CN101817516A - Method for preparing graphene or graphene oxide by using high-efficiency and low-cost mechanical stripping - Google Patents

Abstract

A method for preparing graphene or graphene oxide by mechanical exfoliation with high efficiency and low cost, which relates to a preparation method for graphene or graphene oxide. The invention solves the problems of low efficiency and incapable mass production of the existing micromechanical stripping method. In the present invention, solid particles and liquid working medium (or gas working medium) are separated by mechanical stripping of carbon material; graphene or graphene oxide is obtained; the carbon material is graphite powder, expanded graphite, expandable graphite or graphite oxide pink. The invention uses an automatic machine and a large number of tiny solid particles to assist the peeling process, which greatly increases the contact area and the number of peelings in the peeling process. Through the shearing and impact of solid particles on the carbon material, the carbon material can A large number of exfoliation processes are performed within, thereby significantly improving the exfoliation efficiency, and the cost is low. This method is suitable for industrial mass production of graphene or graphene oxide.

Description

Method for preparing graphene or graphene oxide by mechanical exfoliation with high efficiency and low cost

technical field

The invention relates to a preparation method of graphene or graphene oxide.

Background technique

Graphene is the thinnest two-dimensional material known so far. Single-layer graphene has an ideal two-dimensional crystal structure consisting of hexagonal lattices. Since it was successfully prepared, graphene has caused a new wave of research all over the world. Graphene has many peculiar characteristics, with excellent electrical, optical, thermal and mechanical properties, and is likely to cause revolutionary changes in many fields. The ideal single-layer graphene has a large specific surface area (2630m ² /g), which is a potential energy storage material. Graphene is a semiconductor without an energy gap. It has a much higher carrier mobility (2×10 ⁵ cm ² /(Vs)) than silicon, a micron-scale mean free path and a large coherent length, so graphene is an ideal material for nanometer circuits; graphene has good electrical conductivity, and its electrons move at a speed of 1/300 of the speed of light, far exceeding the speed of electrons in general conductors. At the same time, graphene has With good light transmission, it is a potential substitute for traditional ITO film. Graphene has good thermal properties, with a thermal conductivity of 3080-5150W/mK. Graphene is the material with the highest strength known so far, and its ideal strength is 110-130GPa, which is an ideal reinforcement for various composite materials.

In 2004, Andre K. Geim (AndreK.Geim) of the University of Manchester (Science, 2004, 306:666) used a very simple method - Micromechanical cleavage (Micromechanical cleavage), in high The oriented pyrolytic graphite was repeatedly peeled off with scotch tape to obtain single-layer graphene. In recent years, people have made positive progress in the preparation of graphene. In addition to the micromechanical exfoliation method, the thermal expansion method and reduction method of graphite oxide, crystal epitaxial growth, chemical vapor deposition and organic synthesis have been developed. Preparation. Although the thermal expansion method and reduction method of graphite oxide can prepare a large amount of graphene at a relatively low cost, the electronic structure and crystal integrity of graphene are damaged by strong oxidants, which affects its electronic properties. Crystal epitaxial growth and chemical vapor deposition can prepare large-area continuous graphene thin film semiconductor materials with excellent performance, and are compatible with existing semiconductor processing technologies, making graphene materials prepared by this method have great applications in the field of microelectronics potential, but these methods are still immature at this stage, and for one of the most potential development directions of graphene - the field of composite materials, generally used graphene does not require a large area, but requires a large output , methods such as crystal epitaxial growth and chemical vapor deposition are difficult to meet the demand in this respect.

Graphene oxide is a layered covalent compound obtained by fully exfoliating graphite oxide through physical or chemical methods. _{Graphite is converted into} graphite _{oxide (} GraphiteOxide, GO). In recent years, graphene/polymer conductive nanomaterials and unsupported graphite oxide paper have been developed successively by oxidation method, and related research is very active. At present, the preparation technology of graphite oxide is relatively mature. If graphene oxide is to be prepared from graphite oxide, it is necessary to overcome the constraints of interlayer van der Waals force, and a certain external force must be applied. Many preparation methods have been developed for this purpose, such as pyrolytic expansion, ultrasonic, electrostatic Repulsion, machinery, low temperature, etc., but the work of preparing graphene oxide from graphite oxide is still not perfect. To realize the large-scale and controllable preparation of single-layer graphene oxide, new ideas and ways need to be continuously explored.

Among several graphene preparation methods, the micromechanical exfoliation method directly uses graphite to make graphene in one step, without using large precision equipment, the preparation process is the simplest, and has obvious cost advantages; it does not undergo chemical oxidation and reduction processes, and does not experience high temperatures In the expansion process, graphene has few defects and good quality; no consumption of chemical reagents, it is a green and environmentally friendly method. However, the micromechanical exfoliation method is generally considered impossible to meet the requirements of future industrialization due to its extremely low efficiency.

Contents of the invention

The object of the present invention is to solve the problem that the existing micromechanical exfoliation method has low efficiency and cannot be mass-produced; and provides a method for preparing graphene or graphene oxide by mechanical exfoliation with high efficiency and low cost.

Option 1: The method for preparing graphene or graphene oxide by high-efficiency and low-cost mechanical exfoliation is carried out according to the following steps: carbon material powder with a particle size of 0.05-1000 μm, solid particles with a particle size of 1 nm-100 μm and liquid Mechanical stripping is carried out after the working medium is mixed. The liquid working medium has a surface tension of 10~73mN/m and a viscosity of 1~1×10 ⁹ mPa·s at the working temperature of mechanical stripping. The stripping time is more than 5 minutes, and then the solid particles are removed. and liquid working medium; promptly obtain graphene or graphene oxide; Wherein, described carbon material powder is graphite powder, expanded graphite, expandable graphite or graphite oxide powder, adds dispersant in mechanical exfoliation process, and dispersant consumption is 0~20% of liquid working medium.

Scheme 2: The method for preparing graphene or graphene oxide by high-efficiency and low-cost mechanical exfoliation is carried out according to the following steps: in the jet mill, use a gas working medium and solid particles with a particle size of 1nm~100μm to crush the carbon material The powder is subjected to mechanical peeling, the peeling time is more than 5 minutes, and then the solid particles are removed; that is, graphene or graphene oxide is obtained, and the carbon material powder is graphite powder, expanded graphite, expandable graphite or graphite oxide powder.

The solid particles described in the above two schemes are magnesium, aluminum, iron, cobalt, nickel, copper, zinc, silver, tin, vanadium, chromium, tungsten, copper alloy, aluminum alloy, zinc alloy, iron-carbon alloy, magnesium alloy , lithium alloy, boron oxide, silicon oxide, zirconia, aluminum oxide, calcium carbonate, magnesium oxide, titanium dioxide, iodine, zinc oxide, tin oxide, ferric oxide, ferric oxide, aluminum nitride, aluminum chloride, Titanium nitride, silicon carbide, sodium fluoride, ammonium fluoride, calcium oxide, ammonium bicarbonate, ammonium bromide, ammonium chromate, ammonium dihydrogen phosphate, ammonium formate, ammonium acetate, sodium bicarbonate, ammonium monohydrogen phosphate, Ammonium iodide, ammonium nitrate, ammonium oxalate, ammonium sulfate, ammonium sulfite, ammonium tartrate, ammonium thiocyanate, ammonium acetate, barium iodide, barium nitrate, calcium bromide, calcium iodide, calcium nitrate, calcium nitrite, Potassium acetate, potassium bromate, potassium bromide, potassium carbonate, potassium chlorate, potassium chloride, potassium chromate, potassium dichromate, potassium dihydrogen phosphate, potassium ferricyanide, potassium ferrocyanide, potassium fluoride, potassium formate, Potassium bisulfate, potassium hydroxide, potassium iodide, potassium nitrate, potassium oxalate, potassium sulfate, potassium thiosulfate, lithium acetate, lithium bromide, sodium chloride, lithium chloride, lithium formate, lithium iodide, aluminum nitrate, aluminum sulfate, Magnesium acetate, magnesium bromide, magnesium iodide, magnesium sulfate, sodium acetate, sodium carbonate, sodium dihydrogen phosphate, sodium formate, sodium acetate, sodium nitrate, sodium phosphate, sodium sulfate, nickel chloride, nickel nitrate, ferrous chloride , one of ferrous sulfate, ferric chloride, copper chloride, copper nitrate, copper sulfate, zinc sulfate, sucrose, urea, polymer microspheres, glass powder or a mixture of several of them.

The above method of the present invention utilizes automatic machinery to mechanically peel off the carbon material powder in a system composed of carbon material powder (graphite powder, graphite oxide powder, expanded graphite or non-expanded graphite), solid particles and working medium, to obtain graphene and The compound of the working medium and solid particles, and then use means such as filtration, distillation, vacuum distillation, pickling, water washing, centrifugation, electric field (such as using electrostatic separator, etc.), magnetic field (such as using high gradient magnetic separator, etc.) Or special fractionation and separation equipment (such as linear vibrating screen classification equipment, airflow classifier, three-legged centrifuge-SS450, multi-stage classifier, etc.) to obtain graphene (graphene oxide) from the above compound. The invention uses automatic machinery to replace the manual peeling process, thereby improving the peeling efficiency; using a large number of tiny solid particles to assist the peeling process, greatly increasing the contact area and peeling times of the peeling process, through the shearing and impact of solid particles on graphite, Make graphite undergo a large number of exfoliation processes in a short time, thereby significantly improving the exfoliation efficiency; liquid or gas working medium plays an important role in exfoliation, on the one hand, the working medium can transmit the force required for exfoliation to solid particles and graphite powder, on the other hand , the working medium has a certain dispersion effect on graphene and solid particles, which hinders the recombination between graphene. In addition, the working medium can absorb and conduct the heat generated during the mechanical stripping process, and avoid overheating to cause defects in graphene. Due to the small mass of solid particles, the energy during motion is low, and graphene is the strongest substance in the world (bond energy up to 345kJ/mo1), and it is combined with weak van der Waals force between layers (bond energy 16.7kJ /mol), so it can be realized that the tiny solid particles do not damage the graphene during the collision with graphite, but only open the van der Waals bond between the layers, so as to finally obtain single-layer and thin-layer graphene or graphene oxide. The number of layers is adjustable, and the number of layers of graphene (or graphene oxide) can be controlled by adjusting the peeling time, and single-layer or thin-layer (2~10 layers) graphene (or graphene oxide) can be obtained to produce graphene and oxide The yield of graphene is more than 90%; the product yield is high, the utilization rate of raw materials is improved, and the production efficiency is high, thereby reducing the production cost. The method of the invention is suitable for industrialized mass production of graphene and graphene oxide.

