under room temperature, normal pressure
From initial gained is rich in graphene suspension concentration between 2-7mg/mL.Splitting time is between 1-10 hours.
It is preferred that the number of plies of graphene, between 1-5 layers, size is between 1-10 microns.
It is of the invention can be by adjusting or controlling the additional amount of splitting time, graphite derivative, graphite raw material powder
The conditions such as concentration, size, thickness and the amount of graphene etc. of graphene sheet layer required for obtaining.Experimental result of the invention is,
In a certain range, splitting time is longer, and the size of obtained graphene is smaller, and suspension concentration is higher, and number of plies variation is not
Greatly.
Detailed description of the invention
A specific embodiment of the invention is described in further detail with reference to the accompanying drawing；
Fig. 1 is the SEM figure of the graphene of the removing preparation of the embodiment of the present invention 1；
Fig. 2 is the TEM figure of the graphene of the removing preparation of the embodiment of the present invention 1；
Fig. 3 is the AFM figure of the graphene of the removing preparation of the embodiment of the present invention 1.
Specific embodiment
It is the non-limiting example that the present invention prepares graphene below.The present invention should also include, without departing substantially from model of the present invention
The various changes that those of ordinary skill in the art are able to carry out under conditions of enclosing.
1 this method of embodiment prepares graphene nano material, comprising the following steps: uses high speed homogenization dispersion machine.
It 1) is the corresponding dispersion liquid of 1:10 preparation by graphite oxide and expansible graphite mass ratio, magneton stirring 30min is obtained
The dispersion liquid for being 16.5mg/mL to total concentration.
2) high speed homogenization dispersion machine is placed in shear in the dispersion liquid of step 1) and is dispersed, it is under normal temperature and pressure, dispersion liquid is pre-
3h is removed, suspension is obtained.
3) suspension that step 2) removing obtains is stood for 24 hours, takes supernatant in the case where revolving speed is 3000rpm, centrifugation
10min takes supernatant.
The concentration of graphene is 2mg/mL in the supernatant that above-mentioned centrifugation obtains, and yield 12.2%, length scale is average
It is 8.6 μm, 1-5 layers of the number of plies.
Embodiment 2: in addition to following variations, remaining process is the same as embodiment 1.Graphite raw material uses natural flake graphite, and oxygen
The mass ratio of graphite and natural flake graphite is 1:15, and obtained graphene concentration is 3mg/mL, yield 12.5%, length
9 μm of size average out to, 1-5 layers of the number of plies.
Embodiment 3: in addition to following variations, remaining process is the same as embodiment 1.Graphite raw material uses synthetic graphite, sulfonated graphite
Mass ratio with synthetic graphite is 1:25, and the total concentration of dispersion liquid is 39mg/mL, and obtained graphene concentration is 5mg/mL,
Yield is 12.8%, 10 μm of length scale average out to, 1-5 layers of the number of plies.
Embodiment 4: in addition to following variations, remaining process is the same as embodiment 1.Splitting time is 1h, obtained graphene it is dense
Degree is 1.2mg/mL, and yield 7.3%, 10 μm of length scale average out to, the number of plies is less than 5 layers.
Embodiment 5: in addition to following variations, remaining process is the same as embodiment 1.Splitting time is 2h, obtained graphene it is dense
Spending is 1.6mg/mL, yield 9.7%, 7 μm of length scale average out to, 1-5 layers of the number of plies.
Embodiment 6: in addition to following variations, remaining process is the same as embodiment 1.Splitting time is 4h, obtained graphene it is dense
Spending is 2.5mg/mL, yield 12.5%, 5 μm of length scale average out to, 1-5 layers of the number of plies.
Embodiment 7: in addition to following variations, remaining process is the same as embodiment 1.Splitting time is 6h, obtained graphene it is dense
Spending is 1mg/mL, yield 6.1%, 1 μm of length scale average out to, 1-5 layers of the number of plies.
Embodiment 8: in addition to following variations, remaining process is the same as embodiment 1.The mass ratio of graphite oxide and expansible graphite
For 1:5, the concentration of obtained graphene is 1.1mg/mL, yield 12%, 8.5 μm of length scale average out to, 1-5 layers of the number of plies.
Embodiment 9: in addition to following variations, remaining process is the same as embodiment 1.The quality of edge graphite oxide and crystalline flake graphite it
Than for 1:20, the total concentration of dispersion liquid is 31.5mg/mL, and obtained dispersion liquid is removed with ball mill, dispersion liquid is obtained
Concentration is 4mg/mL, yield 12.7%, 8.7 μm of length scale average out to, 1-5 layers of the number of plies.
Embodiment 10: in addition to following variations, remaining process is the same as embodiment 11.Use carboxyl graphite as dispersing agent, carboxyl
The mass ratio of graphite and expansible graphite is 1:25, and the total concentration of dispersion liquid is 39mg/mL, and the concentration of obtained graphene is
6mg/mL, yield 15.4%, 8.7 μm of length scale average out to, 1-5 layers of the number of plies.
