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

Method for preparing graphene or graphene oxide by using high-efficiency and low-cost mechanical stripping Download PDF

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CN101817516A
CN101817516A CN 201010179119 CN201010179119A CN101817516A CN 101817516 A CN101817516 A CN 101817516A CN 201010179119 CN201010179119 CN 201010179119 CN 201010179119 A CN201010179119 A CN 201010179119A CN 101817516 A CN101817516 A CN 101817516A
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graphene
oxide
efficiency
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present
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王黎东
费维栋
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Harbin Institute of Technology
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Harbin Institute of Technology
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Abstract

The invention provides a method for preparing graphene or graphene oxide by using high-efficiency and low-cost mechanical stripping and relates to a preparation method of the graphene or the graphene oxide, solving the problems that the traditional micro-mechanical stripping method has low efficiency and can not be used for large-batch production. The method comprises the following step of separating carbon materials by utilizing solid particles and a liquid working medium (or gas working medium) and adopting mechanical stripping to obtain the graphene or the graphene oxide, wherein the carbon materials comprise graphite powder, expanded graphite, expandable graphite or graphite powder oxide. By using automatic machinery and using a great deal of solid particles for assisting stripping processes, the invention greatly increases the contact areas and the stripping times of the stripping processes, the carbon materials are subject to a great amount of stripping processes in a short time through the shearing and impacting functions of the solid particles on the carbon materials, and thereby the method obviously improves the stripping efficiency, has low cost and is suitable for the industrial and large-batch production of the graphene or the graphene oxide.

Description

High-efficiency and low-cost mechanical stripping prepares the method for Graphene or graphene oxide
Technical field
The present invention relates to the preparation method of Graphene or graphene oxide.
Background technology
Graphene is present the thinnest known two-dimensional material, and single-layer graphene has desirable two dimensional crystal structure, is made up of hexagonal lattice.Since successfully being prepared, Graphene has caused the research boom that one is new in worldwide.Graphene has many peculiar characteristics, has excellent electricity, optics, calorifics and mechanical property, probably causes revolutionary variation in a lot of fields.The ideal single-layer graphene has the specific surface area (2630m of super large 2/ g), be very potential energy storage material.Graphene is a kind of semi-conductor that does not have energy gap, and it has than the high a lot of carrier mobility (2 * 10 of silicon 5Cm 2/ (V.s)), micron-sized mean free path and big coherence length are at room temperature arranged, so Graphene is the ideal material of nanometer circuit; Graphene has good electrical conductivity, and its electronic motion speed has reached 1/300 of the light velocity, and considerably beyond the movement velocity of electronics in general conductor, Graphene has good light transmittance simultaneously, is the potential substitute products of conventional I TO film.Graphene has good thermal property, and thermal conductivity is 3080～5150W/mK.Graphene is the highest material of present known strength, and its ideal tensile strength is 110 ~ 130GPa, is that the ideal of various matrix materials strengthens body.
2004, the strong K of the peace moral of Univ Manchester UK sea nurse (Science such as (AndreK.Geim), 2004,306:666) very simple method---micromechanics is peeled off method (Micromechanicalcleavage) with a kind of, on highly oriented pyrolytic graphite, carry out tear-off repeatedly, obtain single-layer graphene with scotch tape.In recent years, people except micromechanics is peeled off method, had been developed the dilatometry and the multiple preparation methods such as reduction method, crystal epitaxy, chemical vapour deposition and organic synthesis of graphite oxide having obtained positive progress aspect the preparation of Graphene.Though the dilatometry of graphite oxide and reduction method can be prepared a large amount of Graphenes with relatively low cost, yet the electronic structure of Graphene and perfection of crystal all are subjected to the destruction of strong oxidizer, its electronic property is affected.Crystal epitaxy and chemical vapour deposition can be prepared big area continuously and the graphene film semiconductor material of excellent performance, and with conventional semiconductor processing technology compatibility, the grapheme material that makes this method prepare has huge application potential at microelectronic, yet these method present stage technologies are still immature, and for one of developing direction of the tool potentiality of Graphene---for the field of compound material, general used Graphene does not need very big area, but need very big output, methods such as crystal epitaxy and chemical vapour deposition are difficult to satisfy the demands in this respect.
Graphene oxide is fully to peel off the stratiform covalent compound that obtains by graphite oxide through physics or chemical process.Graphite is at H 2SO 4, HNO 3, HClO 4Deng strong acid and strong oxidizer (as KClO 4, KMnO 4Deng) effect under, or electrochemistry peroxidation (overoxide) effect is down, after hydrolysis, promptly be converted into graphite oxide (GraphiteOxide, GO).In recent years, develop Graphene/polymer conductive nanometer material and unsupported graphite oxide paper in succession with oxidation style, correlative study is very active.At present, preparation graphite oxide technology is ripe relatively, if prepare graphene oxide from graphite oxide, need overcome the constraint of interlayer Van der Waals force, must apply certain external force, develop many preparation methods for this reason, such as pyrolysis expansion, ultrasonic wave, electrostatic repulsion, machinery, low temperature etc., but the work for preparing graphene oxide from graphite oxide is still very imperfect, realize mono-layer graphite oxide alkene a large amount of, controllability preparation also needs constantly to explore new thinking and approach.
In several graphene preparation methods, micromechanics is peeled off method and is directly utilized one step of graphite to make Graphene, does not use large-scale precision equipment, and preparation technology is the simplest, has tangible cost advantage; Do not experience chemical oxidation and reduction process, do not experience the high temperature expansion process, the Graphene defective is few, and quality is good; The consumption of no chemical reagent is a kind of method of environmental protection.But micromechanics is peeled off method because efficient is extremely low, generally is considered to satisfy the requirement of futurity industryization.
Summary of the invention
To peel off the efficient of method low in order to solve existing micromechanics for purpose of the present invention, and can not produce in enormous quantities problem; And provide high-efficiency and low-cost mechanical stripping to prepare the method for Graphene or graphene oxide.
Scheme one: high-efficiency and low-cost mechanical stripping prepares the method for Graphene or graphene oxide to be 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, described carbon materials powder is Graphite Powder 99, expanded graphite, expansible black lead or graphite oxide powder, adds dispersion agent in the mechanically peel process, and dispersant dosage is 0 ~ 20% of a liquid-working-medium.
Scheme two: high-efficiency and low-cost mechanical stripping prepares the method for Graphene or graphene oxide to be 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.
Solid particulate described in above-mentioned two schemes 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.
