CN111591982A - Physical preparation method of graphene by using crystalline flake graphite as raw material - Google Patents
Physical preparation method of graphene by using crystalline flake graphite as raw material Download PDFInfo
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- CN111591982A CN111591982A CN202010450063.2A CN202010450063A CN111591982A CN 111591982 A CN111591982 A CN 111591982A CN 202010450063 A CN202010450063 A CN 202010450063A CN 111591982 A CN111591982 A CN 111591982A
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
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- C01B32/19—Preparation by exfoliation
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- C01B2204/00—Structure or properties of graphene
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- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
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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
- C01B2204/32—Size or surface area
Abstract
The invention provides a physical preparation method of graphene by taking crystalline flake graphite as a raw material, belonging to the field of graphene materials. The physical preparation method of graphene by using crystalline flake graphite as a raw material is characterized by comprising the following steps of: s01: pretreating the flake graphite, and then mixing and stirring the flake graphite with an intercalation agent, a solvent and a penetrating agent; s02: grinding the turbid liquid obtained after stirring in the step S01 in grinding equipment in two steps, gradually increasing the grinding pressure and speed, and after grinding is finished, releasing pressure to obtain a graphene dispersion liquid; s03: and (4) performing spray drying on the graphene dispersion liquid obtained in the step (S02) to obtain graphene powder. The invention has the advantages of very simple operation process and the like.
Description
Technical Field
The invention belongs to the field of graphene materials, and particularly relates to a physical preparation method of graphene by taking crystalline flake graphite as a raw material.
Background
Graphene is a two-dimensional material which is formed by carbon atoms in a planar hybrid orbit into a hexagonal honeycomb structure and has the thickness of only a single carbon atom, and is one of the thinnest and hardest nano materials known in the world.
Graphene has a huge application prospect, so that a method which is high in quality, less in pollution and easy to prepare is urgently needed to be found to meet the application requirement of the currently vigorously developed graphene. At present, the method for preparing graphene at home and abroad mainly adopts an oxidation-reduction method, which has great influence on the structure and performance of the graphene and has the problem of serious environmental pollution. In addition, few physical preparation methods have the problems of low graphene productivity, poor quality, high cost and the like.
As in the prior art:
CN 106335891a discloses a method for preparing graphene by steam explosion, which uses graphite material to prepare graphene, but because the size of graphite raw material is large and there are many impurities, the operation of the method can finally prepare graphene, but the steam explosion method needs to be repeated, which not only increases the cost, but also prolongs the preparation time, and is not favorable for rapid industrial production.
CN 107032332a discloses a physical method for preparing graphene by using the coordination of microwave and mechanical force, which is simple and easy to operate, but only a very small amount of graphene can be generated due to too large energy consumption, and the used liquid contains other metal ions, so the purity of the finished graphene needs to be evaluated.
CN 105712336a discloses a physically peeling production method of graphene, in which graphite flakes are added into a stripping solution and then peeled by using 1-3 atm to prepare graphene, although the method is feasible, chemical substances remaining in the stripping solution still remain in a finished product after the graphene is dried, and the stripping pressure is low and the graphene cannot be effectively and completely peeled, so that the productivity is low and the cost is too high.
Disclosure of Invention
The invention aims to provide a physical preparation method of graphene by taking crystalline flake graphite as a raw material, aiming at the problems in the prior art.
The purpose of the invention can be realized by the following technical scheme: a physical preparation method of graphene by using crystalline flake graphite as a raw material is characterized by comprising the following steps:
s01: pretreating the flake graphite, and then mixing and stirring the flake graphite with an intercalation agent, a solvent and a penetrating agent;
s02: grinding the turbid liquid obtained after stirring in the step S01 in grinding equipment in two steps, gradually increasing the grinding pressure and speed, and after grinding is finished, releasing pressure to obtain a graphene dispersion liquid;
s03: and (4) performing spray drying on the graphene dispersion liquid obtained in the step (S02) to obtain graphene powder.
Preferably, in step S02, the first step of the two-step milling is to gradually increase the milling rate from 1000rpm to 1500rpm under a pressure of 0.5MPa for a milling time of 3 hours.
Preferably, in step S02, the second step of the two-step milling is to increase the pressure to 10MPa, gradually increase the milling rate from 1500rpm to 3000rpm, and mill for 1 hour.
