CN115611271A - Preparation method of graphene - Google Patents
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- CN115611271A CN115611271A CN202211338796.2A CN202211338796A CN115611271A CN 115611271 A CN115611271 A CN 115611271A CN 202211338796 A CN202211338796 A CN 202211338796A CN 115611271 A CN115611271 A CN 115611271A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 226
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 80
- 239000010439 graphite Substances 0.000 claims abstract description 80
- 239000006185 dispersion Substances 0.000 claims abstract description 70
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- 238000000034 method Methods 0.000 claims abstract description 48
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- 238000002156 mixing Methods 0.000 claims abstract description 17
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- 229930091371 Fructose Natural products 0.000 claims description 14
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 14
- 239000005715 Fructose Substances 0.000 claims description 14
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 14
- 239000008103 glucose Substances 0.000 claims description 14
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- 229930182830 galactose Natural products 0.000 claims description 8
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 5
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- 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
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- C—CHEMISTRY; METALLURGY
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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
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Abstract
The invention discloses a preparation method of graphene, which comprises the following steps: (1) Mixing carbon nanospheres, graphite and water to prepare a pretreated carbon nanosphere/graphite dispersion liquid; (2) Stripping the pretreated nano carbon sphere/graphite dispersion liquid obtained in the step (1) to prepare a graphene dispersion liquid; (3) And (3) carrying out freeze drying on the graphene dispersion liquid obtained in the step (2) to obtain graphene. According to the method, monosaccharide is used as a raw material, a hydrothermal method is used for preparing nano carbon spheres, the nano carbon spheres are used as stripping aids, and graphite is stripped into graphene under the action of ultrahigh shearing rate of a micro-jet homogenizer and the like.
Description
Technical Field
The invention relates to the field of graphene preparation, in particular to a method for preparing graphene by using nano carbon spheres as a dispersing agent.
Background
The graphene is represented by sp 2 The hybridized carbon atoms are piled up into a honeycomb-shaped two-dimensional sheet, the two-dimensional sheet has excellent mechanical property, specific surface area, carrier mobility and thermal conductivity, and has quanta at room temperatureThe Hall effect and the dual-polarized electric field effect have wide application prospects in the fields of energy conversion and storage, sensors, display screens, adsorption materials, heat conduction materials, environment-friendly materials and the like. The environment-friendly, cheap and safe preparation of graphene is an important condition for the industrial application of graphene. Therefore, the development of a green graphene preparation method is of great significance.
The preparation method of graphene is various, and is roughly divided into two types, one is a bottom-up method, and is a method for preparing a graphene sheet layer by a chemical method, including a chemical vapor deposition method, an arc discharge method, a SiC epitaxial growth method, a chemical conversion method, a CO reduction method, a decompression carbon nanotube method, a surfactant self-assembly method and the like; the other type is a top-down method, which means that van der waals force between graphite layers is destroyed under the action of external force, and graphite sheets or graphite oxide sheets are peeled off to obtain graphene with few layers, and the method comprises a mechanical peeling method, an electrochemical peeling method, a supercritical fluid peeling method, a microwave peeling method and the like.
At present, the commonly used preparation methods of graphene mainly comprise a chemical vapor deposition method and a separation and stripping method based on a Hummers method, but the methods have obvious advantages and disadvantages. The number of graphene layers prepared by the chemical vapor deposition method is small, the surface is clean, and the shape can be controlled to a certain degree, but the method has the advantages of low efficiency, high cost, harsh production conditions and high difficulty in separating and transferring the graphene film. The Hummers method can intercalate and oxidize graphite, enlarge the interlayer spacing of the graphite, reduce shearing force used for stripping, and reduce the graphite to obtain graphene. However, the Hummers method has disadvantages such as environmental unfriendliness, and although a series of improvements have been made so far, the improved Hummers method is still environmentally unfriendly and can destroy the graphene structure.
In recent years, the liquid phase exfoliation method, in which graphite is exfoliated directly in a liquid phase system to which an auxiliary agent is added without oxidation and reduction, is one of the methods that have received much attention and is considered to be the most likely method for mass production of graphene. The auxiliary agents comprise the following components: ionic liquids, solvents and additives. But ionic liquids are expensive and the experimental conditions are harsh; the use of the solvent is not environment-friendly, and the property of the solvent can improve the experimental conditions; although there are many choices of additives, which can avoid the above problems, and the production process is simple, the production cost is low, and the preparation method is environmentally friendly, the purification of the final graphene is difficult.
