CN101857221A

Movatterモバイル変換

Info

Publication number: CN101857221A
Application number: CN 201010179118
Authority: CN
Inventors: 王黎东; 费维栋
Original assignee: Harbin Institute of Technology Shenzhen
Current assignee: Harbin Institute of Technology Shenzhen
Priority date: 2010-05-21
Filing date: 2010-05-21
Publication date: 2010-10-13

Abstract

高效率制备石墨烯复合物或氧化石墨烯复合物的方法，它涉及石墨烯复合物或氧化石墨烯复合物制备方法。本发明同时解决了石墨烯或氧化石墨烯本身易复合、现有方法制备石墨烯复合物或氧化石墨烯复合物工艺步骤多、成本较高、分散困难的问题。本发明采用机械剥离方法获得石墨烯复合物或氧化石墨烯复合物。本发明使用自动机械，用固体颗粒辅助剥离，极大的增加剥离过程的接触面积和剥离次数，通过剪切和撞击作用，使碳素材料粉在短时间内经历大量的剥离过程，从而显著提高剥离效率，同时达到与复合物之间均匀分散的目的，该方法适于工业化大批量生产石墨烯复合物或氧化石墨烯复合物。A method for preparing graphene composites or graphene oxide composites with high efficiency relates to a method for preparing graphene composites or graphene oxide composites. The invention simultaneously solves the problems that the graphene or graphene oxide itself is easy to compound, and the existing method for preparing the graphene compound or the graphene oxide compound has many process steps, high cost and difficult dispersion. The invention adopts a mechanical exfoliation method to obtain graphene composites or graphene oxide composites. The invention uses automatic machinery and solid particles to assist the peeling, which greatly increases the contact area and peeling times of the peeling process. Through shearing and impact, the carbon material powder undergoes a large number of peeling processes in a short time, thereby significantly improving At the same time, it achieves the purpose of uniform dispersion with the composite. This method is suitable for industrial mass production of graphene composites or graphene oxide composites.

Description

High-level efficiency prepares the method for graphene complex or graphene oxide mixture

Technical field

The present invention relates to the preparation method of graphene complex or graphene oxide mixture.

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.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.Graphene and graphene oxide have caused one research boom in worldwide subsequently.

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 large²/ 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 silicon⁵Cm²/ (V.s)), micron-sized mean free path and big coherence length are at room temperature arranged, so Graphene is the ideal material of nano-device; Graphene has good electrical conductivity, and its electronic motion speed has reached 1/300 of the light velocity, and 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.

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.The dilatometry of graphite oxide and reduction method can prepare graphene oxide and Graphene in a large number in the aforesaid method, but because the effect of process strong oxidizer, defective is more in the structure, and over-all properties descends; Method such as crystal epitaxy, chemical vapour deposition is fit to the large-area Graphene of preparation, be not suitable for preparing many fields needs in enormous quantities, (every area is less than 1mm for small area²) Graphene or graphene oxide.

The general method that Graphene (graphene oxide) is used is to prepare Graphene earlier, then it is used separately or with the use that is combined with each other of other material.And Graphene (graphene oxide) and other material are combined with each other, and to use be very common situation.Also face problem easily compound between the Graphene, difficulties in dispersion during actual the use.

Summary of the invention

The invention provides the method that high-level efficiency prepares graphene complex or graphene oxide mixture, to solve Graphene or graphene oxide itself is easily compound, existing method prepares graphene complex or graphene oxide mixture processing step is many, cost is higher, the problem of difficulties in dispersion.

The present invention realizes by following proposal:

Scheme one: high-level efficiency prepares the method for graphene complex or graphene oxide mixture and is undertaken by following step: carry out mechanically peel after one, carbon materials powder, solid particulate and liquid-working-medium being mixed; Two, remove the material of non-target mixture: remove liquid-working-medium, and that solid particulate keeps at least is a kind of, promptly obtains graphene complex or graphene oxide mixture; Wherein, the median size of described solid particulate is at 1nm ~ 100 μ m, and described liquid-working-medium is that 10 ~ 73mN/m and viscosity are 1 * 10 at the working temperature lower surface tension force of mechanically peel⁹MPas adds dispersion agent in the mechanically peel process, dispersant dosage is 0 ~ 20% of a liquid-working-medium.

Scheme two: high-level efficiency prepares the method for graphene complex or graphene oxide mixture and is undertaken by following step: carry out mechanically peel after one, carbon materials powder, solid particulate and liquid-working-medium being mixed; Two, remove the material of non-target mixture: solid particulate is all removed or is kept a kind of at least; Promptly obtain graphene complex or graphene oxide mixture; Wherein liquid-working-medium is that 10 ~ 73mN/m and viscosity are 1 * 10 at the working temperature lower surface tension force of mechanically peel⁹MPas, the median size of described solid particulate adds dispersion agent at 1nm ~ 100 μ m in the mechanically peel process, and dispersant dosage is 0 ~ 20% of a liquid-working-medium, and liquid-working-medium is a macromolecular compound.

Scheme three: high-level efficiency prepares the method for graphene complex or graphene oxide mixture and is undertaken by following step: one, 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, and splitting time is more than 5 minutes; Two, remove the material of non-target mixture: solid particulate keeps a kind of at least; Promptly obtain graphene complex or graphene oxide mixture.

The carbon materials powder is Graphite Powder 99, expanded graphite, expansible black lead, intercalated graphite or graphite oxide powder described in above-mentioned three schemes; Described solid particulate is a lithium, beryllium, boron, sodium, magnesium, aluminium, silicon, phosphorus, sulphur, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, bromine, rubidium, strontium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, lawrencium, tantalum, tungsten, rhenium, iridium, platinum, gold, plumbous, bismuth, boron oxide, silicon oxide, zirconium white, aluminum oxide, lime carbonate, Vanadium Pentoxide in FLAKES, magnesium oxide, titanium dioxide, zinc oxide, stannic oxide, ferric oxide, Z 250, zirconium boride 99.5004323A8ure, lanthanum boride, titanium boride, tantalum boride, chromium boride, tungsten boride, silicon carbide, norbide, aluminium nitride, magnesium nitride, titanium nitride, Sodium Fluoride, Neutral ammonium fluoride, Cadmium Sulfide, indium phosphide, bicarbonate of ammonia, brometo de amonio, ammonium chromate, primary ammonium phosphate, ammonium formiate, ammonium hydrogen phosphate, ammonium iodide, ammonium nitrate, ammonium oxalate, ammoniumper chlorate, ammonium sulfate, ammonium sulphite, ammonium tartrate, ammonium thiocyanate, barium chlorate, ammonium acetate, bariumchloride, hydrated barta, barium iodide, nitrate of baryta, barium perchlorate, barium sulphide, Calcium Bromide, calcium iodide, nitrocalcite, calcium nitrite, cobaltous bromide, cobaltous chlorate, cobalt chloride, 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, Potassium Iodate, potassiumiodide, saltpetre, potassium oxalate, potassium permanganate, 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, Manganese dibromide, Manganous chloride tetrahydrate, sodium acetate, sodium bromate, yellow soda ash, sodium chlorate, SODIUM PHOSPHATE, MONOBASIC, sodium formiate, sodium iodate, 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, molybdic oxide, Ripon, pure aluminium silicate, ferric metasilicate, Calucium Silicate powder, Magnesium Silicate q-agent, potassium silicate, water glass, iron titanate, calcium titanate, lead titanate, Pb-based lanthanumdoped zirconate titanates, the ferrous acid bismuth, Scium trioxide, chromic oxide, Manganse Dioxide, cobalt oxide, nickel oxide, cupric oxide, zinc oxide, yttrium oxide, zirconium dioxide, Niobium Pentxoxide, molybdic oxide, seven oxidations, two technetiums, ruthenium dioxide, rhodium oxide, palladous oxide, silver suboxide, Cadmium oxide, lutecium oxide, hafnium oxide, tantalum pentoxide, tungstic oxide, four rhenium oxides, perosmic anhydride, iridium dioxide, platinum dioxide, gold trioxide, the oxidation lawrencium, Vanadium Pentoxide in FLAKES, molybdic oxide, hexagonal boron nitride, the metal dithionite thing, metal selenide, metal telluride, Hofmann type compound: Ni (CN)₂NH₃, kaolinite, dickite, agalmatolite, hydrotalcite (LDHs,