Preferably, in step S02, the grinding medium in the grinding device is zirconia grinding beads with a diameter of 0.1 to 0.3 mm.
Preferably, in step S03, the graphene dispersion liquid is placed in a spray dryer, the air inlet temperature is 400-450 ℃, the air outlet temperature is 90-100 ℃, the centrifugal speed of a sprayer is 35000rpm, and graphene powder is obtained after drying.
Preferably, in step S01, 10% of flake graphite, 0.01% of intercalation agent, 0.2% of penetrating agent and 89.79% of solvent are mixed and stirred for 0.5 hour.
Preferably, in step S01, the crystalline flake graphite has a particle size of 1-2um and a carbon content of more than 99.9%.
Preferably, in step S01, the intercalation agent is one or a combination of cetyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide and dodecyl trimethyl ammonium bromide.
Preferably, in step S01, the penetrant is one or more of EMPIMIN OT75, EMPIMIN OP80, SURFONIC DOS. EMPIMIN OT75, EMPIMIN OP80, and SURFONIC DOS are all products of Henscman (HUNTSMAN) chemical industry.
Preferably, in step S01, the solvent is one or a combination of water, ethanol and NMP. The chemical name of NMP is N-methylpyrrolidone.
The working principle of the invention is as follows: according to the invention, the flake graphite is mixed with the intercalation agent, the solvent and the intercalation agent, the intercalation agent reduces Van der Waals force between flake graphite sheets, so that the flake graphite expands, the flake graphite sheets are more easily stripped, the addition of the penetrating agent can help the flake graphite to be fully wetted with water, the subsequent expansion stripping reaction is facilitated, and the expansion of the flake graphite is accelerated; and fully grinding and stripping crystalline flake graphite by adopting a two-step grinding method to obtain a graphene turbid liquid, finally decompressing to obtain a graphene dispersion liquid, and performing spray drying to obtain graphene powder.
Compared with the prior art, the invention has the following advantages:
1. the method has the advantages of simple operation process, short preparation time, less pollution and low cost.
2. According to the invention, the two-step grinding method is adopted to fully grind and strip the crystalline flake graphite, so that the crystalline flake graphite can be effectively stripped, and the finally obtained graphene dispersion liquid has good dispersibility.
3. The invention adopts the matching use of the intercalation agent and the penetrating agent, so that the scale graphite expands, and the scale graphite sheet layer is easier to strip.
4. According to the invention, the material is dried by adopting a spray drying method, the graphene dispersion liquid can be directly dried to obtain a powdery product, and processes such as evaporation and crushing are omitted.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of graphene prepared according to an embodiment of the present invention;
fig. 2 is a projection electron micrograph (TEM) of graphene prepared according to an embodiment of the present invention;
fig. 3 is an Atomic Force Microscope (AFM) image of graphene prepared according to an embodiment of the present invention;
FIG. 4 is an enlarged view of an atomic force microscope of the present invention;
FIG. 5 is an enlarged view of an atomic force microscope of the present invention;
fig. 6 is an X-ray diffraction pattern (XRD) of graphene prepared according to an embodiment of the present invention;
fig. 7 is a Raman spectrum (Raman) of graphene prepared according to an embodiment of the present invention.
Detailed Description
The following is a detailed embodiment of the present invention and the accompanying drawings are incorporated to illustrate the technical solution of the present invention
Further, the present invention is not limited to these examples.
Example 1a method for preparing graphene using crystalline flake graphite as a raw material using a physical method.
(1) Firstly, preparing materials, selecting crystalline flake graphite with the average particle size of 1-2um and the carbon content of more than 99.9%, and pretreating the crystalline flake graphite, namely stirring and dispersing the crystalline flake graphite; cetyl Trimethyl Ammonium Bromide (CTAB) is selected as an intercalation agent; selecting EMPIMIN OT75 (trade name of Hunsman, manufactured in USA of origin, available on the market) as penetrant; water was chosen as the solvent.
(2) Adding 10 weight percent of flake graphite, 0.01 weight percent of intercalation agent and 0.2 weight percent of penetrating agent into 89.79 weight percent of hydrosolvent, and stirring for 0.5 hour;
(3) adding the graphene aqueous solution into a nano grinder for high-pressure grinding, wherein the grinding medium is zirconia grinding beads with the size of 0.3-0.5 mm; grinding at 0.5Mpa for 3 hr, and gradually increasing the grinding speed from 1000rpm to 1500 rpm; then, the mixture was ground for 1 hour under a pressure increased to 10MPa, and the grinding rate was gradually increased from 1500rpm to 3000 rpm. And obtaining the graphene dispersion liquid after grinding.
