CN106672951A - Environment-friendly, high-efficiency and large-scale graphene preparation method - Google Patents
Environment-friendly, high-efficiency and large-scale graphene preparation method Download PDFInfo
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- CN106672951A CN106672951A CN201611153179.XA CN201611153179A CN106672951A CN 106672951 A CN106672951 A CN 106672951A CN 201611153179 A CN201611153179 A CN 201611153179A CN 106672951 A CN106672951 A CN 106672951A
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- graphite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B2204/32—Size or surface area
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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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
Abstract
The invention discloses an environment-friendly, high-efficiency and large-scale graphene preparation method, and belongs to the technical field of graphene preparation. The environment-friendly, high-efficiency and large-scale graphene preparation method comprises the following steps: dispersing graphite to a water-phase dispersion solution of a graphite derivative; stripping in a conventional shear device, thus obtaining a water-phase dispersion solution of which the layer size is 1 to 10 mu m, the layer number is 1 to 5 and the initial graphene concentration is 2 to 7 mg/mL; carrying out treatment of roasting and the like, thus obtaining graphene. The environment-friendly, high-efficiency and large-scale graphene preparation method disclosed by the invention has the advantages of high stripping efficiency, low cost, environment protection and the like, and has an industrial application prospect.
Description
Technical field
The invention belongs to technical field of graphene preparation, also belongs to using graphite derivative be acted in shear stress as dispersant
It is lower to peel off the application for preparing field of graphene.Specifically related to graphite as raw material, by stock dispersion in graphite derivative with cutting
Stress prepares high concentration graphene method.
Background technology
Used as the new nano material of a class, the preparation and application research of Graphene becomes the focus of Material Field.Graphite
Alkene is one kind by SP2The carbon atom of hydridization bonding in the form of hexagon grid, the two dimensional surface monolayer knot of the carbon for being formed
Structure.Graphene is the elementary cell for building other dimension material with carbon elements.Graphene has good electricity-optics performance, mechanical property
Energy, heat-conductive characteristic and high charge carrier mobility, while also outstanding mechanical strength and pliability.Graphene
These properties, allow it to become the focus of research.It is special that the Graphene processed by chemical modification and its derivant are even more had
The material of function, can be used for transistor, liquid-crystal apparatus, electrochemica biological sensor, ultracapacitor, fuel cell, solar energy
Battery etc..At present, although prepared high-quality graphene, but the extensive high quality of production of Graphene is still a difficulty
Point, therefore solve this difficult point and become the focus of attention and research.
At present, people are generally with 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 weak point.For example, mechanical stripping method can prepare high-quality graphene,
But limits throughput.And though vapour deposition process can be used to prepare large-area graphene, its complex manufacturing, preparation condition
The separation of harsh, production cost height 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 for preparing existing defects on the Nomenclature Composition and Structure of Complexes, leverage graphite
The chemical property of alkene.Liquid phase stripping method method prepares Graphene process is simple, low cost, but yield is little etc., stripping used
Equipment is usually supersonic generator, causes product defects many, and area is little, and application is limited, and scale is amplified difficult.Liquid phase stripping method
It is a kind of method for being expected to and realizing high-quality graphene mass production to prepare Graphene.So development one kind can in a large number prepare high property
The new method of energy Graphene is critically important.Liquid phase method prepares the existing release system of Graphene mainly to be included：Organic solvent and help
Agent, water/surfactant, ionic liquid etc...There are some shortcomings when organic solvent is as stripping media, such as toxicity is big, price
Costliness, hardly possible is separated, and biocompatibility is bad etc..Water is good solvent and avirulence, but the surface tension of water can not be with
Graphene matches, it is necessary to add surfactant to reduce the surface tension of water, so as to help peel off graphite.Different surfaces
, due to the difference of its structural property, also each portion one is identical for the effect of stripping Graphene for activating agent, and, same surfactant
Added amount is different, and the peeling effect of graphite is also different.Common surfactant has, dodecylbenzene sodium sulfonate, poly- second
Annulated pyridine alkanone, sodium cholate, Calculus Boviss NaTDC etc..This brings two subject matters again simultaneously, and one is that cost increases, and two are
The surfactant of absorption is difficult to remove, it is difficult to recycle and reuse.
The present invention in the presence of shear stress, raw graphite is shelled with being easily dispersed in the graphite derivative of water as dispersant
From Graphene is prepared, the advantage using this dispersant has：(1) charge stripping efficiency is high, with industrial application value；(2) do not draw
Enter exogenous impurity, the graphite derivative for being added by centrifugation and the means such as can stand while be stripped into two-dimension nano materials
Separate with Graphene, reuse as dispersant or as product；Stone can also be converted into by the means such as reduction and calcining
Black alkene.With water as dispersant, stripping is carried out at normal temperatures and pressures the system for adopting, green, environmental protection, safety.More it is essential that
Shearing equipment of the present invention, is all industrial common equipment, and easy scale is amplified.