Disclosure of Invention
In order to solve the technical problems, the invention provides a liquid phase stripping method for preparing graphene, wherein nano carbon spheres are used as a stripping aid, water is used as a medium, and graphene is prepared by stripping graphite by utilizing the action of ultrahigh shear rate of a micro-jet homogenizer and the like.
The technical scheme of the invention is as follows:
a method for preparing graphene, the method comprising the steps of:
(1) Mixing carbon nanospheres, graphite and water to prepare a pretreated carbon nanosphere/graphite dispersion liquid;
(2) Stripping the pretreated nano carbon sphere/graphite dispersion liquid obtained in the step (1) to prepare a graphene dispersion liquid;
(3) And (3) carrying out freeze drying on the graphene dispersion liquid obtained in the step (2) to obtain graphene.
According to an embodiment of the present invention, in the step (1), the nanocarbon sphere can be prepared by using monosaccharide as a raw material and using a hydrothermal method.
According to an embodiment of the present invention, in the step (1), the raw material for preparing the nanocarbon globules is monosaccharide, and the monosaccharide is at least one selected from glucose, fructose, galactose, and the like.
According to embodiments of the invention, the reaction temperature of the hydrothermal process is in the range of 100 to 300 deg.C, such as 160 to 200 deg.C, and exemplary is 100 deg.C, 120 deg.C, 130 deg.C, 150 deg.C, 160 deg.C, 180 deg.C, 200 deg.C, 220 deg.C, 240 deg.C, 260 deg.C, 280 deg.C, 300 deg.C.
According to an embodiment of the invention, the monosaccharide concentration in the hydrothermal process is 1-60mg/mL, such as 10-50mg/mL, exemplary 1mg/mL, 5mg/mL, 10mg/mL, 20mg/mL, 30mg/mL, 40mg/mL, 50mg/mL, 60mg/mL.
According to an embodiment of the invention, the reaction time of the hydrothermal process is 5-10h, such as 6-8h, exemplary 5h, 6h, 7h, 8h, 9h, 10h.
According to an embodiment of the present invention, in the step (1), the graphite is selected from at least one of natural flake graphite, expanded graphite, graphite powder, and the like. Further, the graphite is in the form of powder, for example, the mesh number of the graphite powder is 80 to 5000 meshes, and is exemplified by 80, 200, 300, 325, 500, 750, 1000, 1200, 1500, 2000, 3000, 4000 or 5000 meshes.
According to an embodiment of the invention, in step (1), the concentration of graphite in the pretreated nanocarbon sphere/graphite dispersion is 1-50mg/mL, such as 5-25mg/mL, exemplary 1mg/mL, 5mg/mL, 10mg/mL, 25mg/mL, 30mg/mL, 40mg/mL, 50mg/mL.
According to an embodiment of the present invention, step (1) may specifically be: (1a) Preparing carbon nanospheres by a hydrothermal method, and adding graphite into a carbon nanosphere aqueous solution to obtain a pretreated carbon nanosphere/graphite dispersion solution.
According to an embodiment of the present invention, step (1) may further be: (1b) Adding graphite and monosaccharide into water, mixing, performing hydrothermal treatment, and preparing the monosaccharide into carbon nanospheres to obtain the pretreated carbon nanosphere/graphite dispersion liquid.
According to an embodiment of the present invention, step (1) may also be: (1c) Adding graphite and monosaccharide into water, carrying out hydrothermal treatment, preparing the monosaccharide into carbon nanospheres, and then mixing to obtain a pretreated carbon nanosphere/graphite dispersion liquid.
According to an embodiment of the present invention, in the step (1 b), mixing may be performed using a high shear dispersion emulsifier.
According to an embodiment of the invention, in step (1 b), the high shear dispersing emulsifier has a treatment time of 1-100min, such as 5-50min, exemplary 5min, 25min, 50min, 75min, 100min.
According to an embodiment of the invention, in step (1 b), the rotational speed of the high shear dispersing emulsifier is 1000-15000rpm, such as 5000-10000rpm, exemplary 5000rpm, 8000rpm, 10000rpm.
