CN110422839B - Synthetic method of graphene - Google Patents
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- CN110422839B CN110422839B CN201910723993.8A CN201910723993A CN110422839B CN 110422839 B CN110422839 B CN 110422839B CN 201910723993 A CN201910723993 A CN 201910723993A CN 110422839 B CN110422839 B CN 110422839B
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- C01B32/182—Graphene
- C01B32/184—Preparation
Abstract
The invention belongs to the technical field of graphene, and particularly relates to a synthesis method of graphene. The graphene obtained by the preparation method has the characteristics of high conductivity and the like.
Description
Technical Field
The invention belongs to the technical field of graphene preparation, and particularly relates to a synthesis method of graphene with high conductivity.
Background
Graphene is a material with a two-dimensional nanostructure, has excellent optical, electrical, magnetic and mechanical properties and the like, and is considered to have great application prospects in the fields of light, electricity and magnetism. The electronic structure of graphene allows it to achieve excellent electrical properties. Has important significance in both academic research and application.
Through retrieval, there are 13 patent reports on graphene synthesis in the prior art: patent document (1) reports a simple method for preparing graphene nanosheets serving as negative electrode materials of lithium ion batteries, wherein ferric nitrate (Fe (NO) is utilized3)3·9H2And transferring the mixed solution of O), vanadyl oxalate and trimesic acid into a hydrothermal reaction kettle to perform hydrothermal reaction, setting a certain temperature and reaction time to obtain a product, washing and drying the product to obtain a precursor material, and then calcining, acidifying, washing and drying the precursor material to obtain the graphene nanosheet. Patent document (2) discloses an electrochemical method for producing an ultrathin graphene nanoplate. In the preparation process, layered graphite is used as an anode, a metal or graphite electrode is used as a cathode, a liquid phase system containing carboxylic acid is used as an electrolyte and an intercalation source, a certain current is applied between the anode and the cathode to perform electrochemical reaction to form a carboxylic acid intercalation graphite compound, then thermal stripping and mechanical stripping are performed, and the steps are repeated for multiple times to finally obtain the ultrathin graphene nanosheet with the average thickness not more than 2nm or the number of layers not more than 5. Patent document (3) discloses a method for producing single-layer graphene based on electrolyte solvent hot-insertion lithium exfoliation. The preparation process takes graphite as a precursor and 1mol/L lithium hexafluorophosphate (LiPF)6) The electrolyte is a solvent for the purpose of intercalating lithium ions between graphite layers. Subsequently mixing LiPF6And transferring the high-pressure reaction kettle of the electrolyte/graphite precursor solution into a forced air drying oven for solvothermal reaction. After reaction cooling, the single-layer graphene is sequentially washed by n-hexane and deionized water, and the preparation of the single-layer graphene is realized by processes such as centrifugal separation and the like. Patent document (4) discloses a process for producing a polypeptideThe method for preparing the porous graphene nanosheet comprises the following steps: the preparation method comprises the steps of taking linear anthracene molecules as a carbon source, mixing nano magnesium oxide and powdered potassium hydroxide to serve as a template agent and an activating agent, grinding and uniformly mixing the nano magnesium oxide and the powdered potassium hydroxide according to a proper proportion, annealing the mixture at a high temperature in a tubular furnace under the protection of flowing argon atmosphere, and finally obtaining the porous graphene-like nanosheet through an acid washing and water washing post-treatment method. Patent document (5) reports a method for producing graphene nanoplatelets by rapidly expanding intercalated graphite flakes by exposing them to a temperature of 1300 to 12000 ℃ for a controlled time of less than 2 seconds, followed by dispersing the expanded graphite in a dispersion medium and completing a high-pressure homogenization process in a homogenizer at a pressure of more than 35 MPa. A dispersion system of graphene nano sheets is realized, wherein the transverse size of at least 90% of the nano sheets is 50-50000 nm, and the thickness of the nano sheets is 0.34-50 nm. Patent document (6) reports a method for preparing graphene or graphene nanosheets by using supercritical sulfur hexafluoride exfoliation. Adding graphite and an oxidant in a mass ratio