CN114763261A - Method for preparing graphene material and graphene material obtained by method - Google Patents
Method for preparing graphene material and graphene material obtained by method Download PDFInfo
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Classifications
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a method for preparing a graphene material and the graphene material obtained by the method, the graphite material and a high molecular polymer are melted and blended, cooled and formed, a formed composite material is stretched by utilizing stretching equipment, the deformed composite material is melted and stirred, and then cooled and formed; repeating the melting and stretching processes for multiple times to obtain a compound; treating the composite with a solvent to obtain the graphene material; the solvent is compatible with the high molecular polymer; the method for preparing the graphene material by stripping in a multi-stretching mode is simple and easy to operate, and the prepared graphene material shows the special high thermal conductivity, high electric conductivity and excellent mechanical properties of graphene, can be used as a precursor of a thermal management material, and can also be used as a carrier or a filler to be widely applied to preparation of rubber, plastic and membrane materials.
Description
Technical Field
The invention belongs to the technical field of graphene, and particularly relates to a method for preparing a graphene material and the graphene material prepared by the method.
Background
The graphene is represented by sp2The two-dimensional crystal with single atom thickness composed of hybridized carbon atoms is a basic structural unit of carbon materials such as graphite, fullerene, carbon nano tube and the like. Each carbon atom of graphene is sp2The graphene with the structure has excellent rigidity and mechanical properties, the theoretical Young modulus of the graphene reaches 1TPa, and the tensile strength of the graphene reaches 130 GPa. And the residual P orbitals of the carbon atoms of the graphene form a large pi bond, so that the graphene is endowed with ultrahigh conductivity, and the electron mobility of the graphene at room temperature reaches 15000cm2/(v·s) conductivity up to 106S/cm. Meanwhile, the graphene also has excellent optical performance and heat conduction performance, the light transmittance of the graphene reaches 97.7%, and the thermal conductivity coefficient of the defect-free single-layer graphene is as high as 5300W/(m.K), so that the graphene is a known carbon material with the highest thermal conductivity coefficient. The excellent performances enable the graphene to have wide application prospects in the fields of energy storage, solar cells, catalyst carriers, nano electronic devices, composite materials and the like. Therefore, developing a low-cost and high-quality graphene material is one of the current research hotspots.
At present, the preparation methods of graphene materials are mainly divided into two types, one is a bottom-to-top method, such as a chemical vapor deposition method and the like, and the chemical vapor deposition method can obtain high-quality graphene but has the problems of low yield, high cost and the like; one is a top-down method, such as a mechanical exfoliation method and a chemical oxidation-reduction method, and due to strong pi bonds between graphene layers, the graphene powder obtained by the mechanical exfoliation method is high in cost, or the obtained graphene is generally multilayer graphene, and the difference between each property of the graphene powder and the property of the single-layer graphene is large. The chemical oxidation-reduction method is to oxidize natural graphite into graphite oxide by a strong oxidant, because the strong oxidant can destroy pi bonds between graphite layers, the distance between the graphite layers is enlarged, and a large amount of oxygen-containing groups with strong hydrophilicity, such as carboxyl, hydroxyl and the like, are generated between the graphite layers and at the edges in the oxidation process, so that the graphite oxide can form a good dispersion effect in water, and graphene oxide with few layers and even single layer can be obtained by simple physical means, such as solvent stirring diffusion, ultrasound and the like. The graphene oxide can be subjected to a reduction reaction to obtain reduced graphene oxide. The chemical oxidation-reduction method has the advantages of relatively simple and convenient process, low cost, high yield and the like, and is suitable for large-scale industrial preparation, so the method becomes one of the important methods for preparing the graphene at present. However, the oxidation-reduction process damages the crystal structure of graphene, so that the electrical conductivity, mechanical strength and other properties of graphene oxide and reduced graphene oxide are greatly reduced compared with those of pure graphene.