Detailed ways

Specific Embodiment 1: In this embodiment, the method for preparing graphene or graphene oxide by high-efficiency and low-cost mechanical exfoliation is carried out according to the following steps: carbon material powder with a particle size of 0.05-1000 μm and a particle size of 1 nm-100 μm The solid particles are mixed with the liquid working medium for mechanical peeling. The liquid working medium has a surface tension of 10~73mN/m and a viscosity of 1~1×10 ⁹ mPa·s at the working temperature of mechanical peeling, and the peeling time is more than 5 minutes. , and then remove solid particles and liquid working medium; that is, to obtain graphene or graphene oxide; wherein, the carbon material powder is graphite powder, expanded graphite, expandable graphite or graphite oxide powder, and a dispersant is added during mechanical exfoliation , the amount of dispersant is 0~20% of the liquid working medium.

The working temperature described in this embodiment should not only meet the equipment requirements, but also ensure that the liquid working medium is in a liquid state during the mechanical stripping process. The dispersant used in this embodiment can be selected from polyetherimide (PEI), cetyltrimethylammonium bromide (CTAB), polyacrylic acid (PAA), sodium dodecyl sulfate (SDS), Sodium dialkyl sulfonate (SDBS), commercial dispersants, etc. Commercial dispersants can choose Disperbyk-163 wetting and dispersing agent, Disperbyk-2150 wetting and dispersing agent, super dispersant Tilo-3000, super dispersant Tilo-5110, Super dispersant Tilo-27000 etc.

The method of this embodiment utilizes an automatic machine to mechanically exfoliate the carbon material powder in a system composed of carbon material powder (graphite powder, graphite oxide powder, expanded graphite or non-expanded graphite), solid particles and a working medium to obtain graphene Composite powder with solid particles, and then use filtration, distillation, vacuum distillation, pickling, water washing, centrifugation, electric field (such as using electrostatic separator, etc.), magnetic field (such as using high gradient magnetic separator, etc.) or other means Specialized fractionation and separation equipment (such as linear vibrating screen classification equipment, airflow classifier, three-legged centrifuge-SS450, multi-stage classifier, etc.) obtains graphene (graphene oxide) from the above compound. This embodiment uses automatic machinery to replace the manual peeling process, thereby improving the peeling efficiency; using a large number of tiny solid particles to assist the peeling process, greatly increasing the contact area and peeling times of the peeling process, through the shearing and impact of solid particles on graphite , so that graphite undergoes a large number of exfoliation processes in a short time, thereby significantly improving the exfoliation efficiency; liquid or gas working medium plays an important role in exfoliation, on the one hand, the working medium can transmit the force required for exfoliation to solid particles and graphite powder, and on the other hand On the one hand, the working medium has a certain dispersion effect on graphene and solid particles, which hinders the recombination between graphene. In addition, the working medium can absorb and conduct the heat generated during the mechanical exfoliation process, and avoid overheating to cause defects in graphene. Tiny solid particles do not cause serious damage to graphene during the collision with graphite, but only open the van der Waals force between layers to ensure that the exfoliation process is carried out between graphene layers, so that single-layer and thin-layer graphene or graphene oxide is finally obtained . The number of layers of graphene (or graphene oxide) can be controlled by adjusting the peeling time, and single-layer or thin-layer (2~10 layers) graphene (or graphene oxide) can be obtained, and the production of graphene (or graphene oxide) The yield is above 90%, and the thickness is in the range of 0.355-5nm; the yield of the product is high, the utilization rate of raw materials is improved, and the production efficiency is high, thereby reducing the production cost. The method of this embodiment is suitable for industrialized mass production of graphene and graphene oxide. The electrical conductivity of graphene obtained by the method of this embodiment is above 10 ³ S/cm, and the thermal conductivity is above 2000 W/mK.

Embodiment 2: This embodiment differs from Embodiment 1 in that: the weight ratio of the carbon material powder to solid particles is 1:0.1~10000, and the weight ratio of the carbon material powder to the liquid working medium is 1: 0.1~10000. Other steps and parameters are the same as in the first embodiment.

Embodiment 3: This embodiment is different from Embodiment 2 in that: the weight ratio of the carbon material powder to solid particles is 1:1-2000. Other steps and parameters are the same as in the second embodiment.

Embodiment 4: This embodiment is different from Embodiment 2 in that: the weight ratio of the carbon material powder to solid particles is 1:5-1000. Other steps and parameters are the same as in the second embodiment.

Embodiment 5: This embodiment is different from Embodiment 2 in that: the weight ratio of the carbon material powder to solid particles is 1:10-500. Other steps and parameters are the same as in the second embodiment.

Embodiment 6: This embodiment is different from Embodiment 2 in that: the weight ratio of the carbon material powder to solid particles is 1:100-200. Other steps and parameters are the same as in the second embodiment.

Embodiment 7: This embodiment differs from Embodiments 2 to 6 in that the weight ratio of the solid particles to the liquid working medium is 1:0.2~5000. Other steps and parameters are the same as those in the second to sixth specific embodiments.

Embodiment 8: This embodiment differs from Embodiments 2 to 5 in that the weight ratio of the solid particles to the liquid working medium is 1:100-2000. Other steps and parameters are the same as those in the second to sixth specific embodiments.

Embodiment 9: This embodiment is different from Embodiment 2 to Embodiment 5 in that: the weight ratio of the solid particles to the liquid working medium is 1:200~500. Other steps and parameters are the same as those in the second to sixth specific embodiments.

Embodiment 10: This embodiment is different from Embodiment 1 to Embodiment 9 in that: the solid particles are magnesium, aluminum, iron, cobalt, nickel, copper, zinc, silver, tin, vanadium, chromium, tungsten, Copper alloy, aluminum alloy, zinc alloy, iron-carbon alloy, magnesium alloy, lithium alloy, boron oxide, silicon oxide, zirconium oxide, aluminum oxide, calcium carbonate, magnesium oxide, titanium dioxide, iodine, zinc oxide, tin oxide, dioxide Iron, ferric oxide, aluminum nitride, aluminum chloride, titanium nitride, silicon carbide, sodium fluoride, ammonium fluoride, calcium oxide, ammonium bicarbonate, ammonium bromide, ammonium chromate, ammonium dihydrogen phosphate, Ammonium formate, ammonium acetate, sodium bicarbonate, ammonium monohydrogen phosphate, ammonium iodide, ammonium nitrate, ammonium oxalate, ammonium sulfate, ammonium sulfite, ammonium tartrate, ammonium thiocyanate, ammonium acetate, barium iodide, barium nitrate, Calcium bromide, calcium iodide, calcium nitrate, calcium nitrite, potassium acetate, potassium bromate, potassium bromide, potassium carbonate, potassium chlorate, potassium chloride, potassium chromate, potassium dichromate, potassium dihydrogen phosphate, ferricyanide Potassium, potassium ferrocyanide, potassium fluoride, potassium formate, potassium bisulfate, potassium hydroxide, potassium iodide, potassium nitrate, potassium oxalate, potassium sulfate, potassium thiosulfate, lithium acetate, lithium bromide, sodium chloride, chloride Lithium, lithium formate, lithium iodide, aluminum nitrate, aluminum sulfate, magnesium acetate, magnesium bromide, magnesium iodide, magnesium sulfate, sodium acetate, sodium carbonate, sodium dihydrogen phosphate, sodium formate, sodium acetate, sodium nitrate, sodium phosphate , sodium sulfate, nickel chloride, nickel nitrate, ferrous chloride, ferrous sulfate, ferric chloride, copper chloride, copper nitrate, copper sulfate, zinc sulfate, sucrose, urea, polymer microspheres, glass powder species or a mixture of them. Other steps and parameters are the same as one of the specific embodiments 1 to 9.