M^IIIBe ionic radius and the approaching trivalent metal ion of magnesium ion; A^N-Be negatively charged ion), houghite (

, M^II=Mg, Fe, Co, Ni, Mn, Zn; M^III=Al, Fe, Cr, Mn, V; A^N-Be negatively charged ion), polynary sulfide, transition metal oxide, NaTiO₂, NaVO₂, NaCrO₂, NaMnO₂, NaFeO₂, NaCoO₂, NaNiO₂, KTiO₂, KVO₂, KCrO₂, KMnO₂, KFeO₂, KCoO₂, KNiO₂, a kind of or wherein several composition in the alkali-metal titanate, alkali-metal niobate, alkali-metal niobate-titanate, uranyl vanadate, graphite oxide, graphite intercalation compound, montmorillonite, saponite, vermiculite, rhombspar, stratiform tertiary iron phosphate, cadmium telluride, indium arsenide, gallium antimonide, copper-indium-galliun-selenium, Cadmium Sulfide, CNT (carbon nano-tube), soccerballene, activated carbon granule, MCMB, polymer microsphere, glass powder; Described polynary sulfide is NaCrS₂, NaVS₂, KCrS₂, KVS₂, ACuFeS₂, NaCuFeS₂, KCuFeS₂, Li₂FeS₂Or K₂Pt₄S₆, the metal in described metal dithionite thing, metal selenide and the metal telluride is Sn, Ti, Zr, Hf, V, Nb, Ta, Mo or W.

Aforesaid method of the present invention utilizes automation in the system that carbon materials powder (Graphite Powder 99, graphite oxide powder, intercalated graphite, expanded graphite or expansible black lead), solid particulate and working medium are formed the carbon materials powder to be carried out mechanically peel, keep at least a solid particulate, obtain Graphene (or graphene oxide) mixture.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; Peel off and reach aim of even dispersion simultaneously, and prevent compound between Graphene (graphene oxide), 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 (or graphene oxide) 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 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.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), method of the present invention is obtained every area of Graphene (or graphene oxide) less than 1mm², productive rate is 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 complex or graphene oxide mixture.The graphene complex or the graphene oxide mixture of the present invention's preparation can be widely used in electrode material of lithium battery, ultracapacitor, solar cell, hydrogen storage material, field emmision material, high performance carbon cellulosic material raw material, performance resins based composites, high-performance metal based composites, high-performance ceramic based composites, rubber functional additive, caking agent functional additive, large-scale microwave tube structure and fields such as electro-conductive material, change-over switch, contact and spot weld electrode.

Embodiment

Embodiment one: the method that high-level efficiency prepares graphene complex or graphene oxide mixture in the present embodiment is undertaken by following step: one, will the carbon materials powder, solid particulate and liquid-working-medium carry out mechanically peel after mixing; Two, remove the material of non-target mixture: remove liquid-working-medium, and that solid particulate keeps at least is a kind of, promptly obtains graphene complex or graphene oxide mixture; Wherein, the median size of described solid particulate is at 1nm ~ 100 μ m, described carbon materials powder is Graphite Powder 99, expanded graphite, expansible black lead, intercalated graphite or graphite oxide powder, and described liquid-working-medium is that 10 ~ 73mN/m and viscosity are 1 * 10 at the working temperature lower surface tension force of mechanically peel⁹MPas adds dispersion agent in the mechanically peel process, 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.Dispersion agent 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 in the present embodiment, 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 present embodiment method 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; Peel off and reach aim of even dispersion simultaneously, and prevent compound between Graphene (graphene oxide), liquid-working-medium plays an important role to peeling off, working medium can (required strength be peeled off in transmission with Graphite Powder 99 to solid particulate 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 (or graphene oxide) 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 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.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), the present embodiment method is obtained every area of Graphene (or graphene oxide) less than 1mm², productive rate is 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 present embodiment method is suitable for industrialized mass graphene complex or graphene oxide mixture.

Embodiment two: what present embodiment and embodiment one were different is: 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 alcoholic solution of organic dye, the aqueous solution of alcohol, the alcoholic solution of alkanes, the alcoholic solution of ketone, the aqueous solution of amine, the alkane solution or the macromolecular compound of aromatics, wherein said macromolecular compound are 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 one with parameter.

Adopt water in the present embodiment, alcohols, aromatics, ketone, amine, ionic liquid, alkanes, heterogeneous ring compound, dithiocarbonic anhydride, tetracol phenixin, gasoline, vegetables oil, diesel oil, wax, the alcoholic solution of organic dye, the aqueous solution of alcohol, the alcoholic solution of alkanes, the alcoholic solution of ketone, the aqueous solution of amine, the alkane solution of aromatics is made liquid-working-medium and is adopted 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 macromolecular compound is made liquid medium and adopted mill, Banbury mixer, clarifixator, colloidal mill, three-roller or screw extrusion press carry out mechanically peel.

Embodiment three: what present embodiment and embodiment two were different is: described alcohols is ethanol, ethylene glycol, 1,2-butyleneglycol, 1,3 butylene glycol, 1, a kind of or wherein several mixing in 4-butyleneglycol, glycerol, butanols and the Virahol.Other step is identical with embodiment two with parameter.

When alcohols is mixture in the present embodiment, press between various alcohols arbitrarily than mixing.

Embodiment four: what present embodiment and embodiment two were different is: described aromatics is benzene, toluene, naphthalene or anthracene.Other step is identical with embodiment two with parameter.