Aforesaid method of the present invention utilizes automation at carbon materials powder (Graphite Powder 99, the graphite oxide powder, expanded graphite or unexpansive graphite), in the system that solid particulate and working medium are formed the carbon materials powder is carried out mechanically peel, obtain the mixture of Graphene and working medium and solid particulate, again with filtering, distillation, underpressure distillation, pickling, washing, centrifugal, electric field (as utilizing electrostatic separator etc.), magnetic field means such as (as utilizing high gradient magnetic separator etc.) or special fractional separation equipment are (as the linear vibrating screen stage equipment, air classifier, tripod pendulum type batch centrifugal-SS450, multistage grading machine etc.) from above-mentioned mixture, obtain Graphene (graphene oxide).The present invention utilizes automation to replace manual stripping process, thereby improves charge stripping efficiency; Utilize a large amount of small solid particulate up-stripping processes, increase the contact area of stripping process greatly and peel off number of times, by shearing and the effect of impact of solid particulate, make graphite experience a large amount of stripping processes at short notice, thereby significantly improve charge stripping efficiency graphite; Liquid or gas working dielectric play an important role to peeling off, working medium can be peeled off required strength to solid particulate and Graphite Powder 99 transmission on the one hand, on the other hand, working medium has certain dissemination to Graphene and solid particulate, hinder compound between the Graphene, in addition, working medium can absorb and conduct the heat that produces in the mechanically peel process, avoids the overheated Graphene that makes to produce defective.Because mass of solid particles is very little, energy is lower in the moving process, and Graphene is the strongest in the world material (bond energy reaches 345kJ/mo1), at interlayer then with faint Van der Waals force combine (bond energy 16.7kJ/mol), so can realize small solid particulate with the graphite knockout process in Graphene is not damaged, and only open the Van der Waals key of interlayer, thereby finally obtain individual layer and thin layer Graphene or graphene oxide.The number of plies is adjustable, by adjusting the number of plies of splitting time may command Graphene (or graphene oxide), can obtain individual layer or thin layer (2 ~ 10 layers) Graphenes (or graphene oxide), and the productive rate of producing Graphene and graphene oxide is all more than 90%; The product yield height has improved utilization ratio of raw materials, and the efficient height of producing, and then has reduced production cost.The inventive method is suitable for industrialized mass Graphene and graphene oxide.
Embodiment
Embodiment one: the method that high-efficiency and low-cost mechanical stripping prepares Graphene or graphene oxide in the present embodiment is 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, described carbon materials powder is Graphite Powder 99, expanded graphite, expansible black lead or graphite oxide powder, adds dispersion agent in the mechanically peel process, and dispersant dosage is 0 ~ 20% of a liquid-working-medium.
The described working temperature of present embodiment promptly will satisfy equipment requirements will guarantee also that simultaneously liquid-working-medium is in liquid state in the mechanically peel process.The dispersion agent that uses in the present embodiment can be selected polyetherimide (PEI), cetyl trimethylammonium bromide (CTAB), polyacrylic acid (PAA), sodium lauryl sulphate (SDS), sodium laurylsulfonate (SDBS), commodity dispersion agent etc. for use, and the commodity dispersion agent can be selected Disperbyk-163 wetting dispersing agent, Disperbyk-2150 wetting dispersing agent, super dispersion agent Tilo-3000, super dispersion agent Tilo-5110, super dispersion agent Tilo-27000 etc. for use.
The method of present embodiment utilizes automation at carbon materials powder (Graphite Powder 99, the graphite oxide powder, expanded graphite or unexpansive graphite), in the system that solid particulate and working medium are formed the carbon materials powder is carried out mechanically peel, obtain the composite granule of Graphene and solid particulate, again with filtering, distillation, underpressure distillation, pickling, washing, centrifugal, electric field (as utilizing electrostatic separator etc.), magnetic field means such as (as utilizing high gradient magnetic separator etc.) or special fractional separation equipment are (as the linear vibrating screen stage equipment, air classifier, tripod pendulum type batch centrifugal-SS450, multistage grading machine etc.) from above-mentioned mixture, obtain Graphene (graphene oxide).Present embodiment utilizes automation to replace manual stripping process, thereby improves charge stripping efficiency; Utilize a large amount of small solid particulate up-stripping processes, increase the contact area of stripping process greatly and peel off number of times, by shearing and the effect of impact of solid particulate, make graphite experience a large amount of stripping processes at short notice, thereby significantly improve charge stripping efficiency graphite; Liquid or gas working dielectric play an important role to peeling off, working medium can be peeled off required strength to solid particulate and Graphite Powder 99 transmission on the one hand, on the other hand, working medium has certain dissemination to Graphene and solid particulate, hinder compound between the Graphene, in addition, working medium can absorb and conduct the heat that produces in the mechanically peel process, avoids the overheated Graphene that makes to produce defective.Small solid particulate with the graphite knockout process in Graphene is not done great damage, and only open the Van der Waals force of interlayer, guarantee that stripping process carries out between graphene layer, thereby finally obtain individual layer and thin layer Graphene or graphene oxide.By adjusting the number of plies of splitting time may command Graphene (or graphene oxide), can obtain individual layer or thin layer (2 ~ 10 layers) Graphenes (or graphene oxide), the productive rate of producing Graphene (or graphene oxide) is all more than 90%, and thickness is in 0.355 ~ 5nm scope; The product yield height has improved utilization ratio of raw materials, and the efficient height of producing, and then has reduced production cost.The present embodiment method is suitable for industrialized mass Graphene and graphene oxide.The present embodiment method obtains the electric conductivity of Graphene 10 3More than the S/cm, thermal conductivity is more than 2000W/mK.
Embodiment two: what present embodiment and embodiment one were different is: weight ratio 1:0.1 ~ 10000 of described carbon materials powder and solid particulate, weight ratio 1:0.1 ~ 10000 of described carbon materials powder and liquid-working-medium.Other step is identical with embodiment one with parameter.
Embodiment three: what present embodiment and embodiment two were different is: weight ratio 1:1 ~ 2000 of described carbon materials powder and solid particulate.Other step is identical with embodiment two with parameter.
Embodiment four: what present embodiment and embodiment two were different is: weight ratio 1:5 ~ 1000 of described carbon materials powder and solid particulate.Other step is identical with embodiment two with parameter.
Embodiment five: what present embodiment and embodiment two were different is: weight ratio 1:10 ~ 500 of described carbon materials powder and solid particulate.Other step is identical with embodiment two with parameter.
Embodiment six: what present embodiment and embodiment two were different is: weight ratio 1:100 ~ 200 of described carbon materials powder and solid particulate.Other step is identical with embodiment two with parameter.
Embodiment seven: what present embodiment was different with one of embodiment two to six is: the weight ratio 1:0.2 of described solid particulate and liquid-working-medium ~ 5000.Other step is identical with one of embodiment two to six with parameter.
Embodiment eight: what present embodiment was different with one of embodiment two to five is: the weight ratio 1:100 of described solid particulate and liquid-working-medium ~ 2000.Other step is identical with one of embodiment two to six with parameter.
Embodiment nine: what present embodiment was different with one of embodiment two to five is: the weight ratio 1:200 of described solid particulate and liquid-working-medium ~ 500.Other step is identical with one of embodiment two to six with parameter.
Embodiment ten: what present embodiment was different with one of embodiment one to nine is: 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.Other step is identical with one of embodiment one to nine with parameter.
When the present embodiment solid particulate is mixture, press between various solid particulates arbitrarily than mixing.Above-mentioned solid particulate can adopt following method to remove respectively according to its character:
The first kind: can be dissolved in the solid particulate of acid, alkaline solution, for example: Al, Cu, Zn, SnO, ZnO, B 2O 3, SiO 2, NaHCO 3, CaCO 3, CaO etc., can remove by pickling or alkali cleaning;
Second class: room temperature-high temperature (for example 100 ℃) solubility with temperature changes material greatly, for example: bicarbonate of ammonia, primary ammonium phosphate, ammonium oxalate, potassium primary phosphate, Repone K, yellow prussiate of potash, vitriolate of tartar, yellow soda ash, SODIUM PHOSPHATE, MONOBASIC, sodium sulfate, sodium phosphate, sucrose, urea, adopt low-temperature working then to heat up the solid particulate dissolving removed;
The 3rd class: the very big material of dissolubility difference in different solvents, for example: most of ionic compounds are (as NaCl, K 2CO 3, KCl, AlCl 3) solubleness is big and at ethanol, benzene, CCl in water 4Less Deng solubleness in the organic solvent, adopt and in organic working medium, to work and the method for after washing is removed;
The 4th class: segregative material under electric field, the action of a magnetic field, for example: Al 2O 3, CaCO 3, Fe 2O 3, Fe 3O 4, Fe etc., remove by electric field, magnetic field, as removing with static classified filtering equipment or magnetic field separation equipment;
The 5th class: volatile during heat, distillation, decompose the solid particulate remove, as sucrose, I 2, urea, NH 4NO 3, NH 4HCO 3, CH 3COONH 4Deng, adopt the way of heat to remove;
The 6th class: heavy solid particulate, as zirconium white, vanadium, chromium, tungsten etc., adopt fractional separation equipment (to remove as linear vibrating screen stage equipment, air classifier, tripod pendulum type batch centrifugal-SS450, multistage grading machine (step Electronics Co., Ltd. is opened in Shenzhen).