In this embodiment, when the solid particles are a mixture, various solid particles are mixed in any ratio. The above solid particles can be removed by the following methods according to their properties:

The first category: solid particles soluble in acid and alkali solutions, such as: Al, Cu, Zn, SnO, ZnO, B ₂ O ₃ , SiO ₂ , NaHCO ₃ , CaCO ₃ , CaO, etc., which can be washed by acid or alkali wash away;

The second category: substances whose solubility varies greatly with temperature at room temperature-high temperature (for example, 100°C), for example: ammonium bicarbonate, ammonium dihydrogen phosphate, ammonium oxalate, potassium dihydrogen phosphate, potassium chloride, potassium ferrocyanide, Potassium sulfate, sodium carbonate, sodium dihydrogen phosphate, sodium sulfate, sodium phosphate, sucrose, urea, work at low temperature and then heat up to dissolve and remove solid particles;

The third category: Substances with great differences in solubility in different solvents, for example: most ionic compounds (such as NaCl, K ₂ CO ₃ , KCl, AlCl ₃ ) are highly soluble in water but in ethanol, benzene, CCl ₄ and other organic compounds The solubility in the solvent is small, and it is removed by working in an organic working medium and then washing with water;

The fourth category: Substances that are easy to separate under the action of electric field and magnetic field, such as: Al ₂ O ₃ , CaCO ₃ , Fe ₂ O ₃ , Fe ₃ O ₄ , Fe, etc., can be removed by electric field and magnetic field, such as electrostatic classification filter equipment or removal of magnetic field separation equipment;

The fifth category: solid particles that are easily volatilized, sublimated, and decomposed when heated at high temperature, such as sucrose, I ₂ , urea, NH ₄ NO ₃ , NH ₄ HCO ₃ , CH ₃ COONH _{4 ,} etc., are removed by high temperature heating;

The sixth category: solid particles with large specific gravity, such as zirconia, vanadium, chromium, tungsten, etc., adopt classification and separation equipment (such as linear vibrating screen classification equipment, airflow classifier, three-legged centrifuge-SS450, multi-stage classifier (Shenzhen Kaibu Electronics Co., Ltd.) removed.

Embodiment 11: This embodiment is different from Embodiments 1 to 10 in that: the surface tension of the liquid working medium is 40-50 mN/m. Other steps and parameters are the same as those in Embodiments 1 to 11.

Embodiment 12: The difference between this embodiment and Embodiments 1 to 10 is that the surface tension of the liquid working medium is 45 mN/m. Other steps and parameters are the same as those in Embodiments 1 to 11.

Embodiment 13: This embodiment is different from Embodiments 1 to 12 in that: the viscosity of the liquid working medium is 100-500000 mPa·s. Other steps and parameters are the same as one of the specific embodiments 1 to 12.

Specific Embodiment 14: This embodiment differs from Specific Embodiments 1 to 12 in that: the viscosity of the liquid working medium is 1000-50000 mPa·s. Other steps and parameters are the same as one of the specific embodiments 1 to 12.

Embodiment 15: This embodiment is different from Embodiment 1 to Embodiment 12 in that: the viscosity of the liquid working medium is 5000 mPa·s. Other steps and parameters are the same as those in Embodiments 1 to 11-2.

Embodiment 16: This embodiment is different from Embodiment 1 to Embodiment 15 in that: the particle diameter of the solid particles is 5 nm to 100 nm. Other steps and parameters are the same as those in Embodiments 1 to 15.

Embodiment 17: This embodiment differs from Embodiment 16 in that: the particle size of the solid particles is 200 nm to 500 nm. Other steps and parameters are the same as those in Embodiments 1 to 16.

Embodiment 18: This embodiment differs from Embodiment 16 in that the particle size of the solid particles is 1 μm to 20 μm. Other steps and parameters are the same as those in Embodiment 16.

Specific Embodiment Nineteen: This Embodiment is different from Specific Embodiment Sixteen in that: the particle size of the solid particles is 50 μm to 80 μm. Other steps and parameters are the same as those in Embodiment 16.

Embodiment 20: The difference between this embodiment and Embodiment 1 to 19 is that a homogenizer, a colloid mill, a three-roll machine, a screw extruder, a ball mill, a disc mill, a sand mill, One or several of them are used in combination to carry out mechanical peeling among vibration mills and ultrasonic equipment. The liquid working medium is water, alcohols, aromatic compounds, ketones, amines, ionic liquids, alkanes, heterocyclic compounds, Carbon disulfide, carbon tetrachloride, gasoline, vegetable oil, diesel oil, wax, aqueous alcohol solution, alcohol solution of alkanes, alcohol solution of ketones, aqueous solution of amine or alkane solution of aromatic compounds. Other steps and parameters are the same as those in Embodiments 1 to 19.

Specific embodiment 21: The difference between this embodiment and specific embodiment 20 is that the alcohols are ethanol, n-propanol, n-butanol, ethylene glycol, propylene glycol, 1,2-butanediol, 1 , One or a mixture of 3-butanediol, 1,4-butanediol, glycerol and isopropanol. Other steps and parameters are the same as in Embodiment 20.

In this embodiment, when the alcohols are a mixture, various alcohols are mixed in any ratio.

Embodiment 22: This embodiment is different from Embodiment 20 in that: the aromatic compound is benzene, toluene, naphthalene or anthracene. Other steps and parameters are the same as in Embodiment 20.

Embodiment 23: This embodiment is different from Embodiment 20 in that: the ketones are acetone or N-methylpyrrolidone. Other steps and parameters are the same as in Embodiment 20.

Embodiment 24: This embodiment is different from Embodiment 20 in that: the amines are methylformamide, N,N-dimethylformamide or N,N-dimethylacetamide. Other steps and parameters are the same as in Embodiment 20.

Embodiment 25: This embodiment is different from Embodiment 20 in that: the ionic liquid is 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methyl Imidazolium hexafluorophosphate or 1-hydroxyethyl-3-methylhexafluorophosphate. Other steps and parameters are the same as in Embodiment 20.

Embodiment 26: This embodiment is different from Embodiment 20 in that: the alkanes are n-hexane, octane or decane. Other steps and parameters are the same as in Embodiment 20.

Embodiment 27: This embodiment is different from Embodiment 20 in that: the heterocyclic compound is furan or pyridine. Other steps and parameters are the same as in Embodiment 20.

Embodiment 28: This embodiment is different from Embodiment 20 in that: the alcohol in the aqueous solution of alcohol is methanol, ethanol, glycerol, butanediol or isopropanol. Other steps and parameters are the same as in Embodiment 20.

Embodiment 29: This embodiment is different from Embodiment 20 in that: the alkanes alcohol solution is octanol solution of n-hexane, decanol of n-hexane or decanol of octadecane. Other steps and parameters are the same as in Embodiment 20.

Embodiment 30: This embodiment is different from Embodiment 20 in that: the ketone alcohol solution is acetone butanediol solution or acetone ethanol solution. Other steps and parameters are the same as in Embodiment 20.

Embodiment 31: This embodiment is different from Embodiment 20 in that: the amine in the amine aqueous solution is N-methylformamide or N,N-dimethylformamide. Other steps and parameters are the same as in Embodiment 20.

Specific Embodiment 32: This embodiment is different from Specific Embodiment 20 in that: the alkane solution of the aromatic compound is benzene in n-hexane or toluene in n-hexane. Other steps and parameters are the same as in Embodiment 20.

Specific embodiment thirty-three: the difference between this embodiment and one of specific embodiments one to nineteen is that mechanical peeling is carried out by using an open mill, internal mixer, homogenizer, colloid mill, three-roll machine or screw extruder , the liquid working medium is a polymer compound. Other steps and parameters are the same as those in Embodiments 1 to 18.

Embodiment 34: The difference between this embodiment and Embodiment 33 is that the polymer compound polyacrylate, polyvinyl alcohol, polyethylene glycol, polyvinyl acetate, starch, polybutadiene, Polybutadiene, epoxy, coal tar or pitch. Other steps and parameters are the same as those in Embodiment 33.

Specific Embodiment Thirty-five: The method of high-efficiency and low-cost mechanical exfoliation of this embodiment to prepare graphene is completed through the following steps: 1 part of graphite powder, 4 parts of silicon oxide with a particle size of 7nm and 500 parts by weight percentage Mix 1,3-butanediol and place it in a homogenizer, then add polyacrylic acid, the amount of polyacrylic acid is 5% of the volume of 1,3-butanediol, and mechanically peel at a speed of 5000 rpm for 0.5~100 hours , filtered to obtain a mixture of graphene and SiO ₂ , adding HF with a concentration of 5% by mass to dissolve SiO ₂ , filtered, and washed with water; that is, graphene was obtained.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Thirty-six: The method for preparing graphene oxide by high-efficiency and low-cost mechanical exfoliation in this embodiment is accomplished through the following steps: 1 part of graphite oxide powder, 40 parts of CaCO ₃ and 200 parts of isopropanol in percentage by weight After mixing, put it in a vibrating grinder, then add cetyltrimethylammonium bromide, the amount of cetyltrimethylammonium bromide is 1% of the volume of isopropanol, mechanically peel for 0.5~100 hours, filter To obtain a mixture of graphene oxide and CaCO ₃ , add HCl with a mass percentage concentration of 10% to 30% to dissolve the CaCO ₃ , filter and wash with water; the graphene oxide is obtained.

The graphene oxide prepared by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355-5 nm, and the yield is over 90%.

Specific Embodiment Thirty-Seven: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is completed through the following steps: 1. Weigh 1 part of graphite powder, 80-200 parts of potassium dihydrogen phosphate and 1 part by weight percentage 100~400 parts of water, then dissolve potassium dihydrogen phosphate in water at 90°C and put in graphite powder, put the mixture in a sand mill, then add sodium dodecylsulfonate, dodecylsulfonate The amount of sodium acid is 1% of the water volume; 2. Cool the above mixture to 20-50°C within 0.1-10 hours and use a sand mill to peel off at a speed of 1000-10000 rpm; 3. Then heat up to 90°C , and then lower the temperature to 20~50°C within 0.1~10 hours and use a sand mill to peel at a speed of 1000~10000 rpm; 4. Repeat steps 2 and 3 for 0~20 times, and continue mechanical peeling for 0.1~ After 100 hours, a mixture of graphene-potassium dihydrogen phosphate-water was obtained, and the mixture was heated to 100°C (in order to dissolve potassium dihydrogen phosphate), filtered and washed to obtain graphene.