According to an embodiment of the present invention, in the step (1 c), the mixing may be performed by means of ultrasound.
According to the embodiment of the invention, in the step (2), the pretreated nano carbon sphere/graphite dispersion liquid is added into a shearing device with an ultrahigh shearing rate for stripping, so as to obtain a graphene dispersion liquid.
According to an embodiment of the present invention, in step (2), the shearing device having an ultra-high shear rate includes, but is not limited to: a microfluidizer, and the like.
According to an embodiment of the present invention, step (2) may specifically be: stripping the pretreated nano carbon sphere/graphite dispersion liquid in a micro-jet homogenizer, wherein the specific process comprises the following steps: the pre-treated nanocarbon sphere/graphite dispersion is first circulated through a nozzle of 200-400 μm (exemplary 200 μm, 300 μm or 400 μm) 1-5 times (exemplary 1, 3 or 5 cycles) at a pressure of 3000-5000psi (exemplary 3000psi, 4000psi or 5000 psi); and then circulated through a nozzle of 100-200 μm (illustratively 100 μm, 150 μm, or 200 μm) 1-50 times (illustratively 3, 5, or 7 times) at a pressure of 15000-22000psi (illustratively 15000psi, 18000psi, or 22000 psi).
According to an embodiment of the present invention, in the step (2), the peeling time is 10 to 100min.
According to an embodiment of the present invention, in the step (3), the freeze-drying time is 1 to 3 days. The temperature of the freeze-drying is-50 ℃ to-10 ℃, and-30 ℃ is exemplary.
The invention also provides graphene obtained by the preparation method.
According to the embodiment of the invention, the number of layers of the graphene obtained by the preparation method of the graphene is 1-10, and the transverse dimension is 0.5-10 μm.
The present invention also provides a liquid phase exfoliation system for preparing graphene, the liquid phase exfoliation system comprising: graphite, nano carbon spheres and water.
According to the embodiment of the invention, in the liquid phase stripping system, the carbon nanospheres can be prepared by taking monosaccharide as a raw material and utilizing a hydrothermal method.
According to an embodiment of the present invention, the monosaccharide is selected from at least one of glucose, fructose, galactose, and the like.
According to an embodiment of the invention, the monosaccharide concentration is 1-60mg/mL, such as 10-50mg/mL.
According to an embodiment of the present invention, the graphite is selected from at least one of natural flake graphite, expanded graphite, graphite powder, and the like. Further, the graphite is in the form of powder, for example, the mesh number of the graphite powder is 80 to 5000 meshes.
According to an embodiment of the present invention, in the liquid-phase exfoliation system, the concentration of the graphite is 1 to 50mg/mL.
The invention has the beneficial effects that:
in the method for preparing graphene by adopting the liquid phase stripping method, monosaccharide is used as a raw material, nano carbon spheres are prepared by a hydrothermal method, the nano carbon spheres are used as a stripping aid, and graphite is stripped into graphene by the action of ultrahigh shear rate of a micro-jet homogenizer and the like. The method (1) has wide raw material source and low cost; (2) The pretreatment process for preparing the carbon nanospheres by the hydrothermal method is simple and green, no harmful substance is generated, the whole preparation process takes water as a medium, acid, strong oxidant and the like are not required to be added, and the preparation method is green and environment-friendly, low in cost, high in efficiency, good in product quality and wide in application prospect; (3) The surface of the prepared graphene is not damaged, adsorbed nano carbon spheres exist, a floating island-shaped active functional group structure is formed on the surface of the graphene, the dispersity of the graphene is improved, and the graphene has high conductivity.
In addition, the number of layers of the required graphene sheet layers, the transverse dimension and the like can be adjusted by adjusting conditions such as the addition amount of monosaccharide, the mesh number of graphite, the cycle number of the micro-jet treatment and the like.