of 1: 0.1-50 into a high-pressure reaction kettle, pumping sulfur hexafluoride when the temperature reaches a preset value, wherein the sulfur hexafluoride is used as an intercalation stripping agent, setting a certain reaction temperature and time, circularly flowing under supercritical pressure and temperature, then reducing the pressure to normal pressure, circularly repeating the process, and finally realizing the preparation of graphene and graphene nanosheets with different sheet diameters and thicknesses by optimizing process parameters. Patent document (7) reports that processes of oxidation, dialysis purification, drying and crushing, thermal reduction and expansion stripping, post-treatment and the like of graphite powder are completed by using the graphite powder as a raw material through three designed continuous reactors, and continuous large-scale production of graphene nanosheets is realized. Patent document (8) proposes a method for producing graphene nanoplatelets: graphite is subjected to expansion treatment at the early stage, then stripping of graphene nanosheets is triggered by gas-phase high-speed collision, and finally the graphene nanosheets are obtained through grinding or stripping and can be used for preparing graphene nanosheet slurry and conductive coatings formed by the graphene nanosheet slurry. Patent document (9) reports a preparation method which is simple and easy to implement, low in cost and easy for large-scale production of graphene nanoplatelets. Stabilization of dispersions with solid polymersThe method comprises mechanically grinding an untreated graphite material to promote exfoliation of graphite during grinding to obtain a large-batch graphene nanosheet material. In the process, the solid high polymer and the graphene nanosheets are fully mixed on a nanoscale, and the exfoliated graphene nanosheets are prevented from being stacked again. And removing the solid high polymer in the post-treatment process to finally obtain the graphene nanosheet, wherein the thickness of the graphene nanosheet is 0.35-7 nm, and the graphene nanosheet is single-layer or multi-layer. Meanwhile, the hydrophilic high polymer endows the surface of the graphene nano sheet with hydrophilic modification, and the obtained graphene nano sheet can also be used as a water-system conductive coating. Patent document (10) discloses a high-efficiency preparation process of graphene oxide nanosheets, which comprises the steps of preparing common graphite powder into graphene oxide by an improved Hummers method, adding potassium permanganate, heating by a microwave oven to obtain a mixture of porous graphene oxide and manganese dioxide, carrying out centrifugal washing by dilute hydrochloric acid and deionized water repeatedly to obtain porous graphene oxide, carrying out ultrasonic treatment by using water bath ultrasound, and finally obtaining a target product. The sample in the graphene oxide nanosheet aqueous solution is characterized by small size, narrow distribution range and stable dispersion. Patent document (11) reports a preparation method of a graphene nanosheet/conductive polymer nanowire composite material, and a preparation part of the graphene nanosheet is to prepare graphite oxide by using a chemical oxidation method, obtain a graphene oxide nanosheet suspension by using ultrasound, adjust the pH value to 9-10 by using sodium hydroxide, add sodium borohydride into the suspension, stir for 1-2 hours at 80-90 ℃ to realize partial reduction of graphene oxide, and finally obtain the graphene nanosheet by vacuum filtration and washing. Patent document (12) discloses the preparation of graphene-based nanomaterials using an electron beam irradiation method: firstly, oxidizing natural graphite to obtain graphite oxide, and then dissolving graphene oxide in ethanol according to the weight ratio of 10-30 to obtain an ethanol solution. Mixing deionized water and the ethanol solution according to the volume ratio of 20-5 to obtain a mixed solution, adding a free radical scavenger, performing electron beam irradiation with the irradiation dose of 70-560kGy, finally performing centrifugal separation, cleaning the obtained precipitate with deionized water and absolute ethyl alcohol, drying and grinding to obtain graphene-based nano powder. Patent document (13) discloses a method for preparing an nitrogen-doped graphene/metal composite from bottom to top, and a product and application thereof. Regarding the synthesis part, carbon precursors, two-dimensional template precursors MA and metal precursors with different proportions at room temperature are ground in a mortar for 30 minutes to be uniformly mixed, then the mixture is placed in a ceramic crucible with a cover, and the mixture is calcined in a tube furnace under the protection of nitrogen to successfully obtain the nitrogen-doped graphene/metal composite.