The whole process of the method described in this embodiment is pollution-free and is a green synthetic route.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific embodiment thirty-eight: the method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is completed through the following steps: 1. Weigh 1 part of graphite powder, 80~200 parts of sucrose and 100~ 400 parts of water, then dissolve sucrose in water at 90°C and put graphite powder into it to obtain the mixture in a sand mill, then add polyacrylic acid, the amount of polyacrylic acid is 2% of the water volume; Cool the above mixture to 25°C within 10 hours and use a sand mill to peel off at a speed of 1000~10000 rpm; 3. Then heat up to 90°C, then cool down to 25°C within 0.1~10 hours while using a sand mill Peel off at a speed of 1000~10000 rpm; 4. Repeat steps 2 and 3 for 0~20 times, continue mechanical peeling for 0.1~100 hours to obtain a mixture of graphene-sucrose-water, and heat the mixture to 100°C ( The purpose is to dissolve sucrose), filter and wash to obtain graphene.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2400W/mK, and the yield is above 90%. .

Specific Embodiment Thirty-Nine: In this embodiment, the method for preparing graphene by mechanical exfoliation with high efficiency and low cost is completed through the following steps: mix 1 part of graphite powder, 50-1000 parts of NaCl and 500-5000 parts of ethanol by weight percentage Put it in a homogenizer, then add polyacrylic acid, the amount of polyacrylic acid is 3% of the volume of ethanol, peel at a speed of 4000 rpm for 0.5~100 hours, then filter to obtain a mixture of graphene and NaCl, add 500~3000 Parts of water (for dissolving NaCl), filtered, and washed with water; that is, graphene was obtained.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Forty: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is completed through the following steps: 1 part of graphite powder, 50-1000 parts of KCl and 250-2500 parts of ethanol and 250 parts by weight percentage ~2500 parts of glycerol are mixed and placed in a homogenizer, then polyacrylic acid is added, the amount of polyacrylic acid is 0.5% of the volume of ethanol, stripped at a speed of 4000 rpm for 0.5~100 hours, and then filtered to obtain graphene and KCl The mixture, add 500~3000 parts of water (for dissolving KCl), filter, wash with water; obtain graphene.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Forty-one: In this embodiment, the method for preparing graphene by mechanical exfoliation with high efficiency and low cost is accomplished through the following steps: 1 part of graphite powder, 150 parts of Al ₂ O ₃ with a diameter of about 200 nm and 100 parts by weight percentage Parts of isopropanol are mixed and placed in a vibrating grinder, and then cetyltrimethylammonium bromide (CTAB) is added. The amount of cetyltrimethylammonium bromide is 2% of the volume of isopropanol. After 0.5 to 100 hours, filter to obtain a mixture of graphene and Al ₂ O ₃ , and remove Al ₂ O ₃ with an electrostatic classification filter device; that is, graphene is obtained.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment 42: In this embodiment, the method for preparing graphene by mechanical exfoliation with high efficiency and low cost is accomplished through the following steps: 1 part of graphite powder, 100 parts of iron powder with a diameter of about 1 μm and 200 parts of iso After mixing the propanol, place it in a vibrating grinder, then add Disperbyk-163, the amount of Disperbyk-163 is 15% of the volume of isopropanol, peel off for 0.5-100 hours, filter to obtain a mixture of graphene and iron powder, wash with water, and use a magnetic field Separation equipment removes iron powder; that is, graphene is obtained.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Forty-Three: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is completed through the following steps: 1. Weigh 1 part of graphite powder, 50-2000 parts of urea and 100-2000 parts by weight percentage Parts of ethanol, then put urea into ethanol at 65°C and then add graphite powder, put the mixture in a homogenizer, then add polyacrylic acid (PAA), the amount of polyacrylic acid is 2.5% of the volume of ethanol; Cool the above mixture to 20°C within 0.1~10 hours and use a homogenizer to peel off at a speed of 1000~10000 rpm; 3. Then heat up to 60°C, then cool down to 30°C within 0.1~10 hours while using sand The mill peels off at a speed of 1000~10000 rpm; 4. Repeat steps 2 and 3 for 0~9 times, and continue mechanical peeling for 0.1~100 hours to obtain a mixture of graphene-urea-ethanol. Filtrate at 55°C to obtain a mixture of graphene-urea, and heat at an environment above 200°C to rapidly decompose residual urea to obtain well-dispersed graphene.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Forty-Four: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is completed through the following steps: 1. Weigh 1 part of graphite powder, 200~2000 parts of ammonium formate and 100~ 1000 parts of water, dissolve ammonium formate in water at 65°C, put graphite powder into it, put the mixture in a homogenizer, then add cetyltrimethylammonium bromide (CTAB), cetyl The amount of trimethylammonium bromide is 2% of the water volume; 2. Cool the above mixture to 20°C within 0.1~10 hours and use a homogenizer to peel off at a speed of 1000~10000 rpm; 3. Then heat up to 60°C, then cool down to 20~50°C within 0.1~10 hours and use a sand mill to peel at a speed of 1000~10000 rpm; 4. Repeat steps 2 and 3 for 0~9 times, and continue mechanical peeling After 0.1~100 hours, a mixture of graphene-ammonium formate-water is obtained, and filtered at 35°C~55°C to obtain a mixture of graphene-ammonium formate, heated at an environment above 200°C to rapidly decompose ammonium formate, and obtain well-dispersed graphite alkene.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 92%. .

Forty-five specific embodiments: the method for preparing graphene with high efficiency and low cost mechanical exfoliation in this embodiment is completed through the following steps: 1 part of graphite powder, 200 parts of copper powder with a diameter of about 100 nm and 150 parts of iso Propanol is mixed and placed in a vibrating grinder, and then cetyltrimethylammonium bromide (CTAB) is added. The amount of cetyltrimethylammonium bromide is 2% of the volume of acetone, and the stripping is 0.5 to 100 hours , filter to obtain a mixture of graphene and copper powder, wash with water, and remove copper powder with an air classifier; that is, obtain graphene.

The method of this embodiment makes graphene with single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and its yield is in More than 90.

Specific Embodiment Forty-six: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is accomplished through the following steps: 1 part of graphite powder, 200 parts of zirconia powder with a diameter of about 200 nm and 500 parts of 1,4-butanediol is mixed and placed in a vibrating mill, then polyacrylic acid (PAA) is added, the amount of polyacrylic acid is 2% of the volume of 1,4-butanediol, stripped for 0.5-100 hours, and filtered to obtain graphene and the mixture of zirconia powder, washing with water, and removing the zirconia powder with a centrifuge; that is, graphene is obtained.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment 47: In this embodiment, the high-efficiency and low-cost mechanical exfoliation method for preparing graphene oxide is completed through the following steps: 1 part of graphite oxide powder, 4 parts of silicon oxide with a particle size of 7 nm and 1 part by weight percentage 200 parts of 1,3-butanediol are mixed and placed in a homogenizer, then polyacrylic acid (PAA) is added, the amount of polyacrylic acid is 2% of the volume of 1,3-butanediol, peeled at a speed of 4000 rpm After 0.5 to 100 hours, filter to obtain a mixture of graphene oxide and SiO ₂ , add 5% HF to dissolve SiO ₂ , and filter and separate to obtain graphene oxide.

The graphene oxide prepared by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355-5 nm, and the yield is over 90%.

Specific Embodiment Forty-Eight: The method for preparing graphene oxide by high-efficiency and low-cost mechanical exfoliation in this embodiment is completed through the following steps: 1 part of graphite oxide powder, 50-1000 parts of NaCl and 500-5000 parts of eighteen The mixture of alkanes and decanol (volume ratio 1:10) is mixed and placed in a homogenizer, and then cetyltrimethylammonium bromide (CTAB) is added, the dosage of cetyltrimethylammonium bromide It is 0.5~3% of the volume of the mixture of octadecane and decanol, stripped at a speed of 4000 rpm for 0.5~100 hours, and then filtered to obtain a mixture of graphene oxide and NaCl, adding 500~3000 parts of water to dissolve NaCl, and filtering, Wash with water; obtain graphene oxide.

The graphene oxide prepared by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355-5 nm, and the yield is over 90%.

Specific Embodiment Forty-nine: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is carried out according to the following steps: 1 part of graphite powder, 4 to 10 parts of silicon oxide with a particle size of 7 nm and 1 part by weight percentage 200 parts of polymethyl acrylate are mixed and placed in a three-roller, and then cetyltrimethylammonium bromide (CTAB) is added, and the amount of cetyltrimethylammonium bromide is 10% of the volume of polymethylacrylate %~20%, mechanical peeling for 4~100 hours, dissolve polymethylacrylate with butyl acetate, filter, dissolve SiO ₂ with 5% HF, and obtain graphene after filtration.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~10nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Fifty: The method for preparing graphene oxide by high-efficiency and low-cost mechanical exfoliation in this embodiment is carried out according to the following steps: 1 part of graphite oxide powder, 5-50 parts of sodium chloride and 200 parts of polyacrylic acid After the methyl ester is mixed, it is placed in a three-roller machine, and then cetyltrimethylammonium bromide (CTAB) is added. The amount of cetyltrimethylammonium bromide is 10%~20% of the volume of polymethylacrylate , mechanical peeling for 4 to 50 hours, dissolving polymethyl acrylate with butyl acetate, filtering, dissolving sodium chloride in water, and obtaining graphene oxide after filtering. Wherein said liquid working medium is high molecular compound.

The graphene oxide prepared by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355-10 nm, and the yield is over 90%.