The content of the invention
The present invention provides a kind of new method for preparing Graphene with shearing equipment.Derivant using graphite is used as dispersion
Agent, is peeled off in water with shearing equipment, obtains Graphene.The method is simple, and the nanometer tablet quality for obtaining is high, big I
Control, high efficiency, low cost is adapted to large-scale production, is with a wide range of applications.
The invention discloses a kind of method for preparing Graphene with shearing equipment stripping, it is characterised in that with following mistake
Journey and step：
Using graphite derivative as dispersant, different graphite raw materials is distributed to into the aqueous dispersion liquid of graphite derivative
In, in shearing equipment, under the regular hour, peeled off and process is obtained Graphene.Mixed liquor after above-mentioned stripping enters
Row stands or is centrifuged, and supernatant is pure graphene solution.Or calcined the suspension rich in Graphene after shearing dispersion
Obtain Graphene.
Graphite raw material is included but is not limited to：Expansible graphite, natural flake graphite, synthetic graphite etc..
Graphite derivative is included but is not limited to：Graphite oxide, edge graphite oxide, sulfonated graphite, carboxyl graphite etc..
The shearing equipment for using includes and is not limited to：Ball mill, high-speed shearing machine, homogenizer etc..
Stand or centrifugation；The purifying graphenes such as high-temperature roasting, between 300-1050 DEG C, the time is in 3- for calcining heat
Between 3600s.
With water as medium, the mass ratio of graphite derivative and graphite raw material is 1：1-1：Between 30.Shell 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 is between 1-5 layers, size is between 1-10 microns.
Can the passing through of the present invention adjusts or controls splitting time, the addition of graphite derivative, graphite raw material powder body
The conditions such as concentration, obtain amount of size, thickness and Graphene of required graphene sheet layer etc..The present invention experimental result be,
Within the specific limits, splitting time is longer, and the size of the Graphene for obtaining is less, and suspension concentration is higher, and the number of plies changes not
Greatly.
Description of the drawings
Below in conjunction with the accompanying drawings specific embodiment of the invention is described in further detail；
Fig. 1 is the SEM figures that the embodiment of the present invention 1 peels off the Graphene for preparing；
Fig. 2 is the TEM figures that the embodiment of the present invention 1 peels off the Graphene for preparing；
Fig. 3 is the AFM figures that the embodiment of the present invention 1 peels off the Graphene for preparing.
Specific embodiment
The following is the non-limiting example that the present invention prepares Graphene.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 can be carried out under conditions of enclosing.
The method of embodiment 1 prepares graphene nano material, comprises the following steps：Using high speed homogenization dispersion machine.
1) it is 1 by graphite oxide and expansible graphite mass ratio:10 prepare corresponding dispersion liquid, and magneton stirring 30min is obtained
To the dispersion liquid that total concentration is 16.5mg/mL.
2) high speed homogenization dispersion machine is placed in into step 1) dispersion liquid in shearing dispersion, it is under normal temperature and pressure, dispersion liquid is pre-
3h is peeled off, suspension is obtained.
3) by step 2) the suspension standing 24h for obtaining is peeled off, supernatant is taken in the case where rotating speed is 3000rpm, it is centrifuged
10min, takes supernatant.
The concentration of Graphene is 2mg/mL in the supernatant that above-mentioned centrifugation is obtained, and yield is 12.2%, and length scale is average
For 8.6 μm, number of plies 1-5 layer.
Embodiment 2：Become outside the pale of civilization except following, remaining process is with embodiment 1.Graphite raw material adopts natural flake graphite, and oxygen
Graphite is 1 with the mass ratio of natural flake graphite:15, the Graphene concentration for obtaining is 3mg/mL, and yield is 12.5%, length
9 μm of size average out to, number of plies 1-5 layer.
Embodiment 3：Become outside the pale of civilization except following, remaining process is with embodiment 1.Graphite raw material adopts synthetic graphite, sulfonated graphite
It is 1 with the mass ratio of synthetic graphite:25, the total concentration of dispersion liquid is 39mg/mL, and the Graphene concentration for obtaining is 5mg/mL,
Yield is 12.8%, 10 μm of length scale average out to, number of plies 1-5 layer.
Embodiment 4：Become outside the pale of civilization except following, remaining process is with embodiment 1.Splitting time is 1h, the Graphene for obtaining it is dense
Spend for 1.2mg/mL, yield is 7.3%, 10 μm of length scale average out to, the number of plies is less than 5 layers.
Embodiment 5：Become outside the pale of civilization except following, remaining process is with embodiment 1.Splitting time is 2h, the Graphene for obtaining it is dense
Spend for 1.6mg/mL, yield is 9.7%, 7 μm of length scale average out to, number of plies 1-5 layer.
Embodiment 6：Become outside the pale of civilization except following, remaining process is with embodiment 1.Splitting time is 4h, the Graphene for obtaining it is dense
Spend for 2.5mg/mL, yield is 12.5%, 5 μm of length scale average out to, number of plies 1-5 layer.
Embodiment 7：Become outside the pale of civilization except following, remaining process is with embodiment 1.Splitting time is 6h, the Graphene for obtaining it is dense
Spend for 1mg/mL, yield is 6.1%, 1 μm of length scale average out to, number of plies 1-5 layer.