Embodiment 11: what present embodiment was different with one of embodiment one to ten is: the surface tension 40 ~ 50mN/m of described liquid-working-medium.Other step is identical with one of embodiment one to ten with parameter.
Embodiment 12: one of present embodiment and embodiment one to ten are not both: the surface tension 45mN/m of described liquid-working-medium.Other step is identical with one of embodiment one to ten with parameter.
Embodiment 13: what present embodiment was different with one of embodiment one to 12 is: the viscosity of described liquid-working-medium is 100 ~ 500000mPas.Other step is identical with one of embodiment one to 12 with parameter.
Embodiment 14: what present embodiment was different with one of embodiment one to 12 is: the viscosity of described liquid-working-medium is 1000 ~ 50000mPas.Other step is identical with one of embodiment one to 12 with parameter.
Embodiment 15: what present embodiment was different with one of embodiment one to 12 is: the viscosity of described liquid-working-medium is 5000mPas.Other step and parameter and embodiment one to 11 two identical.
Embodiment 16: what present embodiment was different with one of embodiment and embodiment one to 15 is: the particle diameter of described solid particulate is 5nm ~ 100nm.Other step is identical with one of embodiment one to 15 with parameter.
Embodiment 17: what present embodiment and embodiment and embodiment 16 were different is: the particle diameter of described solid particulate is 200nm ~ 500nm.Other step is identical with embodiment one to 16 with parameter.
Embodiment 18: what present embodiment and embodiment and embodiment 16 were different is: the particle diameter of described solid particulate is 1 μ m ~ 20 μ m.Other step is identical with embodiment 16 with parameter.
Embodiment 19: what present embodiment and embodiment and embodiment 16 were different is: the particle diameter of described solid particulate is 50 μ m ~ 80 μ m.Other step is identical with embodiment 16 with parameter.
Embodiment 20: what present embodiment was different with one of embodiment one to 19 is: adopt clarifixator, colloidal mill, three-roller, screw extrusion press, ball mill, the pan-milling machine, sand mill, mechanically peel is carried out in a kind of or wherein several logotype in oscillating mill and the ultrasonic device, and described liquid-working-medium is a water, alcohols, aromatics, ketone, amine, ionic liquid, alkanes, heterogeneous ring compound, dithiocarbonic anhydride, tetracol phenixin, gasoline, vegetables oil, diesel oil, wax, the aqueous solution of alcohol, the alcoholic solution of alkanes, the alcoholic solution of ketone, the alkane solution of the aqueous solution of amine or aromatics.Other step is identical with one of embodiment one to 19 with parameter.
Embodiment 21: what present embodiment and embodiment 20 were different is: 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.Other step is identical with embodiment 20 with parameter.
When alcohols is mixture in the present embodiment, press between various alcohols arbitrarily than mixing.
Embodiment 22: what present embodiment and embodiment 20 were different is: described aromatics is benzene, toluene, naphthalene or anthracene.Other step is identical with embodiment 20 with parameter.
Embodiment 23: what present embodiment and embodiment 20 were different is: described ketone is acetone or Ν-methyl-2-pyrrolidone.Other step is identical with embodiment 20 with parameter.
Embodiment 24: what present embodiment and embodiment 20 were different is: described amine is methylformamide, N, dinethylformamide or N,N-dimethylacetamide.Other step is identical with embodiment 20 with parameter.
Embodiment 25: what present embodiment and embodiment 20 were different is: described ionic liquid is 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-Methylimidazole hexafluorophosphate or 1-hydroxyethyl-3-methyl hexafluorophosphate.Other step is identical with embodiment 20 with parameter.
Embodiment 26: what present embodiment and embodiment 20 were different is: described alkanes is normal hexane, octane or decane.Other step is identical with embodiment 20 with parameter.
Embodiment 27: what present embodiment and embodiment 20 were different is: described heterogeneous ring compound is furans or pyridine.Other step is identical with embodiment 20 with parameter.
Embodiment 28: what present embodiment and embodiment 20 were different is: alcohol is methyl alcohol, ethanol, glycerol, butyleneglycol or Virahol in the aqueous solution of described alcohol.Other step is identical with embodiment 20 with parameter.
Embodiment 29: what present embodiment and embodiment 20 were different is: the alcoholic solution of described alkanes is the octanol solution of normal hexane, the decyl alcohol of normal hexane or the decyl alcohol of octadecane.Other step is identical with embodiment 20 with parameter.
Embodiment 30: what present embodiment and embodiment 20 were different is: the alcoholic solution of described ketone is the butanediol solution of acetone or the ethanolic soln of acetone.Other step is identical with embodiment 20 with parameter.
The embodiment hentriaconta-: what present embodiment and embodiment 20 were different is: the amine in the aqueous solution of described amine is N-methylformamide or N, dinethylformamide.Other step is identical with embodiment 20 with parameter.
Embodiment 32: what present embodiment and embodiment 20 were different is: the hexane solution of the alkane solution benzene of described aromatics or the hexane solution of toluene.Other step is identical with embodiment 20 with parameter.
Embodiment 33: what present embodiment was different with one of embodiment one to 19 is: adopt 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.Other step is identical with one of embodiment one to 18 with parameter.
Embodiment 34: what present embodiment and embodiment 33 were different is: described macromolecular compound polyacrylic ester, polyvinyl alcohol, polyoxyethylene glycol, Vinyl Acetate Copolymer, starch, polyhutadiene, poly-butylbenzene diene, Resins, epoxy, coal tar or pitch.Other step is identical with embodiment 33 with parameter.
Embodiment 35: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: the silicon oxide that is 7nm with 1 part of Graphite Powder 99,4 parts of particle diameters and 500 part 1 by weight percentage, the mixing of 3-butyleneglycol is placed in the clarifixator, add polyacrylic acid again, the polyacrylic acid consumption is 1,5% of 3-butyleneglycol volume, peeled off 0.5 ~ 100 hour with 5000 rev/mins speed mechanical, filter and obtain Graphene and SiO 2Mixture, add mass percent concentration and be 5% HF dissolving SiO 2, filter, wash; Promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 36: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for graphene oxide to be finished by following step: by weight percentage with 1 part of graphite oxide powder, 40 parts of CaCO 3Be placed in the oscillating mill with 200 parts of Virahols mixing, add cetyl trimethylammonium bromide then, the cetyl trimethylammonium bromide consumption is 1% of a Virahol volume, and mechanically peel 0.5 ~ 100 hour filters and obtains graphene oxide and CaCO 3Mixture, add mass percent concentration and be 10% ~ 30% HCl dissolving CaCO 3, filter, wash; Promptly obtain graphene oxide.
The present embodiment method makes graphene oxide and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and its productive rate is more than 90%.