Embodiment five: what present embodiment and embodiment two were different is: described ketone is acetone or Ν-methyl-2-pyrrolidone.Other step is identical with embodiment two with parameter.

Embodiment six: what present embodiment and embodiment two were different is: described amine is methylformamide, N, dinethylformamide or N, N-diethylformamide.Other step is identical with embodiment two with parameter.

Embodiment seven: what present embodiment and embodiment two 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 two with parameter.

Embodiment eight: what present embodiment and embodiment two were different is: described alkanes is normal hexane, octane or decane.Other step is identical with embodiment two with parameter.

Embodiment nine: what present embodiment and embodiment two were different is: described heterogeneous ring compound is furans or pyridine.Other step is identical with embodiment two with parameter.

Embodiment ten: what present embodiment and embodiment two 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 two with parameter.

Embodiment 11: what present embodiment and embodiment two 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 two with parameter.

Embodiment 12: what present embodiment and embodiment two 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 two with parameter.

Embodiment 13: what present embodiment and embodiment two were different is: the amine in the aqueous solution of described amine is N-methylformamide or N, dinethylformamide.Other step is identical with embodiment two with parameter.

Embodiment 14: what present embodiment and embodiment two 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 two with parameter.

Embodiment 15: the method that high-level efficiency prepares graphene complex or graphene oxide mixture in the present embodiment is undertaken by following step: one, will the carbon materials powder, solid particulate and liquid-working-medium carry out mechanically peel after mixing; Two, remove the material of non-target mixture: solid particulate is all removed or is kept a kind of at least; Promptly obtain graphene complex or graphene oxide mixture; Wherein, described carbon materials powder is Graphite Powder 99, expanded graphite, expansible black lead, intercalated graphite or graphite oxide powder, and liquid-working-medium is that 10 ~ 73mN/m and viscosity are 1 * 10 at the working temperature lower surface tension force of mechanically peel⁹MPas, the median size of described solid particulate adds dispersion agent at 1nm ~ 100 μ m in the mechanically peel process, and dispersant dosage is 0 ~ 20% of a liquid-working-medium, and liquid-working-medium is a macromolecular compound.

Embodiment 16: what present embodiment and embodiment 15 were different is: described macromolecular compound is a polyethylene, polypropylene, polyvinyl chloride, polystyrene, ABS resin, polyacrylic ester, polyacrylonitrile, polyvinyl alcohol, polyoxyethylene glycol, Vinyl Acetate Copolymer, starch, polyhutadiene, poly-butylbenzene diene, polyaniline, the p-phenylene vinylene, Resins, epoxy, tetrafluoroethylene, nylon, polyimide, polyester, resol, poly-biphenyl, Polybenzoxazine, poly-fluorenes, polypyrrole, Polythiophene, rubber, coal tar, pitch, liquid crystal polymer, xylogen, the combination of one or more of organic fluorine or silicone resin.Other step is identical with embodiment 15 with parameter.

When the present embodiment macromolecular compound is composition, press between various macromolecular compounds arbitrarily than mixing.

Embodiment 17: what present embodiment was different with one of embodiment one to 16 is: weight ratio 1:0.1 ~ 10000 of described carbon materials powder and solid particulate.Other step is identical with one of embodiment one to 16 with parameter.

Embodiment 18: what present embodiment and embodiment 17 were different is: weight ratio 1:1 ~ 2000 of described carbon materials powder and solid particulate.Other step is identical with embodiment 17 with parameter.

Embodiment 19: what present embodiment and embodiment 17 were different is: weight ratio 1:5 ~ 1000 of described carbon materials powder and solid particulate.Other step is identical with embodiment 17 with parameter.

Embodiment 20: what present embodiment and embodiment 17 were different is: weight ratio 1:10 ~ 500 of described carbon materials powder and solid particulate.Other step is identical with embodiment 17 with parameter.

Embodiment 21: what present embodiment and embodiment 17 were different is: weight ratio 1:100 ~ 200 of described carbon materials powder and solid particulate.Other step is identical with embodiment 17 with parameter.

Embodiment 22: what present embodiment was different with one of embodiment one to 21 is: the weight ratio 1:0.1 of described solid particulate and liquid-working-medium ~ 10000.Other step is identical with embodiment one to 21 to parameter.

Embodiment 23: what present embodiment and embodiment 22 were different is: the weight ratio 1:0.2 of described solid particulate and liquid-working-medium ~ 5000.Other step is identical with embodiment 22 with parameter.

Embodiment 24: what present embodiment and embodiment 22 were different is: the weight ratio 1:100 of described solid particulate and liquid-working-medium ~ 2000.Other step is identical with embodiment 24 with parameter.

Embodiment 25: what present embodiment and embodiment 22 were different is: the weight ratio 1:200 of described solid particulate and liquid-working-medium ~ 500.Other step is identical with embodiment 22 with parameter.

Embodiment 26: what present embodiment was different with one of embodiment one to 25 is: described solid particulate is a lithium, beryllium, boron, sodium, magnesium, aluminium, silicon, phosphorus, sulphur, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, bromine, rubidium, strontium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, lawrencium, tantalum, tungsten, rhenium, iridium, platinum, gold, plumbous, bismuth, boron oxide, silicon oxide, zirconium white, aluminum oxide, lime carbonate, Vanadium Pentoxide in FLAKES, magnesium oxide, titanium dioxide, zinc oxide, stannic oxide, ferric oxide, Z 250, zirconium boride 99.5004323A8ure, lanthanum boride, titanium boride, tantalum boride, chromium boride, tungsten boride, silicon carbide, norbide, aluminium nitride, magnesium nitride, titanium nitride, Sodium Fluoride, Neutral ammonium fluoride, Cadmium Sulfide, indium phosphide, bicarbonate of ammonia, brometo de amonio, ammonium chromate, primary ammonium phosphate, ammonium formiate, ammonium hydrogen phosphate, ammonium iodide, ammonium nitrate, ammonium oxalate, ammoniumper chlorate, ammonium sulfate, ammonium sulphite, ammonium tartrate, ammonium thiocyanate, barium chlorate, ammonium acetate, bariumchloride, hydrated barta, barium iodide, nitrate of baryta, barium perchlorate, barium sulphide, Calcium Bromide, calcium iodide, nitrocalcite, calcium nitrite, cobaltous bromide, cobaltous chlorate, cobalt chloride, 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, Potassium Iodate, potassiumiodide, saltpetre, potassium oxalate, potassium permanganate, 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, Manganese dibromide, Manganous chloride tetrahydrate, sodium acetate, sodium bromate, yellow soda ash, sodium chlorate, SODIUM PHOSPHATE, MONOBASIC, sodium formiate, sodium iodate, 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, molybdic oxide, Ripon, pure aluminium silicate, ferric metasilicate, Calucium Silicate powder, Magnesium Silicate q-agent, potassium silicate, water glass, iron titanate, calcium titanate, lead titanate, Pb-based lanthanumdoped zirconate titanates, the ferrous acid bismuth, Scium trioxide, chromic oxide, Manganse Dioxide, cobalt oxide, nickel oxide, cupric oxide, zinc oxide, yttrium oxide, zirconium dioxide, Niobium Pentxoxide, molybdic oxide, seven oxidations, two technetiums, ruthenium dioxide, rhodium oxide, palladous oxide, silver suboxide, Cadmium oxide, lutecium oxide, hafnium oxide, tantalum pentoxide, tungstic oxide, four rhenium oxides, perosmic anhydride, iridium dioxide, platinum dioxide, gold trioxide, the oxidation lawrencium, Vanadium Pentoxide in FLAKES, molybdic oxide, hexagonal boron nitride, the metal dithionite thing, metal selenide, metal telluride, Hofmann type compound: Ni (CN)₂NH₃, kaolinite, dickite, agalmatolite, hydrotalcite (LDHs,