(4) And (3) placing the graphene dispersion liquid into a spray dryer, controlling the air inlet temperature of the dryer to be 450 ℃, the air outlet temperature of the dryer to be 100 ℃, and the rotating speed of a centrifugal disc of a sprayer to be 35000rpm, and drying to obtain the graphene product.
Fig. 1 to 3 and 6 to 7 are SEM, TEM, XRD, AFM and Raman graphs of the graphene article obtained in example 1, and fig. 4 and 5 are enlarged views of fig. 3, and it can be seen from the graphs that the prepared graphene has a complete structure, a good morphology, and the number of layers is mainly distributed between 5 and 10. The results of the performance tests performed on the samples prepared in the specific examples are shown in table 1:
table 1 detection of properties of the prepared graphene
| Specific surface area (m)2/g) | Conductivity S/m | Number of layers | |
| Example 1 | 30.0883 | 170.36 | 5-10 |
The graphene prepared by the method has the advantages of large specific surface area, good representative separation effect, less laminarity of the graphene, high conductivity, high purity of the representative graphene, namely high carbon content.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. A physical preparation method of graphene by using crystalline flake graphite as a raw material is characterized by comprising the following steps:
s01: pretreating the flake graphite, and then mixing and stirring the flake graphite with an intercalation agent, a solvent and a penetrating agent;
s02: grinding the turbid liquid obtained after stirring in the step S01 in grinding equipment in two steps, gradually increasing the grinding pressure and speed, and after grinding is finished, releasing pressure to obtain a graphene dispersion liquid;
s03: and (4) performing spray drying on the graphene dispersion liquid obtained in the step (S02) to obtain graphene powder.
2. The physical preparation method of graphene using flake graphite as raw material according to claim 1, wherein in step S02, the first step of the two-step grinding is to gradually increase the grinding speed from 1000rpm to 1500rpm under a pressure of 0.5Mpa, and the grinding time is 3 hours.
3. The physical preparation method of graphene using flake graphite as a raw material according to claim 1, wherein in step S02, the second step of the two-step grinding is to increase the pressure to 10Mpa, the grinding rate is gradually increased from 1500rpm to 3000rpm, and the grinding time is 1 hour.
4. The physical preparation method of graphene using flake graphite as a raw material according to claim 1, wherein in step S02, the grinding medium in the grinding device is zirconia grinding beads with a diameter of 0.1-0.3 mm.
5. The physical preparation method of graphene using crystalline flake graphite as a raw material according to claim 1, wherein in step S03, the graphene dispersion liquid is placed in a spray dryer, the air inlet temperature is 400-450 ℃, the air outlet temperature is 90-100 ℃, the centrifugal speed of a sprayer is 35000rpm, and graphene powder is obtained after drying.
6. The physical preparation method of graphene using crystalline flake graphite as a raw material according to claim 1, wherein 10% of crystalline flake graphite, 0.01% of intercalation agent, 0.2% of penetrating agent and 89.79% of solvent are mixed and stirred for 0.5 hour in step S01.
7. The physical preparation method of graphene using crystalline flake graphite as a raw material according to claim 1, wherein in step S01, the crystalline flake graphite has a particle size of 1-2um and a carbon content of more than 99.9%.
8. The physical preparation method of graphene using flake graphite as raw material according to claim 1, wherein in step S01, the intercalation agent is one or more of cetyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, and dodecyl trimethyl ammonium bromide.
9. The physical preparation method of graphene using flake graphite as raw material according to claim 1, wherein in step S01, the penetrating agent is one or more of EMPIMIN OT75, EMPIMIN OP80 and SURFONIC DOS.
10. The physical preparation method of graphene using flake graphite as a raw material according to claim 1, wherein in step S01, the solvent is one or a combination of water, ethanol and NMP.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2787431C1 (en) * | 2021-10-29 | 2023-01-09 | Валерий Юлдашевич Ахмедов | Method for producing layered graphite and multilayer graphene |
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Cited By (1)
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| RU2787431C1 (en) * | 2021-10-29 | 2023-01-09 | Валерий Юлдашевич Ахмедов | Method for producing layered graphite and multilayer graphene |
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