Therefore, it is necessary to design and develop a method for preparing thin-layer or even single-layer graphene on a large scale at low cost.
Disclosure of Invention
In view of the problems in the prior art, the present invention aims to provide a method for preparing graphene by multiple melting and stretching modes, wherein the method is simple and efficient to operate, and the prepared graphene material is thin-layer graphene, shows high thermal conductivity, high electrical conductivity and excellent mechanical properties of graphene, and can be used as a precursor of a thermal management material; can also be used as a carrier or a filler to be widely applied to the preparation of rubber, plastic and film materials.
The technical scheme of the invention is as follows:
the invention provides a method for preparing a graphene material, which comprises the following steps:
a method for preparing a graphene material is characterized by comprising the following steps:
(1) carrying out melt blending on a graphite material and a high molecular polymer to obtain a blend;
(2) cooling and molding the blend to obtain a molded composite material;
(3) stretching the formed composite material by utilizing stretching equipment to obtain a deformed composite material;
(4) melting the deformed composite material, stirring, cooling and molding;
(5) repeating the step (3) and the step (4) for N times, wherein N is more than or equal to 1, and obtaining a compound;
(6) treating the composite with a solvent to obtain the graphene material; the solvent is compatible with the high molecular polymer.
As a preferred technical scheme, the graphite material is one of natural crystalline flake graphite, colloidal graphite, thermal cracking graphite, expanded graphite, multilayer graphene oxide, and multilayer reduced graphene oxide.
Preferably, the average number of layers of the graphite material is greater than 10.
Preferably, the ratio of the mass of the graphite material to the mass of the polymer is 1:3 to 1:200, preferably 1:10 or 1:20 at the upper limit and 1:40 at the lower limit.
As a preferred technical solution, the high molecular polymer is one or a blend of at least two of polyethylene, polypropylene, polybutadiene, polyisoprene, polyvinyl chloride, polystyrene, a block copolymer of Styrene and Butadiene (SBS), a hydride of a block copolymer of styrene and butadiene (hydrogenated SBS), starch, polyethylene glycol, cellulose, polymaleic anhydride, polyacrylamide, polyvinylpyrrolidone, epoxy resin, polyethylene oxide, polyurea, polycarbonate, polyaniline, polylactic acid, polyurethane, polyacrylic acid, polymethyl acrylate, polymethyl methacrylate, polyvinyl alcohol, polyethylene terephthalate, polypropylene terephthalate, polyethylene furan dicarboxylate, sucrose, maltose, and polypyrrole;
the number average molecular weight of the high molecular polymer is preferably 300 to 20 ten thousand.
Preferably, the solvent in the step (6) is at least one of water, benzene, toluene, xylene, trimethylbenzene, ethylbenzene, dichloromethane, dichloroethane, chloroform, acetone, ethanol, carbon tetrachloride, tetrachloroethylene, dioxane, pyridine, acetonitrile, diethyl ether, butyl acetate, ethyl acetate, propyl acetate, tributyl phosphate, trioctyl phosphate, propylene oxide, n-pentane, n-hexane, n-octane, cyclohexane, methyl butanone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, methanol and isopropanol.
As a preferable embodiment, the temperature for melt blending in the step (1) and melting in the step (4) is 30 to 300 ℃, preferably the lower limit value of the melting temperature is 80 ℃, 110 ℃, the upper limit temperature is 140 ℃, 150 ℃.
In a preferable embodiment, in the step (2), the cooling temperature is-20 ℃ to 100 ℃, and the upper limit of the cooling temperature is preferably 25 ℃ to 35 ℃.
Preferably, in the step (3), the temperature condition for stretching is-20 ℃ to 100 ℃. The tensile strength is 2-200 Mpa, and the tensile rate is 10-1000%.
The stretching temperature of the method is relatively low and can be lower than the glass transition temperature of a high molecular polymer, theoretically, the lower stretching temperature can increase the stretching strength, and graphene can be more effectively stripped.