Embodiment 37: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: one, take by weighing 1 part of Graphite Powder 99,80 ~ 200 parts of potassium primary phosphates and 100 ~ 400 parts of water by weight percentage, under 90 ℃ of conditions potassium primary phosphate is being put into Graphite Powder 99 after soluble in water then, obtain mixture and place sand mill, add sodium laurylsulfonate again, the sodium laurylsulfonate consumption is 1% of a volume of water; Two, in 0.1 ~ 10 hour said mixture being cooled to 20 ~ 50 ℃ utilizes sand mill to peel off with 1000 ~ 10000 rev/mins speed simultaneously; Three, be warming up to 90 ℃ then, in 0.1 ~ 10 hour, be cooled to 20 ~ 50 ℃ again and utilize sand mill to peel off simultaneously with 1000 ~ 10000 rev/mins speed; Four, the operation of repeating step two and step 3 is 0 ~ 20 time, continues mechanically peel 0.1 ~ 100 hour, obtains the mixture of Graphene-potassium primary phosphate-water, and heated mixt to 100 ℃ (purpose is the dissolving phosphoric acid potassium dihydrogen) obtains Graphene after filtering, cleaning.
The whole process of the described method of present embodiment is pollution-free, is the synthetic route of a green.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 38: the method that the present embodiment high-efficiency and low-cost mechanical stripping prepares Graphene is to finish by following step: one, take by weighing 1 part of Graphite Powder 99,80 ~ 200 portions of sucrose and 100 ~ 400 parts of water by weight percentage, under 90 ℃ of conditions sucrose is being put into Graphite Powder 99 after soluble in water then, obtain mixture and place sand mill, add polyacrylic acid again, the polyacrylic acid consumption is 2% of a volume of water; Two, in 0.1 ~ 10 hour said mixture being cooled to 25 ℃ utilizes sand mill to peel off with 1000 ~ 10000 rev/mins speed simultaneously; Three, be warming up to 90 ℃ then, in 0.1 ~ 10 hour, be cooled to 25 ℃ again and utilize sand mill to peel off simultaneously with 1000 ~ 10000 rev/mins speed; Four, the operation of repeating step two and step 3 is 0 ~ 20 time, continues mechanically peel 0.1 ~ 100 hour, obtains the mixture of Graphene-sucrose-water, and heated mixt to 100 ℃ (purpose is a dissolving saccharose) obtains Graphene after filtering, cleaning.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2400W/mK, and its productive rate is more than 90%.
Embodiment 39: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: 1 part of Graphite Powder 99,50 ~ 1000 parts of NaCl and 500 ~ 5000 parts of ethanol are mixed being placed in the clarifixator by weight percentage, add polyacrylic acid again, the polyacrylic acid consumption is 3% of an ethanol volume, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed, filter the mixture that obtains Graphene and NaCl then, add 500 ~ 3000 parts of water (being used to dissolve NaCl), filter, water cleans; Promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 40: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: by weight percentage 1 part of Graphite Powder 99,50 ~ 1000 parts of KCl and 250 ~ 2500 parts of ethanol and 250 ~ 2500 parts of glycerol mixing are placed in the clarifixator, add polyacrylic acid again, the polyacrylic acid consumption is 0.5% of an ethanol volume, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed, filter the mixture that obtains Graphene and KCl then, add 500 ~ 3000 parts of water (being used to dissolve KCl), filter, water cleans; Promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 41: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: by weight percentage with the Al of 1 part of Graphite Powder 99,150 parts of about 200nm of diameter 2O 3Be placed in the oscillating mill with 100 parts of Virahols mixing, add cetyl trimethylammonium bromide (CTAB) then, the cetyl trimethylammonium bromide consumption is 2% of a Virahol volume, peels off 0.5 ~ 100 hour, filters and obtains Graphene and Al 2O 3Mixture, remove Al with static classified filtering equipment 2O 3Promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 42: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: iron powder and 200 parts of Virahols mixing with 1 part of Graphite Powder 99,100 parts of about 1 μ m of diameter by weight percentage are placed in the oscillating mill, add Disperbyk-163 again, the Disperbyk-163 consumption is 15% of a Virahol volume, peeled off 0.5 ~ 100 hour, filtration obtains the mixture of Graphene and iron powder, washes, removes iron powder with magnetic field separation equipment; Promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 43: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: one, take by weighing 1 part of Graphite Powder 99,50 ~ 2000 parts of urea and 100 ~ 2000 parts of ethanol by weight percentage, under 65 ℃ of conditions, urea is put into the ethanol back then and add Graphite Powder 99, obtain mixture and place clarifixator, add polyacrylic acid (PAA) again, the polyacrylic acid consumption is 2.5% of an ethanol volume; Two, in 0.1 ~ 10 hour said mixture being cooled to 20 ℃ utilizes clarifixator to peel off with 1000 ~ 10000 rev/mins speed simultaneously; Three, be warming up to 60 ℃ then, in 0.1 ~ 10 hour, be cooled to 30 ℃ again and utilize sand mill to peel off simultaneously with 1000 ~ 10000 rev/mins speed; Four, the operation of repeating step two and step 3 is 0 ~ 9 time, continued mechanically peel 0.1 ~ 100 hour, obtain Graphene-urea-alcoholic acid mixture, 35 ℃ ~ 55 ℃ filtrations, get the mixture of Graphene-urea, in environment heating more than 200 ℃ remaining urea is decomposed rapidly, obtain finely disseminated Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 44: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: one, take by weighing 1 part of Graphite Powder 99,200 ~ 2000 parts of ammonium formiates and 100 ~ 1000 parts of water by weight percentage, under 65 ℃ of conditions ammonium formiate is being put into Graphite Powder 99 after soluble in water, obtain mixture and place clarifixator, add cetyl trimethylammonium bromide (CTAB) then, the cetyl trimethylammonium bromide consumption is 2% of a volume of water; Two, in 0.1 ~ 10 hour said mixture being cooled to 20 ℃ utilizes clarifixator to peel off with 1000 ~ 10000 rev/mins speed simultaneously; Three, be warming up to 60 ℃ then, in 0.1 ~ 10 hour, be cooled to 20 ~ 50 ℃ again and utilize sand mill to peel off simultaneously with 1000 ~ 10000 rev/mins speed; Four, the operation of repeating step two and step 3 is 0 ~ 9 time, continued mechanically peel 0.1 ~ 100 hour, obtain the mixture of Graphene-ammonium formiate-water, 35 ℃ ~ 55 ℃ filtrations, get the mixture of Graphene-ammonium formiate, in environment heating more than 200 ℃ ammonium formiate is decomposed rapidly, obtain finely disseminated Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 92%.
Embodiment 45: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: copper powder and 150 parts of Virahols mixing with 1 part of Graphite Powder 99,200 parts of about 100nm of diameter by weight percentage are placed in the oscillating mill, add cetyl trimethylammonium bromide (CTAB) then, the cetyl trimethylammonium bromide consumption is 2% of an acetone volume, peeled off 0.5 ~ 100 hour, filtration obtains the mixture of Graphene and copper powder, washes, removes copper powder with air classifier; Promptly obtain Graphene.
The present embodiment method makes the Graphene that Graphene has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 46: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: by weight percentage with the zirconia powder of 1 part of Graphite Powder 99,200 parts of about 200nm of diameter and 500 part 1, the mixing of 4-butyleneglycol is placed in the oscillating mill, add polyacrylic acid (PAA) again, the polyacrylic acid consumption is 1,2% of 4-butyleneglycol volume, peeled off 0.5 ~ 100 hour, filtration obtains the mixture of Graphene and zirconia powder, washes, removes zirconia powder with whizzer; Promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 47: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for graphene oxide to be finished by following step: the silicon oxide that is 7nm with 1 part of graphite oxide powder, 4 parts of particle diameters and 200 part 1 by weight percentage, the mixing of 3-butyleneglycol is placed in the clarifixator, add polyacrylic acid (PAA) again, the polyacrylic acid consumption is 1,2% of 3-butyleneglycol volume, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed, filter and obtain graphene oxide and SiO 2Mixture, add 5%HF dissolving SiO 2, filtering separation; Promptly obtain graphene oxide.