Drawings
Fig. 1 is an SEM image of graphene prepared in example 2;
fig. 2 is an infrared spectrum of graphene prepared in example 3;
FIG. 3 shows examples 4 and comparative examples 1 to 3Using carbon nanospheres (CS), NMP, PMA, C 2 H 6 O is a comparison graph of the conductivity of graphene prepared by the stripping aid;
fig. 4 is a TEM image of graphene prepared in example 2;
fig. 5 is a raman spectrum of graphene prepared at different monosaccharide concentrations using the method of example 1.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
(1) Firstly, adding 325-mesh graphite powder and glucose into water to prepare graphite powder/glucose dispersion liquid, wherein the concentration of the graphite powder is 25mg/mL, the concentration of the glucose is 10mg/mL, and shearing and mixing the dispersion liquid for 5min at the rotating speed of 8000rpm by using a high-shear dispersion emulsifying machine; preserving the heat at 180 ℃ for 7h, and preparing the glucose into carbon nanospheres to obtain a pretreated carbon nanosphere/graphite dispersion liquid;
(2) Adding the pretreated nano carbon sphere/graphite dispersion liquid into a micro-jet homogenizer, and circulating for 1 time through a nozzle with the diameter of 300 mu m at the pressure of 5000psi; circulating the graphene dispersion solution for 3 times through a nozzle with the diameter of 100 mu m, wherein the pressure is 18000psi, and obtaining graphene dispersion solution;
(3) And freeze-drying the graphene dispersion liquid for 72 hours at the temperature of minus 30 ℃ to obtain graphene.
Example 2
(1) Mixing fructose with water to prepare a fructose/water solution with the concentration of 30 mg/mL; adding 750-mesh graphite powder into the fructose/water solution to prepare a fructose/graphite dispersion liquid with the concentration of 10 mg/mL; shearing and mixing the fructose/graphite dispersion liquid for 25min by using a high-shear dispersion emulsifying machine at the rotating speed of 8000rpm, performing hydrothermal treatment for 7h at the temperature of 200 ℃, and preparing fructose into nano carbon spheres to obtain a pretreated nano carbon sphere/graphite dispersion liquid;
(2) Adding the pretreated nano carbon ball/graphite dispersion liquid into a micro-jet homogenizer, and circulating for 3 times through a nozzle with the diameter of 300 mu m at the pressure of 4000psi; circulating the graphene dispersion solution for 3 times through a nozzle with the diameter of 150 mu m, wherein the pressure is 18000psi, and obtaining graphene dispersion solution;
(3) And (3) freeze-drying the graphene dispersion liquid for 72 hours at the temperature of minus 30 ℃ to obtain the graphene.
Fig. 1 is an SEM image of graphene prepared in example 2; fig. 4 is a TEM image of graphene prepared in example 2.
Example 3
(1) Mixing glucose and water to prepare a glucose/water solution with the concentration of 50mg/mL, and preserving heat at 160 ℃ for 6 hours to prepare a nano carbon sphere/water solution with the concentration of 50 mg/mL; adding 1200-mesh graphite powder into the nano carbon sphere/water solution to prepare nano carbon sphere/graphite dispersion liquid with the concentration of 5mg/mL; stirring until the system is uniform to obtain a pretreated nano carbon sphere/graphite dispersion liquid;
(2) Adding the pretreated nano carbon sphere/graphite dispersion liquid into a micro-jet homogenizer, and circulating for 3 times through a nozzle with the diameter of 250 mu m at the pressure of 5000psi; circulating the graphene dispersion solution for 5 times through a nozzle with the diameter of 100 mu m, wherein the pressure is 18000psi, and obtaining graphene dispersion solution;
(3) And (3) freeze-drying the graphene dispersion liquid for 72 hours at the temperature of minus 30 ℃ to obtain the graphene.
Example 4
(1) Firstly, adding 2000-mesh graphite powder and galactose into water, wherein the concentration of the galactose is 10mg/mL, and the concentration of the graphite powder is 25mg/mL; preserving heat at 180 ℃ for 7h, preparing galactose into carbon nanospheres, and mixing the carbon nanospheres with the galactose by ultrasonic treatment for 5min to obtain a pretreated carbon nanosphere/graphite dispersion liquid;
(2) Adding the pretreated nano carbon sphere/graphite dispersion liquid into a micro-jet homogenizer, and circulating for 5 times through a nozzle with the diameter of 200 mu m at the pressure of 5000psi; circulating the graphene dispersion solution for 7 times through a nozzle with the diameter of 100 mu m under the pressure of 22000psi to obtain graphene dispersion solution;
(3) And freeze-drying the graphene dispersion liquid for 72 hours at the temperature of minus 30 ℃ to obtain graphene.
