CN111484006A - Preparation method of large-area graphene - Google Patents
Preparation method of large-area graphene Download PDFInfo
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- CN111484006A CN111484006A CN202010083947.9A CN202010083947A CN111484006A CN 111484006 A CN111484006 A CN 111484006A CN 202010083947 A CN202010083947 A CN 202010083947A CN 111484006 A CN111484006 A CN 111484006A
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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
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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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
Abstract
The invention discloses a preparation method of large-area graphene, which comprises the steps of providing a graphite dispersion liquid with a first shearing force generated by a liquid flow, wherein the speed of the liquid flow is more than 100 meters per second, and the shearing force acts on graphite flakes of the graphite dispersion liquid to disperse the graphite flakes into the large-area graphene; a second shearing force generated by driving the fluid to rotate and flow is also provided to act on the graphite dispersion liquid; the process of the shearing force generated by driving the fluid to rotate and flow is carried out in a cylindrical cavity, and the graphite sheets dispersed by the first shearing force are continuously dispersed by a second shearing force generated by the rotation of the rotating cylinder in the cylindrical cavity and the driving fluid after the fluid enters the cylindrical cavity. The invention aims to provide a preparation method of large-area graphene, which improves the dispersion efficiency, shortens the preparation period and reduces the cost.
Description
Technical Field
The invention relates to a preparation method of large-area graphene.
Background
Graphene is a planar thin film with hexagonal honeycomb lattice composed of carbon atoms hybridized with SP2 orbitals, and is the thinnest and the hardest nanomaterial in the world. Since graphene has a low resistivity and is almost transparent, it is expected to be used for developing thinner electronic components having a higher conduction speed for applications in fields such as semiconductors, panels, or batteries.
Even though there are many expectations, the international industry has been competitive invested in graphene research and active layout, but at the present stage, the graphene technology has not been applied in a large amount, and it is obvious that there are many technical problems: the graphene is improved in the form of graphene itself or in the form of a formula, so that the graphene has a better effect when applied to a composite material.
The Chinese patent application No. CN201710061768.3 discloses a method for preparing large-area graphene, which comprises the steps of providing a graphitized graphite sheet and providing a shearing force, wherein the shearing force acts on the graphitized graphite sheet to disperse the graphitized graphite sheet into large-area graphene, the number of layers of the large-area graphene is less than 20, the layer number of the large-area graphene has a diameter of L a between 1 mu m and 1000 mu m, and L a is a value obtained by Raman spectroscopy.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method of large-area graphene, which improves the dispersion efficiency, shortens the preparation period and reduces the cost.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing large-area graphene is characterized in that a first shearing force generated by a liquid flow is provided to a graphite dispersion liquid, the speed of the liquid flow is more than 100 meters per second, the shearing force acts on graphite flakes of the graphite dispersion liquid to enable the graphite flakes to be dispersed into the large-area graphene, the number of layers of the large-area graphene is less than 20, the large-area graphene has a diameter of L a between 1 mu m and 1000 mu m, the L a is a value obtained by Raman spectroscopy, the method is characterized by further providing a second shearing force generated by driving the fluid to rotate and act on the graphite dispersion liquid, wherein the process of driving the fluid to rotate and generate the shearing force is carried out in a cylindrical cavity, and the graphite flakes dispersed by the first shearing force are continuously rotated by a rotating cylinder in the cylindrical cavity after entering the cylindrical cavity along with the fluid to generate the second shearing force generated by the rotation of the fluid.
Further, the graphite flakes of the graphite dispersion have a degree of graphitization between 0.8 and 1.0.
Further, the number of layers of the large-area graphene is between 1 and 5.
Further, the action force of the shearing force is larger than the binding force between the graphene.
Furthermore, the direction of an acting force of the fluid is opposite to a moving direction of the graphene.
Further, the velocity of the fluid flow is between 100 meters per second and 500 meters per second.
Further, the graphite flakes dispersed by the first shearing force enter the cavity along with the fluid from an inlet at the lower end of the cylindrical cavity, and the graphite flakes dispersed by the second shearing force generated by the rotation of the fluid driven by the rotation of the rotating drum in the cylindrical cavity enter the circulating pipeline from an inlet at the upper end of the cylindrical cavity after being dispersed in the cavity.