M^IIIBe ionic radius and the approaching trivalent metal ion of magnesium ion; A^N-Be negatively charged ion), houghite (, M^II=Mg, Fe, Co, Ni, Mn, Zn; M^III=Al, Fe, Cr, Mn, V; A^N-Be negatively charged ion), polynary sulfide, transition metal oxide, NaTiO₂, NaVO₂, NaCrO₂, NaMnO₂, NaFeO₂, NaCoO₂, NaNiO₂, KTiO₂, KVO₂, KCrO₂, KMnO₂, KFeO₂, KCoO₂, KNiO₂, a kind of or wherein several composition in the alkali-metal titanate, alkali-metal niobate, alkali-metal niobate-titanate, uranyl vanadate, graphite oxide, graphite intercalation compound, montmorillonite, saponite, vermiculite, rhombspar, stratiform tertiary iron phosphate, cadmium telluride, indium arsenide, gallium antimonide, copper-indium-galliun-selenium, Cadmium Sulfide, CNT (carbon nano-tube), soccerballene, activated carbon granule, MCMB, polymer microsphere, glass powder; Described polynary sulfide is NaCrS₂, NaVS₂, KCrS₂, KVS₂, ACuFeS₂, NaCuFeS₂, KCuFeS₂, Li₂FeS₂Or K₂Pt₄S₆, the metal in described metal dithionite thing, metal selenide and the metal telluride is Sn, Ti, Zr, Hf, V, Nb, Ta, Mo or W.Other step is identical with one of embodiment one to 25 with parameter.

The various solid particulates of present embodiment make up by any ratio.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, B₂O₃, SiO₂, NaHCO₃, CaCO₃, 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, K₂CO₃, KCl, AlCl₃) solubleness is big and at ethanol, benzene, CCl in water₄Less 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: Al₂O₃, CaCO₃, Fe₂O₃, Fe₃O₄, 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, I₂, urea, NH₄NO₃, NH₄HCO₃, CH₃COONH₄Deng, adopt the way of heat to remove;

The 6th class: heavy solid particulate, as zirconium white, vanadium, chromium, tungsten etc., (telling 20-2 μ m as linear vibrating screen stage equipment, air classifier removes with thin micro mist, tripod pendulum type batch centrifugal-SS450, multistage grading machine (step Electronics Co., Ltd. is opened in Shenzhen) to adopt fractional separation equipment.

Embodiment 27: what present embodiment was different with one of embodiment one to 26 is: the surface tension 40 ~ 50mN/m of described liquid-working-medium.Other step is identical with one of embodiment one to 26 with parameter.

Embodiment 28: one of present embodiment and embodiment one to 26 are not both: the surface tension 45mN/m of described liquid-working-medium.Other step is identical with one of embodiment one to 26 with parameter.

Embodiment 29: what present embodiment was different with one of embodiment one to 28 is: the viscosity of described liquid-working-medium is 100 ~ 500000mPas.Other step is identical with one of embodiment one to 28 with parameter.

Embodiment 30: what present embodiment was different with one of embodiment one to 28 is: the viscosity of described liquid-working-medium is 1000 ~ 50000mPas.Other step is identical with one of embodiment one to 28 with parameter.

The embodiment hentriaconta-: what present embodiment was different with one of embodiment one to 28 is: the viscosity of described liquid-working-medium is 5000mPas.Other step and parameter and embodiment one to 28 two identical.

Embodiment 32: present embodiment and embodiment and embodiment one to one of hentriaconta-different be: the particle diameter of described solid particulate is 5nm ~ 100nm.Other step is identical to one of hentriaconta-with embodiment one with parameter.

Embodiment 33: what present embodiment and embodiment and embodiment 32 were different is: the particle diameter of described solid particulate is 200nm ~ 500nm.Other step is identical with embodiment 32 with parameter.

Embodiment 34: what present embodiment and embodiment and embodiment 32 were different is: the particle diameter of described solid particulate is 1 μ m ~ 20 μ m.Other step is identical with embodiment 32 with parameter.

Embodiment 35: what present embodiment and embodiment and embodiment 32 were different is: the particle diameter of described solid particulate is 50 μ m ~ 80 μ m.Other step is identical with embodiment 32 with parameter.

Embodiment 36: the present embodiment high-level efficiency prepares the method for graphene complex and graphene oxide mixture and is undertaken by following step: by ratio of weight and the number of copies with 1 part of Graphite Powder 99,100 parts of particle diameters are the copper powder of 50nm, in 100 parts of NaCl and the 500 parts of ethanol mixing clarifixators, add cetyl trimethylammonium bromide then, the cetyl trimethylammonium bromide consumption is 5% of an ethanol volume, peeled off 0.5 ~ 50 hour with 4000 rev/mins speed mechanical, obtain Graphene-copper-NaCl-alcoholic acid mixture after the filtration, filter, promptly obtain graphene complex (Graphene+copper composite powder body) after the washing.

The graphene complex that present embodiment is obtained adopts existing vacuum hot-pressing process to prepare Graphene enhancing Cu-base composites, this composite hardness:＞83HRB, electric conductivity:＞80%IACS, softening temperature: 900 ℃, abrasion loss reduces by 30%, have high strength, high conductivity, high softening temperature and anti abrasive characteristics, this material can be widely used in large-scale microwave tube structure and aspects such as electro-conductive material, change-over switch, contact and spot weld electrode.

Embodiment 37: the method that the present embodiment high-level efficiency prepares graphene complex realizes by following step: by ratio of weight and the number of copies with 1 part of Graphite Powder 99,50 parts of particle diameters are the silver powder of 20nm, after mixing, 150 parts of potassium primary phosphates and 500 parts of Virahols put into sand mill, add cetyl trimethylammonium bromide then, the cetyl trimethylammonium bromide consumption is 1% of a Virahol volume, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed mechanical, filtration obtains the mixture of Graphene-Yin-SODIUM PHOSPHATE, MONOBASIC-Virahol, filters, promptly obtain graphene complex (Graphene+argentum composite powder body) after the hot water wash.