Example 5
(1) Firstly, adding natural crystalline flake graphite and fructose into water to prepare a natural crystalline flake graphite/fructose dispersion liquid, wherein the concentration of the natural crystalline flake graphite is 5mg/mL, the concentration of the fructose is 30mg/mL, and shearing and mixing the dispersion liquid for 50min at the rotating speed of 5000rpm by using a high-shear dispersion emulsifying machine; preserving the heat at 160 ℃ for 8h, and preparing fructose into carbon nanospheres to obtain a pretreated carbon nanosphere/graphite dispersion liquid;
(2) Adding the pretreated nano carbon sphere/graphite dispersion liquid into a micro-jet homogenizer, and circulating for 5 times through a nozzle with the diameter of 250 mu m at the pressure of 3000psi; circulating the graphene dispersion solution for 3 times through a nozzle with the diameter of 150 mu m, wherein the pressure is 15000psi, and obtaining graphene dispersion solution;
(3) And freeze-drying the graphene dispersion liquid for 72 hours at the temperature of minus 30 ℃ to obtain graphene.
Example 6
(1) Firstly, adding expanded graphite and glucose into water to prepare an expanded graphite/glucose dispersion liquid, wherein the concentration of the expanded graphite is 5mg/mL, the concentration of the glucose is 50mg/mL, and shearing and mixing the dispersion liquid for 50min at the rotating speed of 5000rpm by using a high-shear dispersion emulsifying machine; preserving the heat at 170 ℃ for 6h, and preparing the glucose into carbon nanospheres to obtain a pretreated carbon nanosphere/graphite dispersion liquid;
(2) Adding the pretreated nano carbon sphere/graphite dispersion liquid into a micro-jet homogenizer, and circulating for 3 times through a nozzle with the diameter of 250 mu m at the pressure of 5000psi; circulating the graphene dispersion solution for 5 times through a nozzle with the diameter of 150 mu m under the pressure of 18000psi to obtain graphene dispersion solution;
(3) And (3) freeze-drying the graphene dispersion liquid for 72 hours at the temperature of minus 30 ℃ to obtain the graphene.
The number of layers and lateral dimensions of the graphene sheets prepared in examples 1 to 6 are shown in table 1.
Comparative example 1
Comparative example 1 differs from example 1 in that: and (3) replacing the nano carbon sphere water solution in the step (1) with NMP as a solvent, and mixing the nano carbon sphere water solution with graphite powder.
Comparative example 2
Comparative example 2 differs from example 3 in that: replacing the nano carbon sphere water solution in the step (1) with PMA as a solvent, and mixing the PMA with graphite powder.
Comparative example 3
Comparative example 3 differs from example 4 in that: replacing the nano carbon sphere aqueous solution in the step (1) with C as a solvent 2 H 6 And O, and mixing the graphite powder with the graphite powder.
The product was tested using the following test method.
Testing the layer number of the graphene sheet by adopting an atomic force microscope; testing the transverse size of the graphene sheet by using a transmission electron microscope; and testing the conductivity of the graphene by adopting a four-probe method.
TABLE 1
As can be seen from table 1, the more monosaccharide is added, the fewer the number of graphene sheets; the higher the number of the graphite meshes is, the smaller the transverse size of the graphene is; the more the number of cycles of the microfluidic treatment, the fewer the number of graphene sheets and the smaller the lateral dimension.
Fig. 2 is an infrared spectrogram of graphene prepared in example 3 of the present invention, where curves in fig. 2 sequentially represent a, b, c, d, and e from bottom to top, a represents pure carbon nanospheres, b represents an initial carbon nanosphere/graphite dispersion, c represents a precipitate obtained by centrifuging (3 times, 5 minutes, and 10000 cycles) after a micro-jet circulation, d represents a product obtained by annealing the precipitate, and e represents pure graphite, and it can be seen that characteristic absorption peaks of carbon nanospheres still remain on the surface of graphene after centrifugation, which indicates that carbon nanospheres are attached to the surface of graphene to play roles in assisting exfoliation and preventing reaggregation; in addition, as can be seen from fig. 2, graphene contains a large number of functional groups.