Specific Embodiment Fifty-one: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is carried out according to the following steps: 1 part of expanded graphite powder, 5-50 parts of sodium chloride and 200 parts of polyacrylic acid After the methyl ester is mixed, it is placed in a three-roller machine, and then cetyltrimethylammonium bromide (CTAB) is added. The amount of cetyltrimethylammonium bromide is 10%~20% of the volume of polymethylacrylate , mechanical peeling for 4-50 hours, dissolving polymethylacrylate with butyl acetate, filtering, dissolving sodium chloride with 50-500 parts of water, and obtaining graphene after filtering.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~10nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Fifty-two: The method for preparing graphene by high-efficiency and low-cost mechanical exfoliation in this embodiment is carried out according to the following steps: 1 part of expandable graphite powder, 5-20 parts of sodium chloride and 300 parts of Polymethyl acrylate is mixed and placed in a three-roller, and then cetyltrimethylammonium bromide (CTAB) is added. The amount of cetyltrimethylammonium bromide is 1% of the volume of polymethylacrylate~ 2%, mechanical peeling for 2-25 hours, dissolve polymethylacrylate with butyl acetate, filter, dissolve sodium chloride with 50-500 parts of water, and obtain graphene after filtration.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~10nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Fifty-Three: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is carried out according to the following steps: 1 part of graphite powder, 5~20 parts of sodium chloride, 2~20 parts of Copper powder, 300 parts of ethylene glycol and 50 parts of acetone are mixed and placed in a homogenizer, and then polyacrylic acid (PAA) is added. The amount of polyacrylic acid is 0.1%~2% of the volume of acetone, mechanically stripped for 0.1~10h, filtered, and water Dissolve sodium chloride in 50-500 parts of water, filter, and then use an air classifier to remove copper powder to obtain graphene.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~10nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Fifty-Four: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is carried out according to the following steps: 1 part of graphite powder, 10~20 parts of calcium carbonate, 5~20 parts of oxidized Zirconium and 300 parts of 1,4-butanediol are mixed and placed in a homogenizer, and then polyacrylic acid (PAA) is added. The amount of polyacrylic acid is 2% of the volume of 1,4-butanediol, and the mechanical peeling is 0.1~10h. Filter, then use a centrifuge to remove zirconia, remove calcium carbonate with HCl with a mass concentration of 10% to 30%, and obtain graphene after filtering.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~10nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Fifty-five: The method of high-efficiency and low-cost mechanical exfoliation of this embodiment to prepare graphene is completed through the following steps: 1 part of graphite powder, 5 parts of silicon oxide with a particle size of 7nm and 300 parts by weight percentage 1,3-butanediol is mixed and placed in a homogenizer, mechanically peeled at a speed of 5000 rpm for 0.5-100 hours, filtered to obtain a mixture of graphene and _SiO2 , and dissolved by adding 5% HF concentration SiO ₂ , filtered and washed with water; that is, graphene is obtained.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Fifty-six: The method for preparing graphene oxide by high-efficiency and low-cost mechanical exfoliation in this embodiment is completed through the following steps: 1 part of graphite oxide powder, 40 parts of CaCO ₃ and 200 parts of isopropanol by weight percentage After mixing, put it in a vibrating grinder, mechanically peel it off for 0.5-100 hours, filter to obtain a mixture of graphene oxide and CaCO ₃ , add HCl with a concentration of 10%-30% by mass to dissolve CaCO ₃ , filter, and wash with water; Graphene.

The graphene oxide prepared by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355-5 nm, and the yield is over 90%.

Specific embodiment fifty-seven: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is completed through the following steps: 1. Weigh 1 part of graphite powder, 80-200 parts of potassium dihydrogen phosphate and 1 part by weight percentage 100~400 parts of water, then dissolve potassium dihydrogen phosphate in water at 90°C and put graphite powder into it, and place the mixture in a sand mill; 2. Cool the above mixture to 20~20°C within 0.1~10 hours At 50°C, use a sand mill to peel at a speed of 1000~10000 rpm; 3. Then heat up to 90°C, and then cool down to 20~50°C within 0.1~10 hours while using a sand mill to peel at a speed of 1000~10000 rpm. Peel off at a speed of 1 minute; 4. Repeat steps 2 and 3 for 0-20 times, and continue mechanical peeling for 0.1-100 hours to obtain a mixture of graphene-potassium dihydrogen phosphate-water, and heat the mixture to 100°C (the purpose is to dissolve Potassium dihydrogen phosphate), filtered and washed to obtain graphene.

The whole process of the method described in this embodiment is pollution-free and is a green synthetic route.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific embodiment fifty-eight: the method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is completed through the following steps: 1. Weigh 1 part of graphite powder, 80~200 parts of sucrose and 100~ 400 parts of water, then dissolve sucrose in water at 90°C and put in graphite powder to obtain the mixture and place it in a sand mill; 2. Cool the above mixture to 25°C within 0.1 to 10 hours while using a sand mill Peel off at a speed of 1000~10000 rpm; 3. Then heat up to 90°C, then cool down to 25°C within 0.1~10 hours and use a sand mill to peel off at a speed of 1000~10000 rpm; 4. Repeat the steps Step 2 and step 3 were performed 0-20 times, and mechanical peeling was continued for 0.1-100 hours to obtain a mixture of graphene-sucrose-water. The mixture was heated to 100°C (for the purpose of dissolving sucrose), filtered and washed to obtain graphene.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2400W/mK, and the yield is above 90%. .

Specific Embodiment Fifty-nine: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is completed through the following steps: mix 1 part of graphite powder, 50-1000 parts of NaCl and 200-4000 parts of ethanol by weight percentage Put it in a homogenizer, peel it off at a speed of 4000 rpm for 0.5-100 hours, then filter to obtain a mixture of graphene and NaCl, add 500-3000 parts of water (for dissolving NaCl), filter, and wash with water; Get graphene.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Sixty: The method for preparing graphene by high-efficiency and low-cost mechanical exfoliation in this embodiment is completed through the following steps: 1 part of graphite powder, 50-1000 parts of KCl and 50-1500 parts of ethanol and 50 parts by weight percentage ~1500 parts of glycerol is mixed and placed in a homogenizer, stripped at a speed of 4000 rpm for 0.5~100 hours, then filtered to obtain a mixture of graphene and KCl, adding 500~3000 parts of water (for dissolving KCl) , filtered, and washed with water; that is, graphene is obtained.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Sixty-one: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is accomplished through the following steps: 1 part of graphite powder, 150 parts of Al ₂ O ₃ with a diameter of about 500 nm and 200 parts by weight percentage After mixing with isopropanol, put it in a vibrating grinder, peel it off for 0.5-100 hours, filter to obtain a mixture of graphene and Al ₂ O ₃ , and remove Al ₂ O ₃ with an electrostatic classification filter device; that is, graphene is obtained.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific embodiment sixty-two: The method for preparing graphene with high efficiency and low cost mechanical exfoliation in this embodiment is completed through the following steps: 1 part of graphite powder, 100 parts of iron powder with a diameter of about 1 μm and 200 parts of iso After mixing propanol, put it in a vibrating grinder, peel it off for 0.5-100 hours, filter to obtain a mixture of graphene and iron powder, wash it with water, and use a magnetic field separation device to remove the iron powder; that is, graphene is obtained.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific embodiment sixty-three: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is completed through the following steps: 1. Weigh 1 part of graphite powder, 50-2000 parts of urea and 100-2000 parts by weight percentage Parts of ethanol, then put urea into ethanol at 65°C and then add graphite powder to obtain the mixture in a homogenizer; 2. Cool the above mixture to 20°C within 0.1 to 10 hours and use a homogenizer to Peel off at a speed of 1000~10000 rpm; 3. Then heat up to 60°C, then cool down to 30°C within 0.1~10 hours and use a sand mill to peel off at a speed of 1000~10000 rpm; 4. Repeat step 2 And step 3 operation 0~9 times, continue mechanical peeling for 0.1~100 hours to get a mixture of graphene-urea-ethanol, filter at 35°C~55°C to get a mixture of graphene-urea, heat in an environment above 200°C Rapidly decompose residual urea to obtain well-dispersed graphene.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific implementation mode sixty-four: the method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is completed through the following steps: 1. Weigh 1 part of graphite powder, 200~2000 parts of CH ₃ COONH ₄ and 100~1000 parts of ethanol, dissolve CH ₃ COONH ₄ in ethanol at 65°C and put in graphite powder, the obtained mixture is placed in a homogenizer; 2. Cool the above mixture to 20°C within 0.1~10 hours At the same time, use a homogenizer to peel at a speed of 1000~10000 rpm; 3. Then heat up to 60°C, and then cool down to 20~50°C within 0.1~10 hours. Speed peeling; 4. Repeat steps 2 and 3 for 0-9 times, continue mechanical peeling for 0.1-100 hours to obtain a mixture of graphene-CH ₃ COONH ₄ -ethanol, filter at 35°C~55°C to obtain graphene - A mixture of CH ₃ COONH ₄ , heated above 200°C to rapidly decompose CH ₃ COONH ₄ to obtain well-dispersed graphene.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 92%. .

The sixty-fifth specific embodiment: the method for preparing graphene with high efficiency and low cost mechanical exfoliation in this embodiment is completed through the following steps: 1 part of graphite powder, 200 parts of copper powder with a diameter of about 100 nm and 150 parts of iso After mixing propanol, place it in a vibrating grinder, peel it off for 0.5-100 hours, filter to obtain a mixture of graphene and copper powder, wash it with water, and remove the copper powder with an air classifier; that is, graphene is obtained.

The method of this embodiment makes graphene with single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and its yield is in More than 90.