The graphene complex that present embodiment is obtained adopts existing vacuum hot-pressing process promptly to prepare Graphene enhancing silver-based composite material.Specific conductivity and matrix that this material has excellence are suitable, and tensile strength improves 50%, and this composite granule is fit to do high-grade silver contact raw material.

Embodiment 38: the method that the present embodiment high-level efficiency prepares graphene complex realizes by following step: put into clarifixator after the silicon oxide that is 7nm with 1 part of Graphite Powder 99,4 parts of particle diameters, 100 parts of NaCl and 200 parts of Virahols mix by ratio of weight and the number of copies, add cetyl trimethylammonium bromide then, the cetyl trimethylammonium bromide consumption is 2% ~ 5% of a Virahol volume, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed mechanical, obtain Graphene-SiO after the filtration₂The mixture of-Virahol filters, cleans, and oven dry promptly obtains graphene complex (Graphene+silicon oxide composite granule).

Embodiment 39: the method that the present embodiment high-level efficiency prepares graphene complex realizes by following step: the silicon oxide that is 7nm with 1 part of Graphite Powder 99,0.5 part of particle diameter, 25 parts of particle diameters are to put into clarifixator after 60nm lime carbonate and 200 parts of Virahols mix by ratio of weight and the number of copies, add polyacrylic acid again, the polyacrylic acid consumption is 10% ~ 15% of a Virahol volume, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed mechanical, obtain Graphene-SiO₂The mixture of-lime carbonate-Virahol filters, and drying promptly obtains graphene complex (Graphene+silicon oxide+lime carbonate composite granule).

Embodiment 40: the method that the present embodiment high-level efficiency prepares graphene complex realizes by following step: put into sand mill after by ratio of weight and the number of copies 1 part of expanded graphite, 50 parts of illiteracy holder soil, 150 parts of KCl and 500 parts of acetone being mixed, add sodium laurylsulfonate again, the sodium laurylsulfonate consumption is 0.5% of an acetone volume, with 4000 rev/mins speed 0.5 ~ 100 hour, obtain the mixture of Graphene-Meng Tuo soil-KCl-acetone, promptly obtain graphene complex (Graphene+native composite granule of illiteracy holder) after filtering, washing.

Embodiment 41: the method that the present embodiment high-level efficiency prepares graphene complex realizes by following step: will take by weighing 1 part of graphite oxide powder, 0.1 ~ 100 part of hydrotalcite, 80 ~ 200 parts of potassium primary phosphates and 100 ~ 400 parts of water by ratio of weight and the number of copies, at 90 degrees centigrade potassium primary phosphate is dissolved in the water, add graphite oxide powder and hydrotalcite, obtain mixture; Said mixture is cooled to 20 ~ 50 ℃ utilizes sand mill with 2000 ~ 10000 rev/mins speed 0.1 ~ 100 hour simultaneously, obtain the mixture of graphene oxide-hydrotalcite-potassium primary phosphate-water, heated solution makes the potassium primary phosphate dissolving, filters, cleans the mixture that obtains graphene oxide and hydrotalcite lamellar compound.

Present embodiment is graphite oxide powder and the evenly assembling and compound of the cationic lamellar compound of thin layer, and this can fully adapt to actual needs, has the huge applications potentiality in fields such as catalysts selective, lithium ion cell electrodes.Used abrasive material of present embodiment implementation process and working medium all can be reused, and non-pollutant discharge is the synthetic route of a green, has broad application prospects.

Embodiment 42: the method that high-level efficiency prepares the Graphene composite granule in the present embodiment realizes by following step: by ratio of weight and the number of copies in the copper powder that is 50nm with 1 part of Graphite Powder 99,100 parts of particle diameters and the 500 parts of ethylene glycol mixing clarifixators, peeled off 0.5 ~ 50 hour with 4000 rev/mins speed mechanical, obtain the mixture of Graphene-copper-ethylene glycol, promptly obtain Graphene composite granule (Graphene+copper powder) behind filtration, the vacuum drying.

The Graphene composite granule that present embodiment is obtained adopts existing vacuum hot-pressing process to prepare Graphene enhancing Cu-base composites, this composite hardness:＞83HRB, electric conductivity:＞80%IACS, softening temperature: 900 ℃, abrasion loss reduces by 60%, have high strength, high conductivity, high softening temperature and anti abrasive characteristics, this material can be widely used in large-scale microwave tube structure and aspects such as electro-conductive material, change-over switch, contact and spot weld electrode.

Embodiment 43: the method that the present embodiment high-level efficiency prepares the Graphene composite granule realizes by following step: by ratio of weight and the number of copies with 1 part of Graphite Powder 99, after mixing, the silver powder that 50 parts of particle diameters are 20nm and 500 parts of Virahols put into sand mill, add cetyl trimethylammonium bromide then, the cetyl trimethylammonium bromide consumption is 1% of a Virahol volume, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed mechanical, filtration obtains the mixture of Graphene-Yin-Virahol, filters, promptly obtain Graphene composite granule (Graphene+silver powder) behind the vacuum drying.

The Graphene composite granule that present embodiment is obtained adopts existing vacuum hot-pressing process promptly to prepare Graphene enhancing silver-based composite material.Specific conductivity and matrix that this material has excellence are suitable, and tensile strength improves greater than 50%, and this composite granule is fit to do high-grade silver contact raw material.

Embodiment 44: the method that the present embodiment high-level efficiency prepares the graphene oxide composite granule realizes by following step: by ratio of weight and the number of copies with 1 part of graphite oxide powder, after mixing, the silver powder that 50 parts of particle diameters are 20nm and 500 parts of Virahols put into sand mill, add polyacrylic acid again, the polyacrylic acid consumption is 0.5% ~ 10% of a Virahol volume, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed mechanical, obtain the mixture of graphene oxide-Yin-Virahol, filter, promptly obtain graphene oxide composite granule (graphene oxide+silver powder) after the cleaning.

The graphene oxide composite granule that present embodiment obtains is the raw material of antimicrobial composite material material.

Embodiment 45: the method that the present embodiment high-level efficiency prepares the Graphene composite granule realizes by following step: put into clarifixator after the silicon oxide that is 7nm with 1 part of Graphite Powder 99,4 parts of particle diameters and 200 parts of Virahols mix by ratio of weight and the number of copies, add cetyl trimethylammonium bromide then, the cetyl trimethylammonium bromide consumption is 2% ~ 5% of a Virahol volume, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed mechanical, obtain Graphene-SiO₂The mixture of-Virahol promptly obtains Graphene composite granule (Graphene+silicon oxide) after the filtration.