Compared with the prior art, the invention has the beneficial technical effects that:
the second shearing force generated by driving the fluid to rotate and flow is provided to act on the graphite dispersion liquid, so that the dispersion efficiency can be effectively improved, the preparation period is shortened, and the production cost is reduced.
Drawings
The invention is further illustrated in the following description with reference to the drawings.
FIG. 1 is a schematic diagram of an apparatus for preparing large-area graphene according to the present invention;
description of reference numerals: 3. a nozzle; 29. a graphene dispersion liquid; 31. a pressurizer; 32. a feed inlet; 33. a pipe body; 34. a discharge port; 35. large-area graphene; 4-a cylindrical cavity; 5-rotating the drum.
Detailed Description
Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
Referring to fig. 1, the present invention provides a method for preparing large-area graphene, including the following steps S1 and S2:
s1: providing a graphitized graphite sheet; and
s2, providing a shearing force acting on the graphitized graphite sheet to disperse the graphitized graphite sheet into a large-area graphene, wherein the number of layers of the large-area graphene is less than 20 and has a diameter of L a between 1 μm and 1000 μm, and L a is a value obtained by Raman spectroscopy.
S3: a second shearing force generated by driving the fluid to rotate and flow is also provided to act on the graphite dispersion liquid; the process of the shearing force generated by driving the fluid to rotate and flow is carried out in a cylindrical cavity, and the graphite sheet dispersed by the first shearing force is continuously rotated by the rotating drum in the cylindrical cavity to drive the fluid to rotate to generate a second shearing force dispersion after the graphite sheet enters the cylindrical cavity along with the fluid
In this embodiment, the graphitized graphite sheet is a highly graphitized graphite sheet having a graphitization degree of 0.8 to 1.0. Herein, "degree of graphitization" means a ratio of graphite, which has a theoretical value of a distance between graphene planes (graphene planes) of 3.354 angstroms (angstrom), and thus when the degree of graphitization is 1, it means that graphene is most closely stacked, and a graphite plane spacing (d (0002)) of 3.354 angstroms. The graphitization degree (G) can be calculated by the following formula 1:
formula 1G ═ 3.440-d (0002))/(3.440-3.354)
Accordingly, a higher degree of graphitization corresponds to a larger crystal size, which is determined by the extension of the plane of the hexagonal network of graphene (L a) and the size of the stacked layers (L c). therefore, in general, high graphitization refers to a degree of graphitization greater than or equal to 0.8.
In this embodiment, the number of layers of the large-area graphene may be between 1 to 5.
In this embodiment, the shear force may be a wet shear force depending on the manner of applying the shear force to the highly graphitized graphite sheet, and the shear force is greater than the binding force between the graphenes in order to effectively disperse the highly graphitized graphite sheet.
In detail, the wet shear force may disperse the highly graphitized graphite sheet into the large-area graphene by a fluid force acting in a direction opposite to a moving direction of the graphene. In another aspect of the invention, the fluid force disperses the highly graphitized graphite sheets in a fluid and passes the fluid through a circulation system comprising nozzles to cause the fluid to act on the surfaces or sides of the highly graphitized graphite sheets. In a particular aspect of the invention, the fluid application site is preferably a side of the highly graphitized graphite sheet.
More particularly, the present disclosure provides a shear force generated by a fluid stream having a velocity greater than 100 meters per second to a graphite dispersion, the shear force acting on graphite flakes of the graphite dispersion to disperse the graphite flakes into a large area graphene having a number of layers less than 20 and a diameter of L a between 1 μm and 1000 μm (L a is a value obtained by Raman spectroscopy).
Referring to fig. 1, a schematic diagram of the circulation system includes a nozzle 3 including an inlet 32, an outlet 34, and a tube 33 communicating between the inlet 32 and the outlet 34, and a pressurizer 31 communicating with the inlet for pressurizing a graphite dispersion 29 to enter the cylindrical cavity 4 from the inlet 32 and then enter the tube 33 from the outlet 34 of the cylindrical cavity 4, so that graphite flakes of the graphite dispersion 29 flow through the tube 33 to gradually reduce the number of layers to less than 20 large-area graphene 35, the large-area graphene 35 having a diameter L a between 1 μm and 1000 μm (L a is a value obtained by raman spectroscopy).