Specific Embodiment Sixty-six: The method for preparing graphene by high-efficiency and low-cost mechanical exfoliation in this embodiment is accomplished through the following steps: 1 part of graphite powder, 200 parts of zirconia powder with a diameter of about 200 nm and 500 parts by weight percentage 1,4-Butanediol is mixed and placed in a homogenizer, peeled at a speed of 5000 rpm for 0.5 to 100 hours, filtered to obtain a mixture of graphene and zirconia powder, washed with water, and removed by a centrifuge; ie Get graphene.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific embodiment sixty-seven: The method for preparing graphene oxide by high-efficiency and low-cost mechanical exfoliation in this embodiment is completed through the following steps: 1 part of graphite oxide powder, 4 parts of silicon oxide with a particle size of 7 nm and 1 part by weight percentage 200 parts of 1,3-butanediol are mixed and placed in a homogenizer, stripped at a speed of 4000 rpm for 0.5 to 100 hours, filtered to obtain a mixture of graphene oxide and SiO ₂ , and 5% HF is added to dissolve SiO ₂ , Filtration and separation; that is, graphene oxide is obtained.

The graphene oxide prepared by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355-5 nm, and the yield is over 90%.

Specific embodiment sixty-eight: The method for preparing graphene oxide by high-efficiency and low-cost mechanical exfoliation in this embodiment is completed through the following steps: 1 part of graphite oxide powder, 50-1000 parts of NaCl and 500-5000 parts of The mixture of octadecane and decanol (volume ratio 1:10) is mixed and placed in a homogenizer, stripped at a speed of 4000 rpm for 0.5 to 100 hours, and then filtered to obtain a mixture of graphene oxide and NaCl, adding Dissolve NaCl in 500-3000 parts of water, filter and wash with water; obtain graphene oxide.

The graphene oxide prepared by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355-5 nm, and the yield is over 90%.

Specific embodiment sixty-nine: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is carried out according to the following steps: 1 part of graphite powder, 5 to 10 parts of silicon oxide with a particle size of 7 nm and 1 part by weight percentage 200 parts of polymethyl acrylate were mixed and placed in a three-roll machine, mechanically peeled for 4-50 hours, dissolved in butyl acetate, filtered, and SiO ₂ was dissolved in 5% HF, and graphene was obtained after filtration.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~10nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Seventy: The method for preparing graphene oxide by high-efficiency and low-cost mechanical exfoliation in this embodiment is carried out according to the following steps: 1 part of graphite oxide powder, 5-50 parts of sodium chloride and 200 parts of polyacrylic acid After mixing the methyl esters, place them in a three-roll machine, mechanically peel them off for 4 to 100 hours, dissolve polymethyl acrylate with butyl acetate, filter, dissolve sodium chloride with water, and obtain graphene oxide after filtration. Wherein said liquid working medium is high molecular compound.

The graphene oxide prepared by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355-10 nm, and the yield is over 90%.

Specific Embodiment Seventy-one: The method for preparing graphene by high-efficiency and low-cost mechanical exfoliation in this embodiment is carried out according to the following steps: 1 part of expanded graphite powder, 5-50 parts of sodium chloride and 200 parts of polyacrylic acid After mixing the methyl esters, place them in a three-roll machine, mechanically peel them off for 4 to 100 hours, dissolve the polymethyl acrylate with butyl acetate, filter, dissolve sodium chloride with 50 to 500 parts of water, and obtain graphene after filtration.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~10nm, the electrical conductivity is above 10 ² S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Seventy-two: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is carried out according to the following steps: 1 part of expandable graphite powder, 5-20 parts of sodium chloride and 300 parts of The polymethyl acrylate is mixed and placed in a three-roll machine, mechanically peeled for 2 to 50 hours, the polymethyl acrylate is dissolved with butyl acetate, filtered, and 50 to 500 parts of water is used to dissolve sodium chloride, and graphene is obtained after filtration.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~10nm, the electrical conductivity is above 10 ² S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Seventy-three: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is carried out according to the following steps: 1 part of graphite powder, 5~20 parts of sodium chloride, 2~20 parts of Copper powder, 300 parts of ethylene glycol and 50 parts of acetone are mixed and placed in a homogenizer, mechanically stripped for 0.1~100 hours, filtered, dissolved in 50~500 parts of water with sodium chloride, filtered, and then the copper powder is removed with an airflow classifier Afterwards, graphene is obtained.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~10nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Seventy-Four: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is carried out according to the following steps: 1 part of graphite powder, 10~20 parts of calcium carbonate, 5~20 parts of oxidized Zirconium and 300 parts of 1,4-butanediol are mixed and placed in a homogenizer, mechanically stripped for 0.1~10h, filtered, and then the zirconia is removed by a centrifuge, and the carbonic acid is removed by HCl with a mass concentration of 10%~30% Calcium, after filtration, yields graphene.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~10nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Seventy-five: In this embodiment, the method for preparing graphene or graphene oxide by high-efficiency and low-cost mechanical exfoliation is carried out according to the following steps: in a jet mill, use a gas working medium and a particle size of 1 nm to 100 μm The solid particles of the carbon material powder are mechanically peeled off, and the peeling time is more than 5 minutes, and then the solid particles are removed; that is, graphene or graphene oxide is obtained, and the carbon material powder is graphite powder, expanded graphite, expandable graphite or Graphite oxide powder.

The method of this embodiment utilizes an automatic machine to mechanically exfoliate the carbon material powder in a system composed of carbon material powder (graphite powder, graphite oxide powder, expanded graphite or non-expanded graphite), solid particles and a working medium to obtain graphene Composite powder with solid particles, and then use filtration, distillation, vacuum distillation, pickling, water washing, centrifugation, electric field (such as using electrostatic separator, etc.), magnetic field (such as using high gradient magnetic separator, etc.) or other means Specialized fractionation and separation equipment (such as linear vibrating screen classification equipment, airflow classifier, three-legged centrifuge-SS450, multi-stage classifier, etc.) obtains graphene (graphene oxide) from the above compound. This embodiment uses automatic machinery to replace the manual peeling process, thereby improving the peeling efficiency; using a large number of tiny solid particles to assist the peeling process, greatly increasing the contact area and peeling times of the peeling process, through the shearing and impact of solid particles on graphite , so that graphite undergoes a large number of exfoliation processes in a short time, thereby significantly improving the exfoliation efficiency; liquid or gas working medium plays an important role in exfoliation, on the one hand, the working medium can transmit the force required for exfoliation to solid particles and graphite powder, and on the other hand On the one hand, the working medium has a certain dispersion effect on graphene and solid particles, which hinders the recombination between graphene. In addition, the working medium can absorb and conduct the heat generated during the mechanical exfoliation process, and avoid overheating to cause defects in graphene. Tiny solid particles do not cause serious damage to graphene during the collision with graphite, but only open the van der Waals force between layers to ensure that the exfoliation process is carried out between graphene layers, so that single-layer and thin-layer graphene or graphene oxide is finally obtained . The number of layers of graphene (or graphene oxide) can be controlled by adjusting the peeling time, and a single layer or thin layer (2~10 layers) of graphene (or graphene oxide) can be obtained to produce graphene (or graphene oxide). The yield is above 90%, and the thickness is in the range of 0.355-5nm; the yield of the product is high, the utilization rate of raw materials is improved, and the production efficiency is high, thereby reducing the production cost. The method of this embodiment is suitable for industrialized mass production of graphene and graphene oxide. The electrical conductivity of graphene obtained by the method of this embodiment is above 10 ³ S/cm, and the thermal conductivity is above 2000 W/mK.

Specific embodiment seventy-six: the difference between this embodiment and specific embodiment seventy-five is that the gas working medium is air, He, Ne, Ar, N ₂ , H ₂ , Cl ₂ , Br ₂ , CO, CO _2. One of CH ₄ , NH ₃ , water vapor, and benzene vapor or a mixture of several of them. Other steps and parameters are the same as those in Embodiment 75.

The gas working medium in this embodiment is a mixed gas, and various gas working mediums are mixed in any ratio.

Specific embodiment No. 77: This embodiment is different from specific embodiments No. 75 or No. 76 in that: the particle size of the solid particles is 5 nm to 100 nm. Other steps and parameters are the same as those in Embodiment 75 or 76.

Specific Embodiment No. 78: The difference between this embodiment mode and specific embodiment mode and specific embodiment mode No. 77 is that the particle size of the solid particles is 200nm~500nm. Other steps and parameters are the same as those in Embodiment 77.

Specific Embodiment 79: The difference between this embodiment and specific embodiment 77 is that the particle size of the solid particles is 1 μm to 20 μm. Other steps and parameters are the same as those in Embodiment 77.

Embodiment 80: This embodiment differs from Embodiment 77 in that the particle size of the solid particles is 50 μm to 80 μm. Other steps and parameters are the same as those in Embodiment 77.

Specific Embodiment No. 81: This embodiment differs from Specific Embodiment No. 75 to No. 80 in that: the weight ratio of the carbon material powder to solid particles is 1:0.1~10000. Other steps and parameters are the same as in one of the seventy-fifth to eighty specific embodiments.

Specific embodiment eighty-two: this embodiment is different from specific embodiment eighty-one in that: the weight ratio of the carbon material powder to solid particles is 1:10-100. Other steps and parameters are the same as those in Embodiment 81.

Embodiment 83: This embodiment differs from Embodiment 81 in that: the weight ratio of the carbon material powder to solid particles is 1:200-500. Other steps and parameters are the same as those in Embodiment 81.