Embodiment 46: the method that the present embodiment high-level efficiency prepares the Graphene composite granule realizes by following step: the silicon oxide that is 7nm with 1 part of Graphite Powder 99,0.5 part of particle diameter, 25 parts of particle diameters are to put into clarifixator after 60nm lime carbonate and 200 parts of Virahols mix by ratio of weight and the number of copies, add polyacrylic acid again, the polyacrylic acid consumption is 10% ~ 15% of a Virahol volume, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed mechanical, obtain Graphene-SiO_2-The mixture of lime carbonate-Virahol promptly obtains Graphene composite granule (Graphene+silicon oxide+lime carbonate) after the filtration.

Embodiment 47: the method that the present embodiment high-level efficiency prepares the Graphene composite granule realizes by following step: be to put into clarifixator after NaCl and 200 parts of Resins, epoxy mix with 0.5 part of Graphite Powder 99,0 ~ 1 part of graphite oxide powder, 50 parts of particle diameters by ratio of weight and the number of copies, peeled off 0.5 ~ 100 hour with 3000 rev/mins speed mechanical, obtain the mixture of Graphene-graphene oxide-NaCl-Resins, epoxy, NaCl is removed in washing, promptly obtain Graphene composite granule (Graphene+graphene oxide+Resins, epoxy, liquid state).

Above-mentioned epoxy resin composite can be preserved at liquid state, uses separately or sneaks in other resins and use.Add solidifying agent in the above-mentioned mixture, mix, solidify, promptly obtain Graphene and SiO₂Strengthen the conductive epoxy resin composite material.The tensile strength of matrix material does not more improve more than 40% during doping, and Young's modulus improves more than 50%.

Embodiment 48: the method that the present embodiment high-level efficiency prepares the Graphene composite granule realizes by following step: put into sand mill after by ratio of weight and the number of copies 1 part of expanded graphite, 50 parts of illiteracy holder soil and 500 parts of acetone being mixed, add sodium laurylsulfonate again, the sodium laurylsulfonate consumption is that 0.5% of acetone volume was peeled off 0.5 ~ 100 hour with 4000 rev/mins speed mechanical, obtain the mixture of Graphene-Meng Tuo soil-acetone, promptly obtain Graphene composite granule (Graphene+illiteracy holder soil) after the filtration.

Embodiment 49: the method that the present embodiment high-level efficiency prepares the Graphene composite granule realizes by following step: put into three-roller after by ratio of weight and the number of copies 1 part of expansible black lead, 1 part of CNT (carbon nano-tube), 50 parts of NaCl and 200 parts of polymethyl acrylates being mixed, add sodium laurylsulfonate again, the sodium laurylsulfonate consumption is 5% of a volume of water, mechanically peel 0.1 ~ 100 hour, dissolve polymethyl acrylate with butylacetate, filter, wash with water and remove sodium-chlor, promptly obtain Graphene composite granule (Graphene+CNT (carbon nano-tube)) after the filtration.

Embodiment 50: the method that the present embodiment high-level efficiency prepares the graphene oxide composite granule realizes by following step: by ratio of weight and the number of copies with the silicon oxide of 1 part of Graphite Powder 99,4 parts of about 7nm silicon oxide of diameter, 4 parts of about 20nm of diameter and the silicon oxide of 10 parts of diameter 1 μ m, 500 part 1, the mixing of 4-butyleneglycol is placed in the clarifixator, add polyacrylic acid (PAA) again, the polyacrylic acid consumption is 1,4-butyleneglycol volume 2% with 4000 rev/mins speed 0.5 ~ 50 hour, filter, clean and obtain graphene oxide composite granule (Graphene+silicon oxide).

Graphene and silicon oxide composite granule that present embodiment obtains can be used for preparing Graphene-silicon oxide ceramics matrix material.

Embodiment 51: the present embodiment high-level efficiency prepares the method for graphene complex and graphene oxide mixture and is undertaken by following step: by ratio of weight and the number of copies in the copper powder that is 50nm with 1 part of Graphite Powder 99,100 parts of particle diameters, 100 parts of NaCl and the 500 parts of ethanol mixing clarifixators, peeled off 0.5 ~ 50 hour with 4000 rev/mins speed mechanical, obtain Graphene-copper-NaCl-alcoholic acid mixture after the filtration, washing promptly obtains graphene complex (Graphene+copper powder) after the filtration.

The graphene complex that present embodiment is obtained adopts existing vacuum hot-pressing process to prepare Graphene enhancing Cu-base composites, this composite hardness:＞83HRB, electric conductivity:＞87%IACS, softening temperature: 900 ℃, abrasion loss reduces by 30%, have high strength, high conductivity, high softening temperature and anti abrasive characteristics, this material can be widely used in large-scale microwave tube structure and aspects such as electro-conductive material, change-over switch, contact and spot weld electrode.

Embodiment 52: the method that the present embodiment high-level efficiency prepares graphene complex realizes by following step: put into sand mill after the chromium powder that is 20nm with 1 part of Graphite Powder 99,50 parts of particle diameters, 150 parts of KCl and 500 parts of Virahols mix by ratio of weight and the number of copies, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed mechanical, filtration obtains the mixture of Graphene-chromium-KCl-Virahol, washing promptly obtains graphene complex (Graphene+chromium powder) after the filtration.

Embodiment 53: the method that the present embodiment high-level efficiency prepares graphene complex realizes by following step: put into clarifixator after the silicon oxide that is 7nm with 1 part of Graphite Powder 99,4 parts of particle diameters, 100 parts of NaCl and 200 parts of Virahols mix by ratio of weight and the number of copies, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed mechanical, obtain Graphene-SiO after the filtration₂The mixture of-Virahol, washing promptly obtains graphene complex (Graphene+silicon oxide) after the filtration.

Embodiment 54: the method that the present embodiment high-level efficiency prepares graphene complex realizes by following step: the silicon oxide that is 7nm with 1 part of Graphite Powder 99,0.5 part of particle diameter, 25 parts of particle diameters are to put into clarifixator after 60nm lime carbonate, 25 portions of sucrose and 200 parts of Virahols mix by ratio of weight and the number of copies, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed mechanical, obtain Graphene-SiO₂The mixture of-lime carbonate-Virahol filters, and heating is removed sucrose more than 200 ℃, promptly obtains graphene complex (Graphene+silicon oxide+lime carbonate).

Embodiment 55: the method that the present embodiment high-level efficiency prepares graphene complex realizes by following step: put into sand mill after by ratio of weight and the number of copies 1 part of expanded graphite, 50 parts of illiteracy holder soil, 150 parts of KCl and 500 parts of acetone being mixed, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed mechanical, obtain the mixture of Graphene-Meng Tuo soil-KCl-acetone, washing promptly obtains graphene complex (Graphene+illiteracy holder soil) after the filtration.

Embodiment 56: the method that high-level efficiency prepares the Graphene composite granule in the present embodiment realizes by following step: by ratio of weight and the number of copies in the copper powder that is 50nm with 1 part of Graphite Powder 99,100 parts of particle diameters and the 500 parts of ethylene glycol mixing clarifixators, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed mechanical, obtain the mixture of Graphene-copper-ethylene glycol, promptly obtain Graphene composite granule (Graphene+copper powder) after filtering, cleaning.