In the step (6), the temperature of the solvent-treated complex is preferably-20 to 150 ℃, more preferably 97 ℃ at the upper limit and 25 ℃ at the lower limit.
In another aspect, the present invention provides a graphene material prepared by any of the above methods.
Preferably, the number of layers of graphene in the graphene material is less than 10, preferably less than 3.
Preferably, the mass content of graphene in the graphene material is greater than 80%.
The method for preparing the graphene material by stripping in a multi-melting and stretching mode is simple and easy to operate, and the prepared graphene material shows the specific high thermal conductivity, high electrical conductivity and excellent mechanical properties of graphene, can be used as a precursor of a thermal management material, and can also be used as a carrier or a filler to be widely applied to preparation of rubber, plastics and membrane materials.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to the following embodiments, but the scope of the present invention should not be construed as being limited to the following examples.
Example 1
(1) Adding natural graphite powder and polystyrene (the number average molecular weight is about 10 ten thousand) into a mixing roll according to the mass ratio of 1:40, and carrying out melt blending, wherein the mixing maximum temperature is 140 ℃, so as to obtain a uniformly mixed graphite/polystyrene mixture;
(2) tabletting the graphite/polystyrene mixture, cooling to room temperature of 25 ℃, cutting and molding, stretching by a stretching device, wherein the stretching temperature is 80 ℃, the elongation of the graphite/polystyrene mixture in the stretching process is close to the upper limit of fracture, the fracture is avoided as much as possible, the maximum tensile strength is 40MPa, the maximum elongation is 50%, adding the mixture subjected to plastic deformation after stretching into a mixing roll, melting and mixing again, and the highest mixing temperature is increased to 150 ℃;
(3) repeating the step (2) for 10 times to finally obtain a thin-layer graphene/polystyrene mixture;
(4) and repeatedly soaking and filtering the obtained thin-layer graphene/polystyrene mixture for 10 times by using dimethylbenzene at room temperature, and drying to obtain the graphene material. Through optical microscope detection, 95% of the obtained graphene material is thin-layer graphene with the layer number less than 10.
Example 2
(1) Adding multilayer graphene (obtained by grinding natural graphite) and maltose into a mixing roll according to the mass ratio of 1:20, and carrying out melt blending at the mixing temperature of 110 ℃ at most to obtain a uniformly mixed multilayer graphene/maltose mixture;
(2) cooling the multilayer graphene/maltose mixture to 35 ℃, stretching the mixture through stretching equipment, wherein the stretching temperature is 70 ℃, the elongation of the multilayer graphene/maltose mixture in the stretching process is close to the upper limit of fracture, the fracture does not occur as much as possible, the maximum tensile strength is 2MPa, the maximum elongation is 1000%, adding the mixture which is subjected to plastic deformation after stretching into a mixing roll, and melting and mixing the mixture again, wherein the mixing maximum temperature is 110 ℃;
(3) repeating the step (2) for 20 times to finally obtain a thin-layer graphene/maltose mixture;
(4) and repeatedly soaking and filtering the obtained thin-layer graphene/maltose mixture for 10 times by using deionized water at room temperature, and drying to obtain the graphene material. Through optical microscope detection, 85% of the obtained graphene material is thin-layer graphene with the layer number smaller than 10.