Graphene, as a two-dimensional material having excellent properties in the fields of light, electricity, magnetism, and the like, has properties that are greatly related to size, thickness, and internal structure. A large graphene nanostructure is synthesized through a molecular coupling reaction, so that the graphene nanostructure has excellent electrical properties, and a new material with excellent properties is provided for graphene in the research fields of microelectronics and the like.
Documents of the prior art
Patent document
Patent document 1: CN201810554220.7
Patent document 2: CN201810374798.4
Patent document 3: CN201810063248.0
Patent document 4: CN201810043202.2
Patent document 5: CN201580032693.5
Patent document 6: CN201710138178.6
Patent document 7: CN201410565486.3
Patent document 8: CN201310757079.8
Patent document 9: CN201310628699.1
Patent document 10: CN201510143599.9
Patent document 11: CN201210167617.3
Patent document 12: CN200910052042.9
Patent document 13: CN201410307271.1
Disclosure of Invention
Technical problem to be solved by the invention
The invention aims to provide a wet chemical synthesis method of graphene.
Means for solving the technical problem
In order to solve the above problems, the present invention provides a method for synthesizing graphene, which comprises the following steps:
1) preparing a hexabromobenzene solution at room temperature by taking toluene as a solvent, and then adding an active metal into the solution; the active metal is selected from any one of sodium, lithium and magnesium;
2) placing the mixed solution in a stainless steel reaction kettle with a polytetrafluoroethylene lining, and heating for reaction;
3) washing the precipitate obtained after the reaction in the step 2) with absolute ethyl alcohol, adding deionized water for centrifugal washing, and dialyzing the washing product to obtain a graphene nanosheet aqueous solution; and (4) continuously washing the solid product with water until the supernatant of the solution is colorless, and drying to obtain solid graphene powder.
In one embodiment, the molar ratio of hexabromobenzene to sodium in step 1) is: 0.0694: 1-0.625: 1.
In one embodiment, in the step 2), the heating is performed at a temperature of 170 to 200 ℃ for 24 to 72 hours.
In one embodiment, in step 3), the first washing product of the centrifugal washing with deionized water is added for dialysis for 72 hours.
One embodiment is that, during the drying, the drying temperature is 60-90 ℃, and the drying time is more than or equal to 12 hours.
The invention has the beneficial effects that:
the raw materials used in the synthesis method are easy to obtain, the process is simple and convenient, and the synthesized high-quality graphene nanosheet is large in size, small in thickness and high in spintronic concentration.
Further features of the present invention will become apparent from the following description of exemplary embodiments.
Drawings
FIG. 1: (a) and (b) is a transmission electron micrograph of example 1.
FIG. 2: (a) and (b) is a transmission electron micrograph of example 2.
FIG. 3: (a) and (b) is a transmission electron micrograph of example 3.
FIG. 4: (a) and (b) is a transmission electron micrograph of example 4.
FIG. 5: (a) and (b) is a transmission electron micrograph of example 5.
FIG. 6: (a) and (b) is a transmission electron micrograph of example 6.
FIG. 7: (a) and (b) is a transmission electron micrograph of example 7.
FIG. 8: (a) and (b) is a transmission electron micrograph of example 8.
FIG. 9: (a) and (b) is a transmission electron micrograph of example 9.
FIG. 10: (a) and (b) is a transmission electron micrograph of example 10.
FIG. 11: (a) and (b) is a transmission electron micrograph of example 11.