The present embodiment method makes graphene oxide and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and its productive rate is more than 90%.
Embodiment 48: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for graphene oxide to be finished by following step: by weight percentage with 1 part of graphite oxide powder, the mixed solution of 50 ~ 1000 parts of NaCl and 500 ~ 5000 parts of octadecanes and decyl alcohol (volume ratio 1:10) mixes and is placed in the clarifixator, add cetyl trimethylammonium bromide (CTAB) then, the cetyl trimethylammonium bromide consumption is 0.5 ~ 3% of octadecane and a decanol mixture volume, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed, filter the mixture that obtains graphene oxide and NaCl then, add 500 ~ 3000 parts of water dissolution NaCl, filter, water cleans; Promptly obtain graphene oxide.
The present embodiment method makes graphene oxide and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and its productive rate is more than 90%.
Embodiment 49: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be undertaken by following step: the silicon oxide that is 7nm with 1 part of Graphite Powder 99,4 ~ 10 parts of particle diameters and 200 parts of polymethyl acrylates mix and are placed in the three-roller by weight percentage, add cetyl trimethylammonium bromide (CTAB) then, the cetyl trimethylammonium bromide consumption is 10% ~ 20% of a polymethyl acrylate volume, mechanically peel 4 ~ 100 hours, dissolve polymethyl acrylate with butylacetate, filter, dissolve SiO with 5%HF 2, obtain Graphene after the filtration.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 10nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 50: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for graphene oxide to be undertaken by following step: 1 part of graphite oxide powder, 5 ~ 50 sodium-chlor and 200 parts of polymethyl acrylates are mixed being placed in the three-roller by weight percentage, add cetyl trimethylammonium bromide (CTAB) then, the cetyl trimethylammonium bromide consumption is 10% ~ 20% of a polymethyl acrylate volume, mechanically peel 4 ~ 50 hours, dissolve polymethyl acrylate with butylacetate, filter, water dissolving sodium-chlor obtains graphene oxide after the filtration.Wherein said liquid-working-medium is a macromolecular compound.
The present embodiment method makes graphene oxide and has individual layer or multilayered structure, and thickness is in 0.355 ~ 10nm scope, and its productive rate is more than 90%.
Embodiment 51: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be undertaken by following step: by weight percentage with 1 part of expanded graphite powder, 5 ~ 50 sodium-chlor and 200 parts of polymethyl acrylates mixing are placed in the three-roller, add cetyl trimethylammonium bromide (CTAB) then, the cetyl trimethylammonium bromide consumption is 10% ~ 20% of a polymethyl acrylate volume, mechanically peel 4 ~ 50 hours, dissolve polymethyl acrylate with butylacetate, filter, 50 ~ 500 parts of water dissolution sodium-chlor of water obtain Graphene after the filtration.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 10nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 52: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be undertaken by following step: by weight percentage with 1 part of expansible black lead powder, 5 ~ 20 parts of sodium-chlor and 300 parts of polymethyl acrylates mixing are placed in the three-roller, add cetyl trimethylammonium bromide (CTAB) then, the cetyl trimethylammonium bromide consumption is 1% ~ 2% of a polymethyl acrylate volume, mechanically peel 2 ~ 25 hours, dissolve polymethyl acrylate with butylacetate, filter, 50 ~ 500 parts of water dissolution sodium-chlor of water obtain Graphene after the filtration.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 10nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 53: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be undertaken by following step: 1 part of Graphite Powder 99,5 ~ 20 parts of sodium-chlor, 2 ~ 20 parts of copper powders, 300 parts of ethylene glycol and 50 parts of acetone are mixed being placed in the clarifixator by weight percentage, add polyacrylic acid (PAA) again, the polyacrylic acid consumption is 0.1% ~ 2% of an acetone volume, mechanically peel 0.1 ~ 10h, filter, 50 ~ 500 parts of water dissolution sodium-chlor of water, after the filtration, then with obtaining Graphene behind the air classifier removal copper powder.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 10nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 54: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be undertaken by following step: by weight percentage with 1 part of Graphite Powder 99,10 ~ 20 parts of lime carbonate, 5 ~ 20 parts of zirconium whites, 300 part 1, the mixing of 4-butyleneglycol is placed in the clarifixator, add polyacrylic acid (PAA) again, the polyacrylic acid consumption is 1,2% of 4-butyleneglycol volume, mechanically peel 0.1 ~ 10h, filter, after removing zirconium white with whizzer then, with mass concentration is that 10% ~ 30% HCl removes lime carbonate, after the filtration, obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 10nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 55: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: the silicon oxide that is 7nm with 1 part of Graphite Powder 99,5 parts of particle diameters and 300 part 1 by weight percentage, the mixing of 3-butyleneglycol is placed in the clarifixator, peeled off 0.5 ~ 100 hour with 5000 rev/mins speed mechanical, filter and obtain Graphene and SiO 2Mixture, add mass percent concentration and be 5% HF dissolving SiO 2, filter, wash; Promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 56: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for graphene oxide to be finished by following step: by weight percentage with 1 part of graphite oxide powder, 40 parts of CaCO 3Be placed in the oscillating mill with 200 parts of Virahols mixing, mechanically peel 0.5 ~ 100 hour filters and obtains graphene oxide and CaCO 3Mixture, add mass percent concentration and be 10% ~ 30% HCl dissolving CaCO 3, filter, wash; Promptly obtain graphene oxide.
The present embodiment method makes graphene oxide and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and its productive rate is more than 90%.
Embodiment 57: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: one, take by weighing 1 part of Graphite Powder 99,80 ~ 200 parts of potassium primary phosphates and 100 ~ 400 parts of water by weight percentage, under 90 ℃ of conditions potassium primary phosphate being put into Graphite Powder 99 after soluble in water, obtain mixture and place sand mill then; Two, in 0.1 ~ 10 hour said mixture being cooled to 20 ~ 50 ℃ utilizes sand mill to peel off with 1000 ~ 10000 rev/mins speed simultaneously; Three, be warming up to 90 ℃ then, in 0.1 ~ 10 hour, be cooled to 20 ~ 50 ℃ again and utilize sand mill to peel off simultaneously with 1000 ~ 10000 rev/mins speed; Four, the operation of repeating step two and step 3 is 0 ~ 20 time, continues mechanically peel 0.1 ~ 100 hour, obtains the mixture of Graphene-potassium primary phosphate-water, and heated mixt to 100 ℃ (purpose is the dissolving phosphoric acid potassium dihydrogen) obtains Graphene after filtering, cleaning.