Specific embodiment eighty-four: this embodiment is different from specific embodiment eighty-one in that: the weight ratio of the carbon material powder to solid particles is 1:200-800. Other steps and parameters are the same as those in Embodiment 81.

Specific embodiment eighty-five: this embodiment is different from one of the seventy-five to eighty-four specific embodiments in that: the solid particles are magnesium, aluminum, iron, cobalt, nickel, copper, zinc, silver, tin , vanadium, chromium, tungsten, copper alloy, aluminum alloy, zinc alloy, iron-carbon alloy, magnesium alloy, lithium alloy, boron oxide, silicon oxide, zirconia, aluminum oxide, calcium carbonate, magnesium oxide, titanium dioxide, iodine, zinc oxide , tin oxide, ferric oxide, ferric oxide, aluminum nitride, aluminum chloride, titanium nitride, silicon carbide, sodium fluoride, ammonium fluoride, calcium oxide, ammonium bromide, ammonium chromate, bicarbonate Sodium, ammonium iodide, ammonium sulfate, ammonium sulfite, ammonium tartrate, ammonium thiocyanate, barium iodide, barium nitrate, calcium bromide, calcium iodide, calcium nitrate, calcium nitrite, potassium acetate, potassium bromate, bromide Potassium, potassium carbonate, potassium chloride, potassium chromate, potassium dichromate, potassium dihydrogen phosphate, potassium ferricyanide, potassium ferrocyanide, potassium fluoride, potassium formate, potassium hydrogen sulfate, potassium hydroxide, potassium iodide , potassium sulfate, potassium thiosulfate, lithium acetate, lithium bromide, sodium chloride, lithium chloride, lithium formate, lithium iodide, aluminum sulfate, magnesium acetate, magnesium bromide, magnesium iodide, magnesium sulfate, sodium acetate, carbonic acid Sodium, sodium dihydrogen phosphate, sodium formate, sodium acetate, sodium phosphate, sodium sulfate, nickel chloride, nickel nitrate, ferrous chloride, ferrous sulfate, ferric chloride, copper chloride, copper nitrate, copper sulfate, zinc sulfate , sucrose, urea, polymer microspheres, glass powder or a mixture of several of them. Other steps and parameters are the same as those in one of the seventy-fifth to eighty-fourth specific embodiments.

In this embodiment, when the solid particles are a mixture, various solid particles are mixed in any ratio. The above solid particles can be removed by the following methods according to their properties:

The first category: solid particles soluble in acid and alkali solutions, such as: Al, Cu, Zn, SnO, ZnO, B ₂ O ₃ , SiO ₂ , NaHCO ₃ , CaCO ₃ , CaO, etc., which can be washed by acid or alkali wash away;

The second category: substances whose solubility varies greatly with temperature at room temperature-high temperature (for example, 100°C), for example: ammonium bicarbonate, ammonium dihydrogen phosphate, ammonium oxalate, potassium dihydrogen phosphate, potassium chloride, potassium ferrocyanide, Potassium sulfate, sodium carbonate, sodium dihydrogen phosphate, sodium sulfate, sodium phosphate, sucrose, urea, work at low temperature and then heat up to dissolve and remove solid particles;

The third category: Substances with great differences in solubility in different solvents, for example: most ionic compounds (such as NaCl, K ₂ CO ₃ , KCl, AlCl ₃ ) are highly soluble in water but in ethanol, benzene, CCl ₄ and other organic compounds The solubility in the solvent is small, and it is removed by working in an organic working medium and then washing with water;

The fourth category: Substances that are easily separated under the action of electric field and magnetic field, such as: Al ₂ O ₃ , CaCO ₃ , Fe ₂ O ₃ , Fe ₃ O ₄ , Fe, etc., can be removed by electric field and magnetic field, such as using electrostatic classification filter equipment and magnetic field separation equipment removal;

The fifth category: solid particles that are easily volatilized, sublimated, and decomposed when heated at high temperature, such as sucrose, I ₂ , urea, NH ₄ NO ₃ , NH ₄ HCO ₃ , CH ₃ COONH _{4 ,} etc., are removed by high temperature heating;

The sixth category: solid particles with large specific gravity, such as zirconia, vanadium, chromium, tungsten, etc., using classification and separation equipment (such as linear vibrating screen classification equipment, airflow classifier, three-legged centrifuge-SS450, multi-stage classifier (Shenzhen) Kaibu Electronics Co., Ltd.)) removed.

Specific Embodiment Eighty-six: In this embodiment, the method for preparing graphene by mechanical exfoliation with high efficiency and low cost is completed through the following steps: in a jet mill, use air with a humidity of 90% and silicon oxide with a particle size of 7 nm to 1 part of graphite powder is mechanically exfoliated, the mass ratio of silicon oxide and graphite powder is 4~20:1, HF with a mass percentage concentration of 5% is added to dissolve SiO ₂ , and then filtered to obtain graphene.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2105W/mK, and the yield is above 91%. .

Specific Embodiment Eighty-seven: In this embodiment, the method for preparing graphene by mechanical exfoliation with high efficiency and low cost is carried out according to the following steps: in the jet mill, use air with a humidity of 90% and _Fe2 with a particle size of 7nm~1μm O ₃ mechanically strip graphite powder for 0.1-20 hours, the mass ratio of Fe ₂ O ₃ and graphite powder is 40-1000:1, and then use electrostatic classification filter equipment or magnetic field separation equipment to remove Fe ₂ O ₃ ; that is, graphene is obtained.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2050W/mK, and the yield is above 93%. .

Specific Embodiment Eighty-Eight: The method for preparing graphene oxide by high-efficiency and low-cost mechanical exfoliation in this embodiment is carried out according to the following steps: In the jet mill, use nitrogen and Fe ₂ O ₃ with a particle size of 7 nm on graphite oxide The powder is mechanically exfoliated for 0.1-20 hours, the mass ratio of Fe ₂ O ₃ and graphite oxide powder is 40:1, and then the Fe ₂ O ₃ is removed by electrostatic classification filter equipment or magnetic field separation equipment; graphene oxide is obtained.

The graphene oxide prepared by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355-5 nm, and the yield is over 90%.

Specific embodiment eighty-nine: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is carried out according to the following steps: in the jet mill, use argon and urea to mechanically exfoliate the expanded graphite powder for 0.1 to 20 hours , the mass ratio of urea to expanded graphite powder is 200~2000:1, and then heated at 160~200°C to remove urea to obtain graphene.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ² S/cm, the thermal conductivity is above 2150W/mK, and the yield is above 90%. .

Ninety specific embodiments: the method for preparing graphene with high-efficiency and low-cost mechanical exfoliation in this embodiment is completed through the following steps: in the jet mill, use air with a humidity of 90% and _CaCO to mechanically exfoliate expanded graphite for 0.1~ After 20 hours, the mass ratio of CaCO ₃ to graphite powder is 200-2000:1, and then CaCO ₃ is dissolved in HCl with a concentration of 10%-30% by mass, filtered and washed with water to obtain graphene.

The method of this embodiment makes graphene with single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ² S/cm, the thermal conductivity is above 2100W/mK, and its yield is in More than 90.

Specific Embodiment Ninety-one: The method for preparing graphene by high-efficiency and low-cost mechanical exfoliation in this embodiment is completed through the following steps: in the jet mill, mechanically exfoliate graphite powder with helium and potassium dihydrogen phosphate for 0.1~ After 20 hours, the mass ratio of potassium dihydrogen phosphate to graphite powder is 200~2000:1, add an appropriate amount of water, heat at 100°C, filter and wash to obtain graphene.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2250W/mK, and the yield is above 90%. .

Specific Embodiment Ninety-two: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is completed through the following steps: in the jet mill, use nitrogen and sucrose to mechanically exfoliate graphite powder for 0.1 to 20 hours, and sucrose The mass ratio to graphite powder is 500~1000:1, add water and heat to 100°C, filter and wash to obtain graphene.

The method of this embodiment makes graphene with single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2200W/mK, and its yield is in More than 90.

Specific Embodiment Ninety-three: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is completed through the following steps: in the jet mill, use nitrogen and NaCl to mechanically exfoliate graphite powder for 0.5 to 20 hours, NaCl The mass ratio to graphite powder is 500~1000:1, add 500~3000 parts of water (for dissolving NaCl), filter, and wash with water; the graphene is obtained.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2100W/mK, and the yield is above 90%. .

Specific Embodiment Ninety-Four: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is completed through the following steps: in the jet mill, use nitrogen and KCl to mechanically exfoliate graphite powder for 0.5 to 20 hours, KCl The mass ratio to graphite powder is 500~1000:1, add 500~3000 parts of water (for dissolving KCl), filter, and wash with water; the graphene is obtained.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Ninety-five: In this embodiment, the method for preparing graphene by mechanical exfoliation with high efficiency and low cost is completed through the following steps: in the jet mill, use nitrogen and Al ₂ O ₃ to mechanically exfoliate graphite powder for 0.5-20 Hours, the mass ratio of Al ₂ O ₃ to graphite powder is 50-1000:1, and the Al ₂ O ₃ is removed by electrostatic classification and filtration equipment; that is, graphene is obtained.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2050W/mK, and the yield is above 90%. .

Specific Embodiment Ninety-six: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is completed through the following steps: in the jet mill, use nitrogen and iron powder to mechanically exfoliate graphite powder for 0.5 to 20 hours, The mass ratio of iron powder and graphite powder is 10~2000:1, and the iron powder is removed by magnetic field separation equipment; that is, graphene is obtained.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Ninety-Seven: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is completed through the following steps: in the jet mill, use nitrogen and urea to mechanically exfoliate the expanded graphite powder for 0.5 to 20 hours, The mass ratio of urea to graphite powder is 20-1000:1, filtered, washed with water, and heated at 200°C to rapidly decompose residual urea to obtain well-dispersed graphene.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ² S/cm, the thermal conductivity is above 2300W/mK, and the yield is above 90%. .