FIG. 12: (a) and (b) is a transmission electron micrograph of example 12.
FIG. 13: (a) and (b) is a transmission electron micrograph of example 13.
FIG. 14: (a) and (b) is a transmission electron micrograph of example 14.
Detailed Description
One embodiment of the present disclosure will be specifically described below, but the present disclosure is not limited thereto.
Examples
The present invention is described in more detail by way of examples, but the present invention is not limited to the following examples. Unless otherwise specified, "part" means "part by mass".
Example 1:
with hexabromobenzene (C)6Br6) The method comprises the following steps of preparing a hexabromobenzene solution with the concentration of 1.0 g/400 ml by taking toluene as a solvent at room temperature and taking metal sodium as a raw material, and then adding 0.1 g of metal sodium into the solution.
The mixed solution was placed in a stainless steel autoclave lined with polytetrafluoroethylene and heated at a temperature of 170 ℃ for 24 hours.
And (3) repeatedly washing the precipitate obtained after the reaction by using absolute ethyl alcohol, adding a first washing product obtained by centrifugal washing of deionized water, and dialyzing for 72 hours to obtain the graphene nanosheet aqueous solution. And (3) continuously washing the solid product with water until the supernatant of the solution is colorless, and then drying the solid product in a drying oven (at 60 ℃) for 12 hours to obtain solid graphene powder.
Fig. 1(a) and (b) are transmission electron micrographs of the graphene nanostructure of example 1.
Example 2:
with hexabromobenzene (C)6Br6) The method comprises the following steps of preparing a hexabromobenzene solution with the concentration of 1.0 g/400 ml by taking toluene as a solvent at room temperature and taking metal sodium as a raw material, and then adding 0.1 g of metal sodium into the solution.
The mixed solution was placed in a stainless steel autoclave lined with polytetrafluoroethylene and heated at a temperature of 170 ℃ for 48 hours.
And (3) repeatedly washing the precipitate obtained after the reaction by using absolute ethyl alcohol, adding a first washing product obtained by centrifugal washing of deionized water, and dialyzing for 72 hours to obtain the graphene nanosheet aqueous solution. And (3) continuously washing the solid product with water until the supernatant of the solution is colorless, and then drying the solid product in a drying oven (at 60 ℃) for 12 hours to obtain solid graphene powder.
Fig. 2(a) and (b) are transmission electron micrographs of the graphene nanostructure of example 2.
Example 3:
with hexabromobenzene (C)6Br6) The method comprises the following steps of preparing a hexabromobenzene solution with the concentration of 1.0 g/400 ml by taking toluene as a solvent at room temperature and taking metal sodium as a raw material, and then adding 0.1 g of metal sodium into the solution.
The mixed solution was placed in a stainless steel autoclave lined with polytetrafluoroethylene and heated at a temperature of 170 ℃ for 72 hours.
And (3) repeatedly washing the precipitate obtained after the reaction by using absolute ethyl alcohol, adding a first washing product obtained by centrifugal washing of deionized water, and dialyzing for 72 hours to obtain the graphene nanosheet aqueous solution. And (3) continuously washing the solid product with water until the supernatant of the solution is colorless, and then drying the solid product in a drying oven (at 60 ℃) for 12 hours to obtain solid graphene powder.
Fig. 3(a) and (b) are transmission electron micrographs of the graphene nanostructure of example 3.
Example 4:
with hexabromobenzene (C)6Br6) The method comprises the following steps of preparing a hexabromobenzene solution with the concentration of 1.0 g/400 ml by taking toluene as a solvent at room temperature and taking metal sodium as a raw material, and then adding 0.6 g of metal sodium into the solution.
The mixed solution was placed in a stainless steel reactor lined with polytetrafluoroethylene and heated at 180 ℃ for 55 hours.