The whole process of the described method of present embodiment is pollution-free, is the synthetic route of a green.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 58: the method that the present embodiment high-efficiency and low-cost mechanical stripping prepares Graphene is to finish by following step: one, take by weighing 1 part of Graphite Powder 99,80 ~ 200 portions of sucrose and 100 ~ 400 parts of water by weight percentage, under 90 ℃ of conditions sucrose being put into Graphite Powder 99 after soluble in water, obtain mixture and place sand mill then; Two, in 0.1 ~ 10 hour said mixture being cooled to 25 ℃ utilizes sand mill to peel off with 1000 ~ 10000 rev/mins speed simultaneously; Three, be warming up to 90 ℃ then, in 0.1 ~ 10 hour, be cooled to 25 ℃ again and utilize sand mill to peel off simultaneously with 1000 ~ 10000 rev/mins speed; Four, the operation of repeating step two and step 3 is 0 ~ 20 time, continues mechanically peel 0.1 ~ 100 hour, obtains the mixture of Graphene-sucrose-water, and heated mixt to 100 ℃ (purpose is a dissolving saccharose) obtains Graphene after filtering, cleaning.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2400W/mK, and its productive rate is more than 90%.
Embodiment 59: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: 1 part of Graphite Powder 99,50 ~ 1000 parts of NaCl and 200 ~ 4000 parts of ethanol are mixed being placed in the clarifixator by weight percentage, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed, filter the mixture that obtains Graphene and NaCl then, add 500 ~ 3000 parts of water (being used to dissolve NaCl), filter, water cleans; Promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 60: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: by weight percentage 1 part of Graphite Powder 99,50 ~ 1000 parts of KCl and 50 ~ 1500 parts of ethanol and 50 ~ 1500 parts of glycerol mixing are placed in the clarifixator, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed, filter the mixture that obtains Graphene and KCl then, add 500 ~ 3000 parts of water (being used to dissolve KCl), filter, water cleans; Promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 61: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: by weight percentage with the Al of 1 part of Graphite Powder 99,150 parts of about 500nm of diameter 2O 3Be placed in the oscillating mill with 200 parts of Virahols mixing, peeled off 0.5 ~ 100 hour, filter and obtain Graphene and Al 2O 3Mixture, remove Al with static classified filtering equipment 2O 3Promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 62: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: iron powder and 200 parts of Virahols mixing with 1 part of Graphite Powder 99,100 parts of about 1 μ m of diameter by weight percentage are placed in the oscillating mill, peeled off 0.5 ~ 100 hour, filtration obtains the mixture of Graphene and iron powder, washes, removes iron powder with magnetic field separation equipment; Promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 63: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: one, take by weighing 1 part of Graphite Powder 99,50 ~ 2000 parts of urea and 100 ~ 2000 parts of ethanol by weight percentage, under 65 ℃ of conditions, urea is put into the ethanol back then and add Graphite Powder 99, obtain mixture and place clarifixator; Two, in 0.1 ~ 10 hour said mixture being cooled to 20 ℃ utilizes clarifixator to peel off with 1000 ~ 10000 rev/mins speed simultaneously; Three, be warming up to 60 ℃ then, in 0.1 ~ 10 hour, be cooled to 30 ℃ again and utilize sand mill to peel off simultaneously with 1000 ~ 10000 rev/mins speed; Four, the operation of repeating step two and step 3 is 0 ~ 9 time, continued mechanically peel 0.1 ~ 100 hour, obtain Graphene-urea-alcoholic acid mixture, 35 ℃ ~ 55 ℃ filtrations, get the mixture of Graphene-urea, in environment heating more than 200 ℃ remaining urea is decomposed rapidly, obtain finely disseminated Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 64: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: one, take by weighing 1 part of Graphite Powder 99,200 ~ 2000 parts of CH by weight percentage 3COONH 4With 100 ~ 1000 parts of ethanol, under 65 ℃ of conditions with CH 3COONH 4Put into Graphite Powder 99 after being dissolved in the ethanol, obtain mixture and place clarifixator; Two, in 0.1 ~ 10 hour said mixture being cooled to 20 ℃ utilizes clarifixator to peel off with 1000 ~ 10000 rev/mins speed simultaneously; Three, be warming up to 60 ℃ then, in 0.1 ~ 10 hour, be cooled to 20 ~ 50 ℃ again and utilize sand mill to peel off simultaneously with 1000 ~ 10000 rev/mins speed; Four, the operation of repeating step two and step 3 is 0 ~ 9 time, continues mechanically peel 0.1 ~ 100 hour, obtains Graphene-CH 3COONH 4-alcoholic acid mixture 35 ℃ ~ 55 ℃ filtrations, gets Graphene-CH 3COONH 4Mixture, make CH in environment heating more than 200 ℃ 3COONH 4Decompose rapidly, obtain finely disseminated Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 92%.
Embodiment 65: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: copper powder and 150 parts of Virahols mixing with 1 part of Graphite Powder 99,200 parts of about 100nm of diameter by weight percentage are placed in the oscillating mill, peeled off 0.5 ~ 100 hour, filtration obtains the mixture of Graphene and copper powder, washes, removes copper powder with air classifier; Promptly obtain Graphene.
The present embodiment method makes the Graphene that Graphene has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 66: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: by weight percentage with the zirconia powder of 1 part of Graphite Powder 99,200 parts of about 200nm of diameter and 500 part 1, the mixing of 4-butyleneglycol is placed in the clarifixator, 5000 rev/mins speed was peeled off 0.5 ~ 100 hour, filtration obtains the mixture of Graphene and zirconia powder, washes, removes zirconia powder with whizzer; Promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 67: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for graphene oxide to be finished by following step: the silicon oxide that is 7nm with 1 part of graphite oxide powder, 4 parts of particle diameters and 200 part 1 by weight percentage, the mixing of 3-butyleneglycol is placed in the clarifixator, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed, filter and obtain graphene oxide and SiO 2Mixture, add 5%HF dissolving SiO 2, filtering separation; Promptly obtain graphene oxide.
The present embodiment method makes graphene oxide and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and its productive rate is more than 90%.
Embodiment 68: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for graphene oxide to be finished by following step: the mixed solution of 1 part of graphite oxide powder, 50 ~ 1000 parts of NaCl and 500 ~ 5000 parts of octadecanes and decyl alcohol (volume ratio 1:10) is mixed being placed in the clarifixator by weight percentage, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed, filter the mixture that obtains graphene oxide and NaCl then, add 500 ~ 3000 parts of water dissolution NaCl, filter, water cleans; Promptly obtain graphene oxide.
The present embodiment method makes graphene oxide and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and its productive rate is more than 90%.
Embodiment 69: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be undertaken by following step: the silicon oxide that is 7nm with 1 part of Graphite Powder 99,5 ~ 10 parts of particle diameters and 200 parts of polymethyl acrylates mix and are placed in the three-roller by weight percentage, mechanically peel 4 ~ 50 hours, dissolve polymethyl acrylate with butylacetate, filter, dissolve SiO with 5%HF 2, obtain Graphene after the filtration.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 10nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 70: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for graphene oxide to be undertaken by following step: 1 part of graphite oxide powder, 5 ~ 50 sodium-chlor and 200 parts of polymethyl acrylates are mixed being placed in the three-roller by weight percentage, mechanically peel 4 ~ 100 hours, dissolve polymethyl acrylate with butylacetate, filter, water dissolving sodium-chlor obtains graphene oxide after the filtration.Wherein said liquid-working-medium is a macromolecular compound.
The present embodiment method makes graphene oxide and has individual layer or multilayered structure, and thickness is in 0.355 ~ 10nm scope, and its productive rate is more than 90%.