Specific Embodiment Ninety-eight: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is completed through the following steps: in the jet mill, use nitrogen and urea to mechanically exfoliate the expanded graphite powder for 0.5 to 20 hours, The mass ratio of urea to graphite powder is 10~500:1, and the urea is rapidly decomposed by heating at 200°C to obtain well-dispersed graphene.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ² S/cm, the thermal conductivity is above 2000W/mK, and the yield is above 90%. .

Specific Embodiment Ninety-Nine: The method for preparing graphene by mechanical exfoliation with high efficiency and low cost in this embodiment is completed through the following steps: in the jet mill, use nitrogen and copper powder to mechanically exfoliate graphite powder for 0.5 to 20 hours, The mass ratio of copper powder and graphite powder is 50~1000:1, and the copper powder is removed by an air classifier; that is, graphene is obtained.

The graphene obtained by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355~5nm, the electrical conductivity is above 10 ³ S/cm, the thermal conductivity is above 2100W/mK, and the yield is above 90%. .

One hundred specific embodiments: the method for preparing graphene oxide by high-efficiency and low-cost mechanical exfoliation in this embodiment is completed through the following steps: in the jet mill, use air with a humidity of 90% and zirconia powder to process the graphene oxide powder Mechanical exfoliation for 0.5-20 hours, the mass ratio of zirconia powder and graphite oxide powder is 50-1000:1, and the zirconia powder is removed by air separator; graphene oxide is obtained.

The graphene oxide prepared by the method of this embodiment has a single-layer or multi-layer structure, the thickness is in the range of 0.355-5 nm, and the yield is over 90%. the

the

Claims (11)

1. high-efficiency and low-cost mechanical stripping prepares the method for Graphene or graphene oxide, it is characterized in that the method that high-efficiency and low-cost mechanical stripping prepares Graphene or graphene oxide undertaken by following step: with particle diameter is that carbon materials powder, the particle diameter of 0.05 ~ 1000 μ m is to carry out mechanically peel after the solid particulate of 1nm ~ 100 μ m and liquid-working-medium mix, and liquid-working-medium is that 10 ~ 73mN/m and viscosity are 1 ~ 1 * 10 at the working temperature lower surface tension force of mechanically peel ⁹MPas, splitting time is removed solid particulate and liquid-working-medium then more than 5 minutes; Promptly obtain Graphene or graphene oxide; Wherein, add dispersion agent in the mechanically peel process, dispersant dosage is 0 ~ 20% of a liquid-working-medium, and described carbon materials powder is Graphite Powder 99, expanded graphite, expansible black lead or graphite oxide powder.

2. high-efficiency and low-cost mechanical stripping according to claim 1 prepares the method for Graphene or graphene oxide, weight ratio 1:0.1 ~ 10000 that it is characterized in that described carbon materials powder and solid particulate, the weight ratio 1:0.1 of described solid particulate and liquid-working-medium ~ 10000.

3. high-efficiency and low-cost mechanical stripping according to claim 2 prepares the method for Graphene or graphene oxide, it is characterized in that described solid particulate is a magnesium, aluminium, iron, cobalt, nickel, copper, zinc, silver, tin, vanadium, chromium, tungsten, copper alloy, aluminium alloy, zinc alloy, iron-carbon, magnesium alloy, lithium alloy, boron oxide, silicon oxide, zirconium white, aluminum oxide, lime carbonate, magnesium oxide, titanium dioxide, iodine, zinc oxide, stannic oxide, ferric oxide, Z 250, aluminium nitride, aluminum chloride, titanium nitride, silicon carbide, Sodium Fluoride, Neutral ammonium fluoride, calcium oxide, bicarbonate of ammonia, brometo de amonio, ammonium chromate, primary ammonium phosphate, ammonium formiate, ammonium acetate, sodium bicarbonate, ammonium hydrogen phosphate, ammonium iodide, ammonium nitrate, ammonium oxalate, ammonium sulfate, ammonium sulphite, ammonium tartrate, ammonium thiocyanate, ammonium acetate, barium iodide, nitrate of baryta, Calcium Bromide, calcium iodide, nitrocalcite, calcium nitrite, potassium acetate, potassium bromate, Potassium Bromide, salt of wormwood, Potcrate, Repone K, potassiumchromate, potassium bichromate, potassium primary phosphate, the Tripotassium iron hexacyanide, yellow prussiate of potash, Potassium monofluoride, potassium formiate, sal enixum, potassium hydroxide, potassiumiodide, saltpetre, potassium oxalate, vitriolate of tartar, Potassium Thiosulphate, lithium acetate, lithiumbromide, sodium-chlor, lithium chloride, lithium formate, lithium iodide, aluminum nitrate, Tai-Ace S 150, magnesium acetate, magnesium bromide, magnesium iodide, sal epsom, sodium acetate, yellow soda ash, SODIUM PHOSPHATE, MONOBASIC, sodium formiate, sodium acetate, SODIUMNITRATE, sodium phosphate, sodium sulfate, nickelous chloride, nickelous nitrate, iron protochloride, ferrous sulfate, iron(ic) chloride, cupric chloride, cupric nitrate, copper sulfate, zinc sulfate, sucrose, urea, polymer microsphere, a kind of or wherein several mixing of glass powder.

4. high-efficiency and low-cost mechanical stripping according to claim 3 prepares the method for Graphene or graphene oxide, it is characterized in that the surface tension 40 ~ 50mN/m of described liquid-working-medium.

5. high-efficiency and low-cost mechanical stripping according to claim 4 prepare Graphene or OxidationThe method of Graphene, the viscosity that it is characterized in that described liquid-working-medium is 100 ~ 500000mPas.

6. the method for preparing Graphene or graphene oxide according to the described high-efficiency and low-cost mechanical stripping of each claim of claim 1-5 is characterized in that adopting in clarifixator, colloidal mill, three-roller, screw extrusion press, ball mill, pan-milling machine, sand mill, oscillating mill and the ultrasonic device a kind of or wherein several logotype to carry out mechanically peel; Described liquid-working-medium is the aqueous solution, the alcoholic solution of alkanes, the alcoholic solution of ketone, the aqueous solution of amine or the alkane solution of aromatics of water, alcohols, aromatics, ketone, amine, ionic liquid, alkanes, heterogeneous ring compound, dithiocarbonic anhydride, tetracol phenixin, gasoline, vegetables oil, diesel oil, wax, alcohol.

7. the method for preparing Graphene or graphene oxide according to the described high-efficiency and low-cost mechanical stripping of claim 6, it is characterized in that described alcohols is ethanol, n-propyl alcohol, propyl carbinol, ethylene glycol, propylene glycol, 1,2-butyleneglycol, 1,3-butyleneglycol, 1, a kind of or wherein several mixing in 4-butyleneglycol, glycerol and the Virahol; Described aromatics is benzene, toluene, naphthalene or anthracene; Described ketone is acetone or Ν-methyl-2-pyrrolidone; Described amine is N-methylformamide, N, dinethylformamide or N, N-diethylformamide; Described ionic liquid is 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-Methylimidazole hexafluorophosphate or 1-hydroxyethyl-3-methyl hexafluorophosphate; Described alkanes is normal hexane, octane or decane; Described heterogeneous ring compound is furans or pyridine; Alcohol is methyl alcohol, ethanol, glycerol, butyleneglycol or Virahol in the aqueous solution of described alcohol; The alcoholic solution of described alkanes is the octanol solution of normal hexane, the decyl alcohol solution of normal hexane or the decyl alcohol solution of octadecane; The alcoholic solution of described ketone is the butanediol solution of acetone or the ethanolic soln of acetone; Amine in the aqueous solution of described amine is N-methylformamide solution or N, dinethylformamide solution; The alkane solution of described aromatics is the hexane solution of benzene or the hexane solution of toluene.

8. the method for preparing Graphene or graphene oxide according to the described high-efficiency and low-cost mechanical stripping of each claim of claim 1-5, it is characterized in that adopting mill, Banbury mixer, clarifixator, colloidal mill, three-roller or screw extrusion press to carry out mechanically peel, described liquid-working-medium is a macromolecular compound.

9. described according to Claim 8 high-efficiency and low-cost mechanical stripping prepares the method for Graphene or graphene oxide, it is characterized in that described macromolecular compound polyacrylic ester, polyvinyl alcohol, polyoxyethylene glycol, Vinyl Acetate Copolymer, starch, polyhutadiene, poly-butylbenzene diene, Resins, epoxy, coal tar or pitch.

10. high-efficiency and low-cost mechanical stripping prepares the method for Graphene or graphene oxide, it is characterized in that the method that high-efficiency and low-cost mechanical stripping prepares Graphene or graphene oxide undertaken by following step: in micronizer mill, with gas working dielectric and particle diameter is that the solid particulate of 1nm ~ 100 μ m carries out mechanically peel to the carbon materials powder, splitting time is removed solid particulate then more than 5 minutes; Promptly obtain Graphene or graphene oxide, described carbon materials powder is Graphite Powder 99, expanded graphite, expansible black lead or graphite oxide powder.

11. prepare the method for Graphene or graphene oxide according to the described high-efficiency and low-cost mechanical stripping of claim 10, it is characterized in that described gas working dielectric is air, He, Ne, Ar, N ₂, H ₂, Cl ₂, Br ₂, CO, CO ₂, CH ₄, NH ₃, a kind of or wherein several mixing in the water vapour, benzene vapor.