And (3) repeatedly washing the precipitate obtained after the reaction by using absolute ethyl alcohol, adding a first washing product obtained by centrifugal washing of deionized water, and dialyzing for 72 hours to obtain the graphene nanosheet aqueous solution. And (3) continuously washing the solid product with water until the supernatant of the solution is colorless, and then drying the solid product in a drying oven (at 60 ℃) for 12 hours to obtain solid graphene powder.
Fig. 4(a) and (b) are transmission electron micrographs of the graphene nanostructure of example 4.
Example 5:
with hexabromobenzene (C)6Br6) The method comprises the following steps of preparing a hexabromobenzene solution with the concentration of 1.0 g/400 ml by taking toluene as a solvent at room temperature and taking metal sodium as a raw material, and then adding 0.1 g of metal sodium into the solution.
The mixed solution was placed in a stainless steel autoclave lined with polytetrafluoroethylene and heated at 190 ℃ for 24 hours.
And (3) repeatedly washing the precipitate obtained after the reaction by using absolute ethyl alcohol, adding a first washing product obtained by centrifugal washing of deionized water, and dialyzing for 72 hours to obtain the graphene nanosheet aqueous solution. And (3) continuously washing the solid product with water until the supernatant of the solution is colorless, and then drying the solid product in a drying oven (at 60 ℃) for 12 hours to obtain solid graphene powder.
Fig. 5(a) and (b) are transmission electron micrographs of the graphene nanostructure of example 5.
Example 6:
with hexabromobenzene (C)6Br6) The method comprises the following steps of preparing a hexabromobenzene solution with the concentration of 1.0 g/400 ml by taking toluene as a solvent at room temperature and taking metal sodium as a raw material, and then adding 0.1 g of metal sodium into the solution.
The mixed solution was placed in a stainless steel autoclave lined with polytetrafluoroethylene and heated at a temperature in the range of 200 ℃ for 48 hours.
And (3) repeatedly washing the precipitate obtained after the reaction by using absolute ethyl alcohol, adding a first washing product obtained by centrifugal washing of deionized water, and dialyzing for 72 hours to obtain the graphene nanosheet aqueous solution. And (3) continuously washing the solid product with water until the supernatant of the solution is colorless, and then drying the solid product in a drying oven (at 60 ℃) for 12 hours to obtain solid graphene powder.
Fig. 6(a) and (b) are transmission electron micrographs of the graphene nanostructure of example 6.
Example 7:
with hexabromobenzene (C)6Br6) The preparation method comprises the following steps of taking metallic sodium as a raw material, taking toluene as a solvent at room temperature, preparing 1.0 g/400 ml of hexabromobenzene solution, and then adding 0.08 g of metallic sodium into the solution.
The mixed solution was placed in a stainless steel autoclave lined with polytetrafluoroethylene and heated at a temperature of 170 ℃ for 48 hours.
And (3) repeatedly washing the precipitate obtained after the reaction by using absolute ethyl alcohol, adding a first washing product obtained by centrifugal washing of deionized water, and dialyzing for 72 hours to obtain the graphene nanosheet aqueous solution. And (3) continuously washing the solid product with water until the supernatant of the solution is colorless, and then drying the solid product in a drying oven (at 60 ℃) for 12 hours to obtain solid graphene powder.
Fig. 7(a) and (b) are transmission electron micrographs of the graphene nanostructure of example 7.
Example 8:
with hexabromobenzene (C)6Br6) The preparation method comprises the following steps of preparing a hexabromobenzene solution with the concentration of 1.0 g/400 ml by taking toluene as a solvent at room temperature and taking metal sodium as a raw material, and then adding 0.12 g of metal sodium into the solution.
The mixed solution was placed in a stainless steel autoclave lined with polytetrafluoroethylene and heated at a temperature of 170 ℃ for 48 hours.