FIG. 3 shows the carbon nanospheres (CS), NMP, PMA and C used in example 4 and comparative examples 1 to 3, respectively 2 H 6 O is a comparison of the electrical conductivities of the graphenes prepared with the exfoliation aid, and it can be seen from fig. 3 that the electrical conductivity of the product obtained using the exfoliation system of the present invention comprising carbon nanospheres is superior to that obtained using other exfoliation systems.
Fig. 5 is a raman spectrum of graphene prepared at different monosaccharide concentrations using the method of example 1. As can be seen from FIG. 5, as the amount of monosaccharide added (monosaccharide concentrations were 0mg/ml, 10mg/ml, 20mg/ml, 30mg/ml and 40mg/ml in this order), the intensity ratio of the D peak to the G peak (I) D /I G ) The gradual increase indicates that more edge defects are introduced during the micro-jet treatment process, and the graphene stripping effect is better, wherein the curves in fig. 5 sequentially represent 0mg/ml, 10mg/ml, 20mg/ml, 30mg/ml and 40mg/ml from bottom to top.
The embodiments of the present invention have been described above by way of example. However, the scope of the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of graphene is characterized by comprising the following steps:
(1) Mixing carbon nanospheres, graphite and water to prepare a pretreated carbon nanosphere/graphite dispersion liquid;
(2) Stripping the pretreated nano carbon sphere/graphite dispersion liquid obtained in the step (1) to prepare a graphene dispersion liquid;
(3) And (3) carrying out freeze drying on the graphene dispersion liquid obtained in the step (2) to obtain graphene.
2. The method according to claim 1, wherein in the step (1), the nanocarbon spheres are prepared by using monosaccharide as a raw material and using a hydrothermal method.
Preferably, in the step (1), the raw material for preparing the carbon nanospheres is monosaccharide, and the monosaccharide is at least one selected from glucose, fructose and galactose.
3. The process according to claim 1 or 2, characterized in that the reaction temperature of the hydrothermal process is between 100 and 300 ℃; the reaction time of the hydrothermal method is 5-10h.
Preferably, the concentration of monosaccharide in the hydrothermal process is 1-60mg/mL.
4. The method according to any one of claims 1 to 3, wherein in step (1), the graphite is selected from at least one of natural flake graphite, expanded graphite, and graphite powder.
Preferably, the form of the graphite is powder, and the mesh number of the graphite powder is 80-5000 meshes.
Preferably, in the step (1), the concentration of graphite in the pretreated nano carbon sphere/graphite dispersion liquid is 1-50mg/mL.
5. The method according to any one of claims 1 to 4, wherein in the step (2), the pretreated nanocarbon sphere/graphite dispersion liquid is added into a shearing device with an ultrahigh shearing rate for stripping, so as to obtain a graphene dispersion liquid.
Preferably, in the step (2), the shearing device with the ultrahigh shear rate is a microfluidizer.
6. The method according to any one of claims 1 to 5, wherein step (2) is in particular: stripping the pretreated nano carbon sphere/graphite dispersion liquid in a micro-jet homogenizer: circulating the pretreated nano carbon sphere/graphite dispersion liquid for 1-5 times through a nozzle with the diameter of 200-400 mu m, wherein the pressure is 3000-5000psi; and circulating the mixture through a 100-200 μm nozzle for 1-50 times at 15000-22000psi.
7. The method according to any one of claims 1 to 6, wherein in step (2), the peeling time is 10 to 100min.
8. Graphene prepared by the method of any one of claims 1 to 7.
9. The graphene according to claim 8, wherein the number of graphene layers is 1-10 and the lateral dimension is 0.5-10 μm.
10. A liquid phase exfoliation system to produce graphene, wherein the liquid phase exfoliation system comprises: graphite, nano carbon spheres and water.
Preferably, the nanocarbon sphere can be prepared by using monosaccharide as a raw material and utilizing a hydrothermal method.
Preferably, the monosaccharide is at least one selected from glucose, fructose and galactose.
Preferably, the concentration of the monosaccharide is 1-60mg/mL.
Preferably, the graphite is selected from at least one of natural flake graphite, expanded graphite, and graphite powder.
Preferably, the form of the graphite is powder, and the mesh number of the graphite powder is 80-5000 meshes.
Preferably, in the liquid phase exfoliation system, the concentration of the graphite is 1-50mg/mL.
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