In the present embodiment, the outlet 34 is connected back to the inlet 32, so that the graphite dispersion liquid 29 can be repeatedly circulated in the circulation system with nozzles, effectively dispersing the highly graphitized graphite sheets therein into large-area graphene 35.
In this embodiment, the number of times the graphite dispersion 29 is circulated in the circulation system is not particularly limited as long as the structure of the large-area graphene 35 can be manufactured to have a desired number of layers.
In this embodiment, the shearing force of the highly graphitized graphite sheet in the circulating system may be, for example, 1MPa to 500MPa, preferably 10MPa to 500MPa, and more preferably 50MPa to 200 MPa. Accordingly, in an embodiment of the present invention, when the number of cycles of the graphite dispersion liquid 29 in the circulation system is 200, the shearing force of the highly graphitized graphite sheet generated by the circulation system acting thereon may be 200MPa, so as to achieve the optimal dispersion effect, but the present invention is not limited thereto.
In the present embodiment, the type and the position of the pressurizer 31 are not particularly limited as long as the required liquid force can be provided. For example, the pressurizer 31 used in this embodiment is a pump. In addition, the pressure provided by the pressurizer 31 to the graphite dispersion 29 is preferably between 100MPa and 500MPa, but in some embodiments, the pressure can be adjusted to a suitable range according to the actual situation.
In this embodiment, in order to effectively disperse the highly graphitized graphite sheet by the liquid force, the highly graphitized graphite sheet may be formed with a bending angle, so that the liquid force is applied to the side of the highly graphitized graphite sheet to disperse into the large area graphene 35. For example, the angle of the bend of the highly graphitized graphite sheet may be 30 ° to 150 °, thereby allowing the liquid force to be effectively applied to the sides of the highly graphitized graphite sheet to disperse it into the large area graphene 35. To achieve the above object, for example, a convex wall may be provided in the tube 34, whereby the highly graphitized graphite sheet in the liquid can form a 90 ° bending angle by flowing through the convex wall.
In addition, in order to avoid the "soft condensation phenomenon" of the large-area graphene 35 due to the thermodynamic effect, in the embodiment, the temperature of the graphite dispersion liquid 29 in the whole preparation process may be 25 ℃ to 100 ℃, preferably 20 ℃ to 50 ℃, so as to avoid re-condensation of the dispersed graphene 35, and any conventional method for controlling the liquid temperature may be applied to the present embodiment without any particular limitation.
In the present embodiment, the inner diameter of the feed inlet 32 can be larger than the inner diameter of the discharge outlet 34, however, the specific inner diameter size can be adjusted according to the graphite flake solid content of the graphite dispersion 29. For example, in one embodiment, for example, when the graphite flake solids content of graphite dispersion 29 is less than 30 wt.%, feed inlet 32 can have an inner diameter of between 5cm and 10cm and discharge outlet 34 can have an inner diameter of between 100 μm and 200 μm; or in another embodiment, when the graphite flake solid content of the graphite dispersion 29 is greater than or equal to 80 wt.%, the inlet 32 has an inner diameter of 100cm to 500cm, and the outlet 34 has an inner diameter of 5mm to 10mm, which can be adjusted by those skilled in the art according to the actual circumstances, and the present invention is not limited thereto.
In the present embodiment, the speed of the liquid flow is not particularly limited and can be adjusted according to actual requirements, for example, the speed can be between 100 meters per second and 1000 meters per second, and preferably between 100 meters per second and 500 meters per second.
The concentration of the highly graphitized graphite flakes in the graphite dispersion 29 is not particularly limited in this embodiment, as long as the highly graphitized graphite flakes can be effectively dispersed in a liquid into the large-area graphene 35 by the force of the liquid. For example, in one embodiment, the graphite flake solids content can be less than 30 wt.%; in yet another embodiment, the graphite flake solids content can be greater than or equal to 80 wt.%.
The present embodiment is directed to achieving the effect of dispersing highly graphitized graphite flakes in the graphite dispersion 29 by using different wet shear forces, which are liquid forces provided by the equipment for producing large-area graphene 35. Therefore, the kind of liquid used in this embodiment is not particularly limited as long as it can provide the force required by the preparation method of the large-area graphene 35. For example, the liquid may be at least one selected from the group consisting of water, N-methylpyrrolidone (NMP), surfactants, salts, and combinations thereof. In a particular aspect of the invention, the liquid can be N-methylpyrrolidone (NMP).