Example 3
(1) Adding natural graphite powder and polyvinyl alcohol (the number average molecular weight is about 3 ten thousand) into a mixing roll according to the mass ratio of 1:10, and carrying out melt blending at the mixing temperature of 80 ℃ at most to obtain a uniformly mixed graphite/polyvinyl alcohol mixture;
(2) cooling the multilayer graphene/polyvinyl alcohol mixture to the room temperature of 25 ℃, cutting and molding, stretching by using stretching equipment, wherein the stretching temperature is room temperature, the elongation of the polymer in the stretching process is close to the upper limit of fracture, the polymer is not fractured as much as possible, the maximum tensile strength is 25MPa, the maximum elongation is 20%, adding the mixture subjected to plastic deformation after stretching into a mixing roll, melting and mixing again, and the mixing maximum temperature is 80 ℃;
(3) repeating the step (2) for 8 times to finally obtain a thin-layer graphene/polyvinyl alcohol mixture;
(4) and repeatedly soaking and filtering the obtained thin-layer graphene/polyvinyl alcohol mixture for 10 times by using deionized water at 97 ℃, and drying to obtain the graphene material. Through optical microscope detection, 90% of the obtained graphene material is thin-layer graphene with the layer number less than 10.
Claims (10)
1. A method for preparing a graphene material is characterized by comprising the following steps:
(1) carrying out melt blending on a graphite material and a high molecular polymer to obtain a blend;
(2) cooling and molding the blend to obtain a molded composite material;
(3) stretching the molded composite material by utilizing stretching equipment to obtain a deformed composite material;
(4) melting the deformed composite material, stirring, cooling and molding;
(5) repeating the step (3) and the step (4) for N times, wherein N is more than or equal to 1, and obtaining a compound;
(6) treating the compound with a solvent to obtain the graphene material; the solvent is compatible with the high molecular polymer.
2. The method of claim 1, wherein the graphite material is one of natural flake graphite, colloidal graphite, thermal cracked graphite, expanded graphite, multi-layered graphene oxide, multi-layered reduced graphene oxide.
3. The method of claim 1, wherein the average number of layers of graphite material is greater than 10.
4. The method according to claim 1, 2 or 3, characterized in that the mass ratio of the graphite material to the high molecular polymer is 1:3 to 1: 200.
5. The method according to claim 1, wherein the high molecular polymer is one or a blend of at least two of polyethylene, polypropylene, polybutadiene, polyisoprene, polyvinyl chloride, polystyrene, a block copolymer of styrene and butadiene, a hydride of a block copolymer of styrene and butadiene, starch, polyethylene glycol, cellulose, polymaleic anhydride, polyacrylamide, polyvinylpyrrolidone, epoxy resin, polyethylene oxide, polyurea, polycarbonate, polyaniline, polylactic acid, polyurethane, polyacrylic acid, polymethyl acrylate, polymethyl methacrylate, polyvinyl alcohol, polyethylene terephthalate, polypropylene terephthalate, polyethylene furan dicarboxylate, sucrose, maltose, and polypyrrole;
the number average molecular weight of the high molecular polymer is preferably 300 to 20 ten thousand.
6. The method according to claim 1, wherein the solvent in step (6) is at least one of water, benzene, toluene, xylene, trimethylbenzene, ethylbenzene, dichloromethane, dichloroethane, chloroform, acetone, ethanol, carbon tetrachloride, tetrachloroethylene, dioxane, pyridine, acetonitrile, diethyl ether, butyl acetate, ethyl acetate, propyl acetate, tributyl phosphate, trioctyl phosphate, propylene oxide, n-pentane, n-hexane, n-octane, cyclohexane, methyl butanone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, methanol, and isopropanol.
7. The method of claim 1,
the melting temperature of the step (1) and the melting temperature of the step (4) are 30-300 ℃;
the cooling temperature in the step (2) is-20 ℃ to 100 ℃;
in the step (3), the stretching temperature is-20 ℃ to 100 ℃; the tensile strength is 2-200 Mpa, and the tensile rate is 10-1000%;
in the step (6), the temperature condition of the solvent treatment compound is-20 ℃ to 150 ℃.
8. Graphene material obtainable by a process according to any one of claims 1 to 7.
9. The graphene material according to claim 8, wherein the number of layers of graphene in the graphene material is less than 10, preferably less than 3.
10. The graphene material of claim 9, wherein the graphene material has a mass content of graphene greater than 80%.
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