The Graphene composite granule that present embodiment is obtained adopts existing vacuum hot-pressing process to prepare Graphene enhancing Cu-base composites, this composite hardness:＞80HRB, electric conductivity:＞80%IACS, softening temperature: 900 ℃, abrasion loss reduces by 30%, have high strength, high conductivity, high softening temperature and anti abrasive characteristics, this material can be widely used in large-scale microwave tube structure and aspects such as electro-conductive material, change-over switch, contact and spot weld electrode.

Embodiment 57: the method that the present embodiment high-level efficiency prepares the Graphene composite granule realizes by following step: put into sand mill after the silver powder that is 20nm with 1 part of Graphite Powder 99,50 parts of particle diameters and 300 parts of Virahols mix by ratio of weight and the number of copies, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed mechanical, filtration obtains the mixture of Graphene-Yin-Virahol, promptly obtains Graphene composite granule (Graphene+silver powder) after the filtration.

Embodiment 58: the method that the present embodiment high-level efficiency prepares the graphene oxide composite granule realizes by following step: put into sand mill after the silver powder that is 20nm with 1 part of graphite oxide powder, 50 parts of particle diameters and 500 parts of Virahols mix by ratio of weight and the number of copies, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed mechanical, obtain the mixture of graphene oxide-Yin-Virahol, promptly obtain graphene oxide composite granule (graphene oxide+silver powder) after the filtration.

Embodiment 59: the method that the present embodiment high-level efficiency prepares the Graphene composite granule realizes by following step: put into clarifixator after the silicon oxide that is 7nm with 1 part of Graphite Powder 99,4 parts of particle diameters and 200 parts of Virahols mix by ratio of weight and the number of copies, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed mechanical, obtain Graphene-SiO after the filtration₂The mixture of-Virahol promptly obtains Graphene composite granule (Graphene+silicon oxide) after the filtration.

Embodiment 60: the method that the present embodiment high-level efficiency prepares the Graphene composite granule realizes by following step: the silicon oxide that is 7nm with 1 part of Graphite Powder 99,0.5 part of particle diameter, 25 parts of particle diameters are to put into clarifixator after 60nm lime carbonate and 200 parts of Virahols mix by ratio of weight and the number of copies, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed mechanical, obtain Graphene-SiO_2-The mixture of lime carbonate-Virahol promptly obtains Graphene composite granule (Graphene+silicon oxide+lime carbonate) after the filtration.

Embodiment 61: the method that the present embodiment high-level efficiency prepares the Graphene composite granule realizes by following step: put into sand mill after by ratio of weight and the number of copies 1 part of expanded graphite, 50 parts of illiteracy holder soil and 500 parts of acetone being mixed, peeled off 0.5 ~ 100 hour with 4000 rev/mins speed mechanical, obtain the mixture of Graphene-Meng Tuo soil-acetone, promptly obtain Graphene composite granule (Graphene+illiteracy holder soil) after the filtration.

Embodiment 62: the method that the present embodiment high-level efficiency prepares the Graphene composite granule realizes by following step: put into three-roller after by ratio of weight and the number of copies 1 part of expansible black lead, 0.5 part of CNT (carbon nano-tube), 100 parts of NaCl and 400 parts of polymethyl acrylates being mixed, mechanically peel 0.1 ~ 100 hour, dissolve polymethyl acrylate with butylacetate, filter, use water dissolution NaCl, promptly obtain Graphene composite granule (Graphene+CNT (carbon nano-tube)) after the filtration.

Embodiment 63: the method that the present embodiment high-level efficiency prepares the graphene oxide composite granule realizes by following step: by ratio of weight and the number of copies with 1 part of graphite oxide powder, 50 parts of zirconia powders and 150 part 1, the mixing of 4-butyleneglycol is placed in the oscillating mill, peeled off 0.5 ~ 50 hour, and filtered and obtain graphene oxide composite granule (graphite oxide powder+zirconium white).

Embodiment 64: the method that high-level efficiency prepares graphene complex or graphene oxide mixture in the present embodiment is undertaken by following step: one, 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, and splitting time is more than 5 minutes; Two, remove the material of non-target mixture: solid particulate keeps a kind of at least; Promptly obtain graphene complex or graphene oxide mixture; Described carbon materials powder is Graphite Powder 99, expanded graphite, expansible black lead, intercalated graphite or graphite oxide powder.

Embodiment 65: what present embodiment and embodiment 64 were different is: described gas working dielectric is air, He, Ne, Ar, N₂, H₂, Cl₂, Br₂, CO, CO₂, CH₄, a kind of or wherein several mixing among the NH3, water vapour, benzene vapor.Other is identical with embodiment 64.

Embodiment 66: when gas working dielectric is mixture in the present embodiment, press between all gases working medium arbitrarily than mixing.

Embodiment 67: what present embodiment was different with embodiment 65 or 66 is: the mass ratio of described plural components particle and carbon materials is 1:0.1 ~ 10000.Other step is identical with embodiment 65 or 66 with parameter.

Embodiment 68: what present embodiment was different with embodiment 65 or 66 is: the mass ratio of described plural components particle and carbon materials is 1:1 ~ 1000.Other step is identical with embodiment 65 or 66 with parameter.

Embodiment 69: what present embodiment was different with embodiment 65 or 66 is: the mass ratio of described plural components particle and carbon materials is 1:10 ~ 500.Other step is identical with embodiment 65 or 66 with parameter.

Embodiment 70: what present embodiment was different with embodiment 65 or 66 is: the mass ratio of described plural components particle and carbon materials is 1:100 ~ 300.Other step is identical with embodiment 65 or 66 with parameter.