And (3) repeatedly washing the precipitate obtained after the reaction by using absolute ethyl alcohol, adding a first washing product obtained by centrifugal washing of deionized water, and dialyzing for 72 hours to obtain the graphene nanosheet aqueous solution. And (3) continuously washing the solid product with water until the supernatant of the solution is colorless, and then drying the solid product in a drying oven (at 60 ℃) for 12 hours to obtain solid graphene powder.
Fig. 8(a) and (b) are transmission electron micrographs of the graphene nanostructure of example 8.
Example 9:
with hexabromobenzene (C)6Br6) Sodium metal was used as a starting material, toluene was used as a solvent at room temperature to prepare a solution of 1.0 g/400 ml of hexabromobenzene, and 0.2484 g of sodium metal was added to the solution.
The mixed solution was placed in a stainless steel autoclave lined with polytetrafluoroethylene and heated at a temperature of 170 ℃ for 48 hours.
And (3) repeatedly washing the precipitate obtained after the reaction by using absolute ethyl alcohol, adding a first washing product obtained by centrifugal washing of deionized water, and dialyzing for 72 hours to obtain the graphene nanosheet aqueous solution. And (3) continuously washing the solid product with water until the supernatant of the solution is colorless, and then drying the solid product in a drying oven (at 60 ℃) for 12 hours to obtain solid graphene powder.
Fig. 9(a) and (b) are transmission electron micrographs of the graphene nanostructure of example 9.
Example 10:
with hexabromobenzene (C)6Br6) Sodium metal was used as a starting material, toluene was used as a solvent at room temperature to prepare a solution of 1.0 g/400 ml of hexabromobenzene, and 0.3312 g of sodium metal was added to the solution.
The mixed solution was placed in a stainless steel autoclave lined with polytetrafluoroethylene and heated at a temperature of 170 ℃ for 48 hours.
And (3) repeatedly washing the precipitate obtained after the reaction by using absolute ethyl alcohol, adding a first washing product obtained by centrifugal washing of deionized water, and dialyzing for 72 hours to obtain the graphene nanosheet aqueous solution. And (3) continuously washing the solid product with water until the supernatant of the solution is colorless, and then drying the solid product in a drying oven (at 60 ℃) for 12 hours to obtain solid graphene powder.
Fig. 10(a) and (b) are transmission electron micrographs of the graphene nanostructure of example 10.
Example 11:
with hexabromobenzene (C)6Br6) The preparation method comprises the following steps of taking sodium metal as a raw material, taking toluene as a solvent at room temperature, preparing 0.5 g/400 ml of hexabromobenzene solution, and then adding 0.1 g of sodium metal into the solution.
The mixed solution was placed in a stainless steel autoclave lined with polytetrafluoroethylene and heated at a temperature of 170 ℃ for 48 hours.
And (3) repeatedly washing the precipitate obtained after the reaction by using absolute ethyl alcohol, adding a first washing product obtained by centrifugal washing of deionized water, and dialyzing for 72 hours to obtain the graphene nanosheet aqueous solution. And (3) continuously washing the solid product with water until the supernatant of the solution is colorless, and then drying the solid product in a drying oven (at 60 ℃) for 12 hours to obtain solid graphene powder.
Fig. 11(a) and (b) are transmission electron micrographs of the graphene nanostructure of example 11.
Example 12:
with hexabromobenzene (C)6Br6) The method comprises the following steps of preparing a hexabromobenzene solution of 1.5 g/400 ml by taking toluene as a solvent at room temperature and taking metal sodium as a raw material, and then adding 0.1 g of metal sodium into the solution.
The mixed solution was placed in a stainless steel autoclave lined with polytetrafluoroethylene and heated at a temperature of 170 ℃ for 48 hours.
And (3) repeatedly washing the precipitate obtained after the reaction by using absolute ethyl alcohol, adding a first washing product obtained by centrifugal washing of deionized water, and dialyzing for 72 hours to obtain the graphene nanosheet aqueous solution. And (3) continuously washing the solid product with water until the supernatant of the solution is colorless, and then drying the solid product in a drying oven (at 60 ℃) for 12 hours to obtain solid graphene powder.