In the present embodiment, in order to more effectively disperse highly-graphitized graphite flakes in the graphite dispersion 29 into large-area graphene 35 by using shear force, the highly-graphitized graphite flakes may be subjected to a pretreatment, whereby the highly-graphitized graphite flakes are expanded by the pretreatment to increase the inter-planar distance (d (0002)) of the graphene, thereby making it easier to disperse the highly-graphitized graphite flakes into the large-area graphene 35. In detail, any pretreatment method may be used as long as the hexagonal network planar structure of the graphene is not damaged, and the present invention is not particularly limited, such as an explosion method, a chemical delamination method, an ultrasonic oscillation method, a ball milling method, or any combination thereof.
Through tests, the high-degree graphitized graphite flake can be rapidly dispersed into large-area graphene by virtue of the wet shearing force generated by a circulating system containing a nozzle, and the large-area graphene has a perfect hexagonal reticular planar structure.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (7)
1. A method for preparing large-area graphene is characterized in that a first shearing force generated by a liquid flow is provided to a graphite dispersion liquid, the speed of the liquid flow is more than 100 meters per second, the shearing force acts on graphite flakes of the graphite dispersion liquid to enable the graphite flakes to be dispersed into the large-area graphene, the number of layers of the large-area graphene is less than 20, the large-area graphene has a diameter of L a between 1 mu m and 1000 mu m, the L a is a value obtained by Raman spectroscopy, the method is characterized by further providing a second shearing force generated by driving the fluid to rotate and act on the graphite dispersion liquid, wherein the process of driving the fluid to rotate and generate the shearing force is carried out in a cylindrical cavity, and the graphite flakes dispersed by the first shearing force are continuously rotated by a rotating cylinder in the cylindrical cavity after entering the cylindrical cavity along with the fluid to generate the second shearing force generated by the rotation of the fluid.
2. The method of claim 1, wherein the graphite flakes of the graphite dispersion have a degree of graphitization between 0.8 and 1.0.
3. The method of claim 1, wherein the number of layers of the large area graphene is between 1 and 5.
4. The method of claim 1, wherein the shear force is greater than the bonding force between the graphene layers.
5. The method of claim 1, wherein a direction of an action of the fluid is opposite to a moving direction of the graphene.
6. The method of claim 1, wherein the flow rate is between 100 m/s and 500 m/s.
7. The method for preparing large-area graphene according to claim 1, wherein the graphite flakes dispersed by the first shear force enter the chamber along with the fluid from the inlet at the lower end of the cylindrical chamber, and enter the circulating pipeline from the inlet at the upper end of the cylindrical chamber after being dispersed by the second shear force generated by the rotation of the fluid driven by the rotation of the rotating drum in the cylindrical chamber.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150076105A (en) * | 2013-12-26 | 2015-07-06 | 주식회사 엘지화학 | Preparation method of graphene |
| CN106809823A (en) * | 2017-01-26 | 2017-06-09 | 北京清烯科技有限公司 | Equipment for manufacturing large-area graphene |
| CN106829928A (en) * | 2017-01-26 | 2017-06-13 | 北京清烯科技有限公司 | The preparation method of large-area graphene |
| CN107624105A (en) * | 2015-06-24 | 2018-01-23 | 嘉泉大学校产学协力团 | Utilize the high-quality graphene preparation method and preparation facilities of shear flow |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150076105A (en) * | 2013-12-26 | 2015-07-06 | 주식회사 엘지화학 | Preparation method of graphene |
| CN107624105A (en) * | 2015-06-24 | 2018-01-23 | 嘉泉大学校产学协力团 | Utilize the high-quality graphene preparation method and preparation facilities of shear flow |
| CN106809823A (en) * | 2017-01-26 | 2017-06-09 | 北京清烯科技有限公司 | Equipment for manufacturing large-area graphene |
| CN106829928A (en) * | 2017-01-26 | 2017-06-13 | 北京清烯科技有限公司 | The preparation method of large-area graphene |
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