Embodiment 71: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be undertaken by following step: 1 part of expanded graphite powder, 5 ~ 50 sodium-chlor and 200 parts of polymethyl acrylates are mixed being placed in the three-roller by weight percentage, mechanically peel 4 ~ 100 hours, dissolve polymethyl acrylate with butylacetate, filter, 50 ~ 500 parts of water dissolution sodium-chlor of water obtain Graphene after the filtration.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 10nm scope, and electric conductivity is 10 2More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 72: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be undertaken by following step: 1 part of expansible black lead powder, 5 ~ 20 parts of sodium-chlor and 300 parts of polymethyl acrylates are mixed being placed in the three-roller by weight percentage, mechanically peel 2 ~ 50 hours, dissolve polymethyl acrylate with butylacetate, filter, 50 ~ 500 parts of water dissolution sodium-chlor of water obtain Graphene after the filtration.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 10nm scope, and electric conductivity is 10 2More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 73: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be undertaken by following step: 1 part of Graphite Powder 99,5 ~ 20 parts of sodium-chlor, 2 ~ 20 parts of copper powders, 300 parts of ethylene glycol and 50 parts of acetone are mixed being placed in the clarifixator by weight percentage, mechanically peel 0.1 ~ 100h, filter, 50 ~ 500 parts of water dissolution sodium-chlor of water, after the filtration, then with obtaining Graphene behind the air classifier removal copper powder.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 10nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 74: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be undertaken by following step: by weight percentage with 1 part of Graphite Powder 99,10 ~ 20 parts of lime carbonate, 5 ~ 20 parts of zirconium whites, 300 part 1, the mixing of 4-butyleneglycol is placed in the clarifixator, mechanically peel 0.1 ~ 10h, filter, after removing zirconium white with whizzer then, with mass concentration is that 10% ~ 30% HCl removes lime carbonate, after the filtration, obtains Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 10nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 75: the method that high-efficiency and low-cost mechanical stripping prepares Graphene or graphene oxide in the present embodiment is 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.
The method of present embodiment utilizes automation at carbon materials powder (Graphite Powder 99, the graphite oxide powder, expanded graphite or unexpansive graphite), in the system that solid particulate and working medium are formed the carbon materials powder is carried out mechanically peel, obtain the composite granule of Graphene and solid particulate, again with filtering, distillation, underpressure distillation, pickling, washing, centrifugal, electric field (as utilizing electrostatic separator etc.), magnetic field means such as (as utilizing high gradient magnetic separator etc.) or special fractional separation equipment are (as the linear vibrating screen stage equipment, air classifier, tripod pendulum type batch centrifugal-SS450, multistage grading machine etc.) from above-mentioned mixture, obtain Graphene (graphene oxide).Present embodiment utilizes automation to replace manual stripping process, thereby improves charge stripping efficiency; Utilize a large amount of small solid particulate up-stripping processes, increase the contact area of stripping process greatly and peel off number of times, by shearing and the effect of impact of solid particulate, make graphite experience a large amount of stripping processes at short notice, thereby significantly improve charge stripping efficiency graphite; Liquid or gas working dielectric play an important role to peeling off, working medium can be peeled off required strength to solid particulate and Graphite Powder 99 transmission on the one hand, on the other hand, working medium has certain dissemination to Graphene and solid particulate, hinder compound between the Graphene, in addition, working medium can absorb and conduct the heat that produces in the mechanically peel process, avoids the overheated Graphene that makes to produce defective.Small solid particulate with the graphite knockout process in Graphene is not done great damage, and only open the Van der Waals force of interlayer, guarantee that stripping process carries out between graphene layer, thereby finally obtain individual layer and thin layer Graphene or graphene oxide.By adjusting the number of plies of splitting time may command Graphene (or graphene oxide), can obtain individual layer or thin layer (2 ~ 10 layers) Graphenes (or graphene oxide), the productive rate of producing Graphene (or graphene oxide) is all more than 90%, and thickness is in 0.355 ~ 5nm scope; The product yield height has improved utilization ratio of raw materials, and the efficient height of producing, and then has reduced production cost.The present embodiment method is suitable for industrialized mass Graphene and graphene oxide.The present embodiment method obtains the electric conductivity of Graphene 10 3More than the S/cm, thermal conductivity is more than 2000W/mK.
Embodiment 76: what present embodiment and embodiment 75 were different is: 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.Other step is identical with embodiment 75 with parameter.
The described gas working dielectric of present embodiment is in the gas mixture, presses between all gases working medium arbitrarily than mixing.
Embodiment 77: present embodiment and embodiment and embodiment 75 or 76 different are: the particle diameter of solid particulate is 5nm ~ 100nm.Other step is identical with embodiment 75 or 76 with parameter.
Embodiment 78: what present embodiment and embodiment and embodiment 77 were different is: the particle diameter of solid particulate is 200nm ~ 500nm.Other step is identical with embodiment 77 with parameter.
Embodiment 79: what present embodiment and embodiment and embodiment 77 were different is: the particle diameter of solid particulate is 1 μ m ~ 20 μ m.Other step is identical with embodiment 77 with parameter.
Embodiment 80: what present embodiment and embodiment and embodiment 77 were different is: the particle diameter of solid particulate is 50 μ m ~ 80 μ m.Other step is identical with embodiment 77 with parameter.
Embodiment 81: what present embodiment was different with one of embodiment 75 to 80 is: weight ratio 1:0.1 ~ 10000 of described carbon materials powder and solid particulate.Other step is identical with one of embodiment 75 to 80 with parameter.
Embodiment 82: what present embodiment and embodiment 81 were different is: weight ratio 1:10 ~ 100 of described carbon materials powder and solid particulate.Other step is identical with embodiment 81 with parameter.
Embodiment 83: what present embodiment and embodiment 81 were different is: weight ratio 1:200 ~ 500 of described carbon materials powder and solid particulate.Other step is identical with embodiment 81 with parameter.
Embodiment 84: what present embodiment and embodiment 81 were different is: weight ratio 1:200 ~ 800 of described carbon materials powder and solid particulate.Other step is identical with embodiment 81 with parameter.
Embodiment 85: what present embodiment was different with one of embodiment 75 to 84 is: 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, brometo de amonio, ammonium chromate, sodium bicarbonate, ammonium iodide, ammonium sulfate, ammonium sulphite, ammonium tartrate, ammonium thiocyanate, barium iodide, nitrate of baryta, Calcium Bromide, calcium iodide, nitrocalcite, calcium nitrite, potassium acetate, potassium bromate, Potassium Bromide, salt of wormwood, 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, vitriolate of tartar, Potassium Thiosulphate, lithium acetate, lithiumbromide, sodium-chlor, lithium chloride, lithium formate, lithium iodide, Tai-Ace S 150, magnesium acetate, magnesium bromide, magnesium iodide, sal epsom, sodium acetate, yellow soda ash, SODIUM PHOSPHATE, MONOBASIC, sodium formiate, sodium acetate, 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 in the glass powder.Other step is identical with one of embodiment 75 to 84 with parameter.