Embodiment 8：Become outside the pale of civilization except following, remaining process is with embodiment 1.The mass ratio of graphite oxide and expansible graphite
For 1:5, the concentration of the Graphene for obtaining is 1.1mg/mL, and yield is 12%, 8.5 μm of length scale average out to, number of plies 1-5 layer.
Embodiment 9：Become outside the pale of civilization except following, remaining process is with 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 the dispersion liquid for obtaining is peeled off with ball mill, obtains dispersion liquid
Concentration is 4mg/mL, and yield is 12.7%, 8.7 μm of length scale average out to, number of plies 1-5 layer.
Embodiment 10：Become outside the pale of civilization except following, remaining process is with embodiment 11.With carboxyl graphite as dispersant, carboxyl
Graphite is 1 with the mass ratio of expansible graphite:25, the total concentration of dispersion liquid is 39mg/mL, and the concentration of the Graphene for obtaining is
6mg/mL, yield is 15.4%, 8.7 μm of length scale average out to, number of plies 1-5 layer.
Embodiment 11：Become outside the pale of civilization except following, remaining process is with 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 the Graphene for obtaining is 7mg/mL, and yield is 15%, and length is put down
Size is 8.6 μm, number of plies 1-5 layer.
Embodiment 12：Become outside the pale of civilization except following, remaining process is with embodiment 1.Dispersion liquid is peeled off with kitchen blender, is obtained
Graphene concentration be 2.1mg/mL, yield is 12.7%, length mean size be 9 μm, number of plies 1-5 layer.
Or by embodiment 1 shearing dispersion after rich in Graphene be suspended in 1000 DEG C at calcine 600s obtain stone
Black alkene, by elementary analysiss, the high purity 99% of Graphene.
The suspension rich in Graphene after shearing dispersion in embodiment 2 is calcined into 1800s at 900 DEG C and obtains graphite
Alkene, by elementary analysiss, the high purity 99% of Graphene.
The suspension rich in Graphene after shearing dispersion in embodiment 3 is calcined into 3000s at 700 DEG C and obtains graphite
Alkene, by elementary analysiss, the high purity 98% of Graphene.
The above embodiment of the present invention is merely to detailed description examples of the invention, every to belong to the present invention's
Row of the change that technical scheme is amplified out still in protection scope of the present invention.
Claims (10)
1. a kind of method for preparing Graphene with shearing equipment stripping, it is characterised in that with following process and step：
Using graphite derivative as dispersant, different graphite raw materials is distributed in the aqueous dispersion liquid of graphite derivative,
In shearing equipment, under the regular hour, peeled off and process is obtained Graphene.Mixed liquor after above-mentioned stripping is stood
Or centrifugation, supernatant is pure graphene solution.Or the suspension rich in Graphene after shearing is disperseed carries out calcining and obtains stone
Black alkene.
2. according to a kind of method for preparing Graphene with shearing equipment stripping of claim 1, it is characterised in that graphite raw material is selected
From expansible graphite, natural flake graphite, synthetic graphite.
3. according to a kind of method for preparing Graphene with shearing equipment stripping of claim 1, it is characterised in that graphite derivative
Selected from graphite oxide, edge graphite oxide, sulfonated graphite, carboxyl graphite.
4. according to a kind of method for preparing Graphene with shearing equipment stripping of claim 1, it is characterised in that the shearing for using
Equipment is selected from：Ball mill, high-speed shearing machine, homogenizer.
5. according to a kind of method for preparing Graphene with shearing equipment stripping of claim 1, it is characterised in that calcining purification stone
Black alkene, calcining heat is between 300-1050 DEG C.
6. according to a kind of method for preparing Graphene with shearing equipment stripping of claim 1, it is characterised in that calcining purification stone
Black alkene, calcination time is between 3s-3600s.
7. according to a kind of method for preparing Graphene with shearing equipment stripping of claim 1, it is characterised in that with water to be situated between
The mass ratio of matter, graphite derivative and graphite raw material is 1：1-1：Between 30.
8. according to a kind of method for preparing Graphene with shearing equipment stripping of claim 1, it is characterised in that in room temperature, often
Pressure is peeled off, and initial gained is rich in graphene suspension concentration between 2-7mg/mL.
9. according to a kind of method for preparing Graphene with shearing equipment stripping of claim 1, it is characterised in that splitting time exists
Between 1-10 hours.
10. according to a kind of method for preparing Graphene with shearing equipment stripping of claim 1, it is characterised in that Graphene
Between 1-5 layers, size is between 1-10 microns for the number of plies.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN115611271A (en) * | 2022-10-28 | 2023-01-17 | 中国科学院福建物质结构研究所 | Preparation method of graphene |
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| CN104692363A (en) * | 2013-12-04 | 2015-06-10 | 北京化工大学 | Method for preparing graphene through hypergravity technology |
| CN104973591A (en) * | 2014-04-11 | 2015-10-14 | 中国科学院上海硅酸盐研究所 | High-quality graphene and preparation method thereof |
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| 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 |
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| CN106672951B (en) | 2019-06-11 |
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