Embodiment 11: in addition to following variations, remaining process is the same as embodiment 10.The mass ratio of carboxyl graphite and synthetic graphite
For 1:30, the total concentration of dispersion liquid is 46.5mg/mL, and the concentration of obtained graphene is 7mg/mL, yield 15%, and length is flat
Equal size is 8.6 μm, 1-5 layers of the number of plies.
Embodiment 12: in addition to following variations, remaining process is the same as embodiment 1.Dispersion liquid is removed with kitchen blender, is obtained
Graphene concentration be 2.1mg/mL, yield 12.7%, length mean size be 9 μm, 1-5 layers of the number of plies.
Or being suspended at 1000 DEG C rich in graphene after the shearing dispersion in embodiment 1 is calcined into 600s and obtains stone
Black alkene, by elemental analysis, the purity of graphene is up to 99%.
The suspension rich in graphene after shearing dispersion in embodiment 2 is calcined into 1800s at 900 DEG C and obtains graphite
Alkene, by elemental analysis, the purity of graphene is up to 99%.
The suspension rich in graphene after shearing dispersion in embodiment 3 is calcined into 3000s at 700 DEG C and obtains graphite
Alkene, by elemental analysis, the purity of graphene is up to 98%.
The above embodiment of the present invention merely to detailed description examples of the invention, it is all belong to it is of the invention
The variation that technical solution is amplified out is still in the scope of protection of the present invention.
Claims (9)
1. a kind of method for preparing graphene with shearing equipment removing, which is characterized in that have process below and step:
Using graphite derivative as dispersing agent, different graphite raw materials is distributed in the aqueous dispersion liquid of graphite derivative,
In shearing equipment, under the regular hour, carries out removing and processing obtains graphene；Mixed liquor after above-mentioned removing is stood
Or centrifugation, supernatant are pure graphene solution；Or it is calcined the suspension rich in graphene after shearing dispersion to obtain stone
Black alkene；Graphite derivative is selected from sulfonated graphite, carboxyl graphite.
2. according to a kind of method for preparing graphene with shearing equipment removing of claim 1, which is characterized in that graphite raw material choosing
From expansible graphite, natural flake graphite, synthetic graphite.
3. according to a kind of method for preparing graphene with shearing equipment removing of claim 1, which is characterized in that the shearing used
Equipment is selected from: ball mill, high-speed shearing machine, high-speed mixer.
4. according to a kind of method for preparing graphene with shearing equipment removing of claim 1, which is characterized in that calcining purifying stone
Black alkene, calcination temperature is between 300-1050 DEG C.
5. according to a kind of method for preparing graphene with shearing equipment removing of claim 1, which is characterized in that calcining purifying stone
Black alkene, calcination time is between 3s-3600s.
6. according to a kind of method for preparing graphene with shearing equipment removing of claim 1, which is characterized in that with water be situated between
The mass ratio of matter, graphite derivative and graphite raw material is between 1:1-1:30.
7. according to a kind of method for preparing graphene with shearing equipment removing of claim 1, which is characterized in that in room temperature, often
Pressure removing, initial gained is rich in graphene suspension concentration between 2-7mg/mL.
8. according to a kind of method for preparing graphene with shearing equipment removing of claim 1, which is characterized in that splitting time exists
Between 1-10 hours.
9. according to a kind of method for preparing graphene with shearing equipment removing of claim 1, which is characterized in that the layer of graphene
Number is between 1-5 layers, and size is between 1-10 microns.
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| CN107381559A (en) * | 2017-09-05 | 2017-11-24 | 北京中元龙港矿业科技有限公司 | Two-dimensional graphene and preparation method thereof |
| CN108720998A (en) * | 2018-06-06 | 2018-11-02 | 张小伏 | A kind of speed suction high air permeable sanitary towel of antibacterial |
| CN109019577A (en) * | 2018-09-29 | 2018-12-18 | 深圳市通产丽星股份有限公司 | A kind of graphene and preparation method thereof |
| CN115611271B (en) * | 2022-10-28 | 2024-02-23 | 中国科学院福建物质结构研究所 | Preparation method of graphene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102009976A (en) * | 2010-12-28 | 2011-04-13 | 东南大学 | Method for preparing graphene film |
| CN104071784A (en) * | 2014-07-10 | 2014-10-01 | 中南林业科技大学 | Method for preparing graphene through reduction of oxidized graphene |
| CN104692363A (en) * | 2013-12-04 | 2015-06-10 | 北京化工大学 | Method for preparing graphene through hypergravity technology |
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| CN104973591B (en) * | 2014-04-11 | 2017-02-08 | 中国科学院上海硅酸盐研究所 | High-quality graphene and preparation method thereof |
| CN103935999B (en) * | 2014-05-09 | 2016-04-13 | 中国科学院上海微***与信息技术研究所 | A kind of preparation method of Graphene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102009976A (en) * | 2010-12-28 | 2011-04-13 | 东南大学 | Method for preparing graphene film |
| CN104692363A (en) * | 2013-12-04 | 2015-06-10 | 北京化工大学 | Method for preparing graphene through hypergravity technology |
| CN104071784A (en) * | 2014-07-10 | 2014-10-01 | 中南林业科技大学 | Method for preparing graphene through reduction of oxidized graphene |
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