Fig. 12(a) and (b) are transmission electron micrographs of the graphene nanostructure of example 12.
Example 13:
hexabromobenzene (C6Br6) and lithium metal were used as raw materials, toluene was used as a solvent at room temperature to prepare a solution of 0.1 g/40 ml of hexabromobenzene, and then 0.0183 g of lithium metal was added to the solution.
The mixed solution was placed in a stainless steel reactor lined with polytetrafluoroethylene and heated at 180 ℃ for 50 hours.
And (3) repeatedly washing the precipitate obtained after the reaction by using absolute ethyl alcohol, adding a first washing product obtained by centrifugal washing of deionized water, and dialyzing for 72 hours to obtain the graphene nanosheet aqueous solution. And (3) continuously washing the solid product with water until the supernatant of the solution is colorless, and then drying the solid product in a drying oven (at 60 ℃) for 12 hours to obtain solid graphene powder.
Fig. 13(a) and (b) are transmission electron micrographs of the graphene nanostructure of example 13.
Example 14:
hexabromobenzene (C6Br6) and magnesium metal were used as raw materials, toluene was used as a solvent at room temperature to prepare a solution of hexabromobenzene (0.1 g/40 ml), and then 0.0313 g of magnesium metal was added to the solution.
The mixed solution was placed in a stainless steel reactor lined with polytetrafluoroethylene and heated at 180 ℃ for 50 hours.
And (3) repeatedly washing the precipitate obtained after the reaction by using absolute ethyl alcohol, adding a first washing product obtained by centrifugal washing of deionized water, and dialyzing for 72 hours to obtain the graphene nanosheet aqueous solution. And (3) continuously washing the solid product with water until the supernatant of the solution is colorless, and then drying the solid product in a drying oven (at 60 ℃) for 12 hours to obtain solid graphene powder.
Fig. 14(a) and (b) are transmission electron micrographs of the graphene nanostructure of example 14.
The present invention is not limited to the above embodiments, and any changes or substitutions that can be easily made by those skilled in the art within the technical scope of the present invention are also within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (1)
1. A method for synthesizing graphene is characterized by comprising the following steps:
1) preparing a hexabromobenzene solution at room temperature by taking toluene as a solvent, and then adding an active metal into the solution; the active metal is selected from any one of sodium, lithium and magnesium;
2) placing the mixed solution in a stainless steel reaction kettle with a polytetrafluoroethylene lining, and heating for reaction;
3) washing the precipitate obtained after the reaction in the step 2) with absolute ethyl alcohol, adding deionized water for centrifugal washing, and dialyzing the washing product to obtain a graphene nanosheet aqueous solution; continuously washing the solid product with water until the supernatant of the solution is colorless, and drying to obtain solid graphene powder; wherein the molar ratio of hexabromobenzene to active metal in the step 1) is as follows: 0.0694: 1-0.625: 1; wherein, in the step 2), the mixture is heated for 24 to 72 hours at the temperature of 170 to 200 ℃; wherein, in the step 3), a first washing product obtained by centrifugal washing of deionized water is added for dialysis; wherein, the drying temperature is 60-90 ℃ during drying, and the drying time is more than or equal to 12 hours.
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| CN101462719A (en) * | 2009-01-16 | 2009-06-24 | 北京大学 | Preparation of graphene |
| CN102408107A (en) * | 2010-09-26 | 2012-04-11 | 中国科学院上海硅酸盐研究所 | Method for preparing high-quality graphene |
| CN104058399A (en) * | 2014-07-17 | 2014-09-24 | 山东理工大学 | Direct preparation method of high-purity high-quality graphene |
| CN104201357A (en) * | 2014-09-18 | 2014-12-10 | 温州大学 | Graphene quantum dot-graphene composite material as well as preparation method and application thereof |
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