When the present embodiment solid particulate is mixture, press between various solid particulates arbitrarily than mixing.Above-mentioned solid particulate can adopt following method to remove respectively according to its character:
The first kind: can be dissolved in the solid particulate of acid, alkaline solution, for example: Al, Cu, Zn, SnO, ZnO, B 2O 3, SiO 2, NaHCO 3, CaCO 3, CaO etc., can remove by pickling or alkali cleaning;
Second class: room temperature-high temperature (for example 100 ℃) solubility with temperature changes material greatly, for example: bicarbonate of ammonia, primary ammonium phosphate, ammonium oxalate, potassium primary phosphate, Repone K, yellow prussiate of potash, vitriolate of tartar, yellow soda ash, SODIUM PHOSPHATE, MONOBASIC, sodium sulfate, sodium phosphate, sucrose, urea, adopt low-temperature working then to heat up the solid particulate dissolving removed;
The 3rd class: the very big material of dissolubility difference in different solvents, for example: most of ionic compounds are (as NaCl, K 2CO 3, KCl, AlCl 3) solubleness is big and at ethanol, benzene, CCl in water 4Less Deng solubleness in the organic solvent, adopt and in organic working medium, to work and the method for after washing is removed;
The 4th class: segregative material under electric field, the action of a magnetic field, for example: Al 2O 3, CaCO 3, Fe 2O 3, Fe 3O 4, Fe etc., remove by electric field, magnetic field, remove as adopting static classified filtering equipment and magnetic field separation equipment;
The 5th class: volatile during heat, distillation, decompose the solid particulate remove, as sucrose, I 2, urea, NH 4NO 3, NH 4HCO 3, CH 3COONH 4Deng, adopt the way of heat to remove;
The 6th class: heavy solid particulate, as zirconium white, vanadium, chromium, tungsten etc., adopt fractional separation equipment (as linear vibrating screen stage equipment, air classifier, tripod pendulum type batch centrifugal-SS450, multistage grading machine (step Electronics Co., Ltd. is opened in Shenzhen)) to remove.
Embodiment 86: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: in micronizer mill, the silicon oxide that is 7nm with the air and the particle diameter of humidity 90% carries out mechanically peel to 1 part of Graphite Powder 99, silicon oxide and Graphite Powder 99 mass ratio are 4 ~ 20:1, and the adding mass percent concentration is 5% HF dissolving SiO 2, filter; Promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2105W/mK, and its productive rate is more than 91%.
Embodiment 87: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be undertaken by following step: in airflow milling, be the Fe of 7nm ~ 1 μ m with the air and the particle diameter of humidity 90% 2O 3Graphite Powder 99 was carried out mechanically peel 0.1 ~ 20 hour, Fe 2O 3With the Graphite Powder 99 mass ratio be 40 ~ 1000:1, utilize static classified filtering equipment or magnetic field separation equipment to remove Fe then 2O 3Promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2050W/mK, and its productive rate is more than 93%.
Embodiment 88: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for graphene oxide to be undertaken by following step: in airflow milling, be the Fe of 7nm with nitrogen and particle diameter 2O 3The graphite oxide powder was carried out mechanically peel 0.1 ~ 20 hour, Fe 2O 3With graphite oxide powder mass ratio be 40:1, utilize static classified filtering equipment or magnetic field separation equipment to remove Fe then 2O 3Promptly obtain graphene oxide.
The present embodiment method makes graphene oxide and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and its productive rate is more than 90%.
Embodiment 89: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be undertaken by following step: in airflow milling, with argon gas and urea the expanded graphite powder was carried out mechanically peel 0.1 ~ 20 hour, urea and expanded graphite powder mass ratio are 200 ~ 2000:1, add heat abstraction urea then under 160 ~ 200 ℃ of conditions and promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 2More than the S/cm, thermal conductivity is more than 2150W/mK, and its productive rate is more than 90%.
Embodiment 90: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: in airflow milling, with the air and the CaCO of humidity 90% 3Expanded graphite was carried out mechanically peel 0.1 ~ 20 hour, CaCO 3With the Graphite Powder 99 mass ratio be 200 ~ 2000:1, mass percent concentration is 10% ~ 30% HCl dissolving CaCO then 3, filtration, washing promptly obtain Graphene.
The present embodiment method makes the Graphene that Graphene has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 2More than the S/cm, thermal conductivity is more than 2100W/mK, and its productive rate is more than 90%.
Embodiment 91: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: in airflow milling, with helium and potassium primary phosphate Graphite Powder 99 was carried out mechanically peel 0.1 ~ 20 hour, potassium primary phosphate and Graphite Powder 99 mass ratio are 200 ~ 2000:1, add 100 ℃ of suitable quantity of water post-heating, filter the back cleaning and promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2250W/mK, and its productive rate is more than 90%.
Embodiment 92: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: in airflow milling, with nitrogen and sucrose Graphite Powder 99 was carried out mechanically peel 0.1 ~ 20 hour, sucrose and Graphite Powder 99 mass ratio are 500 ~ 1000:1, add water post-heating to 100 ℃, filter the back and clean and promptly obtain Graphene.
The present embodiment method makes the Graphene that Graphene has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2200W/mK, and its productive rate is more than 90%.
Embodiment 93: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: in airflow milling, with nitrogen and NaCl Graphite Powder 99 was carried out mechanically peel 0.5 ~ 20 hour, NaCl and Graphite Powder 99 mass ratio are 500 ~ 1000:1, add 500 ~ 3000 parts of water (being used to dissolve NaCl), filter washing; Promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2100W/mK, and its productive rate is more than 90%.
Embodiment 94: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: in airflow milling, with nitrogen and KCl Graphite Powder 99 was carried out mechanically peel 0.5 ~ 20 hour, KCl and Graphite Powder 99 mass ratio are 500 ~ 1000:1, add 500 ~ 3000 parts of water (being used to dissolve KCl), filter washing; Promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 95: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: in airflow milling, with nitrogen and Al 2O 3Graphite Powder 99 was carried out mechanically peel 0.5 ~ 20 hour, Al 2O 3With the Graphite Powder 99 mass ratio be 50 ~ 1000:1, utilize static classified filtering equipment to remove Al 2O 3Promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2050W/mK, and its productive rate is more than 90%.
Embodiment 96: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: in airflow milling, with nitrogen and iron powder Graphite Powder 99 was carried out mechanically peel 0.5 ~ 20 hour, iron powder and Graphite Powder 99 mass ratio are 10 ~ 2000:1, remove iron powder with magnetic field separation equipment; Promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 97: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: in airflow milling, with nitrogen and urea the expanded graphite powder was carried out mechanically peel 0.5 ~ 20 hour, urea and Graphite Powder 99 mass ratio are 20 ~ 1000:1, filter, wash, 200 ℃ of environment heating remaining urea is decomposed rapidly, obtain finely disseminated Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 2More than the S/cm, thermal conductivity is more than 2300W/mK, and its productive rate is more than 90%.
Embodiment 98: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: in airflow milling, with nitrogen and urea the expanded graphite powder was carried out mechanically peel 0.5 ~ 20 hour, urea and Graphite Powder 99 mass ratio are 10 ~ 500:1,200 ℃ of environment heating urea is decomposed rapidly, obtain finely disseminated Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 2More than the S/cm, thermal conductivity is more than 2000W/mK, and its productive rate is more than 90%.
Embodiment 99: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for Graphene to be finished by following step: in airflow milling, with nitrogen and copper powder Graphite Powder 99 was carried out mechanically peel 0.5 ~ 20 hour, copper powder and Graphite Powder 99 mass ratio are 50 ~ 1000:1, remove copper powder with air classifier; Promptly obtain Graphene.
The present embodiment method makes Graphene and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and electric conductivity is 10 3More than the S/cm, thermal conductivity is more than 2100W/mK, and its productive rate is more than 90%.
Embodiment 100: the present embodiment high-efficiency and low-cost mechanical stripping prepares the method for graphene oxide to be finished by following step: in airflow milling, air and zirconia powder with humidity 90% carried out mechanically peel 0.5 ~ 20 hour to the graphene oxide powder, zirconia powder and graphite oxide powder mass ratio are 50 ~ 1000:1, remove zirconia powder with the pneumatic separation machine; Promptly obtain graphene oxide.
The present embodiment method makes graphene oxide and has individual layer or multilayered structure, and thickness is in 0.355 ~ 5nm scope, and its productive rate is more than 90%.
 

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.
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Application publication date: 20100901