Embodiment 71: what present embodiment was different with one of embodiment 65 to 70 is: described solid particulate is a lithium, beryllium, boron, sodium, magnesium, aluminium, silicon, phosphorus, sulphur, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, bromine, rubidium, strontium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, lawrencium, tantalum, tungsten, rhenium, iridium, platinum, gold, plumbous, bismuth, boron oxide, silicon oxide, zirconium white, aluminum oxide, lime carbonate, Vanadium Pentoxide in FLAKES, magnesium oxide, titanium dioxide, zinc oxide, stannic oxide, ferric oxide, Z 250, zirconium boride 99.5004323A8ure, lanthanum boride, titanium boride, tantalum boride, chromium boride, tungsten boride, silicon carbide, norbide, aluminium nitride, magnesium nitride, titanium nitride, Sodium Fluoride, Neutral ammonium fluoride, Cadmium Sulfide, indium phosphide, bicarbonate of ammonia, brometo de amonio, ammonium chromate, primary ammonium phosphate, ammonium formiate, ammonium hydrogen phosphate, ammonium iodide, ammonium nitrate, ammonium oxalate, ammoniumper chlorate, ammonium sulfate, ammonium sulphite, ammonium tartrate, ammonium thiocyanate, barium chlorate, ammonium acetate, bariumchloride, hydrated barta, barium iodide, nitrate of baryta, barium perchlorate, barium sulphide, Calcium Bromide, calcium iodide, nitrocalcite, calcium nitrite, cobaltous bromide, cobaltous chlorate, cobalt chloride, 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, Potassium Iodate, potassiumiodide, saltpetre, potassium oxalate, potassium permanganate, 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, Manganese dibromide, Manganous chloride tetrahydrate, sodium acetate, sodium bromate, yellow soda ash, sodium chlorate, SODIUM PHOSPHATE, MONOBASIC, sodium formiate, sodium iodate, 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, molybdic oxide, Ripon, pure aluminium silicate, ferric metasilicate, Calucium Silicate powder, Magnesium Silicate q-agent, potassium silicate, water glass, iron titanate, calcium titanate, lead titanate, Pb-based lanthanumdoped zirconate titanates, the ferrous acid bismuth, Scium trioxide, chromic oxide, Manganse Dioxide, cobalt oxide, nickel oxide, cupric oxide, zinc oxide, yttrium oxide, zirconium dioxide, Niobium Pentxoxide, molybdic oxide, seven oxidations, two technetiums, ruthenium dioxide, rhodium oxide, palladous oxide, silver suboxide, Cadmium oxide, lutecium oxide, hafnium oxide, tantalum pentoxide, tungstic oxide, four rhenium oxides, perosmic anhydride, iridium dioxide, platinum dioxide, gold trioxide, the oxidation lawrencium, Vanadium Pentoxide in FLAKES, molybdic oxide, hexagonal boron nitride, the metal dithionite thing, metal selenide, metal telluride, Hofmann type compound: Ni (CN)₂NH₃, kaolinite, dickite, agalmatolite, hydrotalcite (LDHs,

, M^II=Mg, Fe, Co, Ni, Mn, Zn; M^III=Al, Fe, Cr, Mn, V; A^N-Be negatively charged ion), polynary sulfide, transition metal oxide, NaTiO₂, NaVO₂, NaCrO₂, NaMnO₂, NaFeO₂, NaCoO₂, NaNiO₂, KTiO₂, KVO₂, KCrO₂, KMnO₂, KFeO₂, KCoO₂, KNiO₂, a kind of or wherein several composition in the alkali-metal titanate, alkali-metal niobate, alkali-metal niobate-titanate, uranyl vanadate, graphite oxide, graphite intercalation compound, montmorillonite, saponite, vermiculite, rhombspar, stratiform tertiary iron phosphate, cadmium telluride, indium arsenide, gallium antimonide, copper-indium-galliun-selenium, Cadmium Sulfide, CNT (carbon nano-tube), soccerballene, activated carbon granule, MCMB, polymer microsphere, glass powder; Described polynary sulfide is NaCrS₂, NaVS₂, KCrS₂, KVS₂, ACuFeS₂, NaCuFeS₂, KCuFeS₂, Li₂FeS₂Or K₂Pt₄S₆, the metal in described metal dithionite thing, metal selenide and the metal telluride is Sn, Ti, Zr, Hf, V, Nb, Ta, Mo or W.Other step is identical with one of embodiment 65 to 70 with parameter.

Embodiment 72: the present embodiment high-level efficiency prepares the method for graphene complex and finishes by following step: in airflow milling, with nitrogen, particle diameter is that silicon oxide and the NaCl of 7nm carried out mechanically peel 0.5 ~ 100 hour to Graphite Powder 99, use water dissolution NaCl, filter and obtain graphene complex (silicon oxide and Graphene composite powder), wherein silicon oxide and Graphite Powder 99 mass ratio are 4:1, and NaCl and Graphite Powder 99 mass ratio are 20 ~ 100:1.

Embodiment 73: the present embodiment high-level efficiency prepares the method for graphene oxide mixture and finishes by following step: in airflow milling, with argon gas and particle diameter is that zirconium white and KCl carried out mechanically peel 0.5 ~ 100 hour to the graphite oxide powder, use water dissolution NaCl, filter and obtain graphene complex (zirconium white and Graphene composite powder), wherein zirconium white and Graphite Powder 99 mass ratio are 4 ~ 10:1, and KCl and Graphite Powder 99 mass ratio are 20 ~ 100:1.

Embodiment 74: the present embodiment high-level efficiency prepares the method for graphene complex and finishes by following step: in airflow milling, with hydrogen and nitrogen (volume ratio 1:1), polynite and urea expanded graphite is carried out mechanically peel and got polynite, urea and expanded graphite mixture in 0.5 ~ 100 hour, be heated to more than 200 ℃ and make urea decomposition, obtain graphene complex (polynite and Graphene), wherein polynite and expanded graphite mass ratio are 50 ~ 100:1, and urea and Graphite Powder 99 mass ratio are 100 ~ 1000:1.

Nnnn embodiment 75: the present embodiment high-level efficiency prepares the method for graphene complex and finishes by following step: in airflow milling, the copper powder that with nitrogen, particle diameter is 50nm carried out mechanically peel 0.5 ~ 100 hour to expansible black lead, obtain graphene complex (Graphene+copper powder), wherein copper powder and expansible black lead mass ratio are 100:1.

Embodiment 76: the method that the present embodiment high-level efficiency prepares graphene complex realizes by following step: in airflow milling, with argon gas, Fe₂O₃With particle diameter be that the silver powder of 20nm carried out mechanically peel 0.5 ~ 50 hour to Graphite Powder 99, magnetic field separation goes out Fe₂O₃, obtain graphene complex (Graphene+silver powder), wherein silver powder and Graphite Powder 99 mass ratio are 50:1, Fe₂O₃With the Graphite Powder 99 mass ratio be 20 ~ 100:1.

The graphene complex that present embodiment is obtained adopts existing vacuum hot-pressing process promptly to prepare Graphene enhancing silver-based composite material.Specific conductivity and matrix that this material has excellence are suitable, and tensile strength improves greater than 50%, and this composite granule is fit to do high-grade silver contact raw material.

Embodiment 77: the method that the present embodiment high-level efficiency prepares graphene complex realizes by following step: in airflow milling, use nitrogen, NaCl, activity charcoal powder, particle diameter is that silicon oxide and the particle diameter of 7nm is that 60nm lime carbonate carried out mechanically peel 0.5 ~ 50 hour to Graphite Powder 99, use water dissolution NaCl, filter the back and obtain graphene complex (silicon oxide, lime carbonate, activity charcoal powder and graphene complex), silicon oxide wherein, lime carbonate, activity charcoal powder and Graphite Powder 99 mass ratio are 0.1 ~ 4:0 ~ 100:0 ~ 20:1, and NaCl and Graphite Powder 99 mass ratio are 20 ~ 1000:1.

The present embodiment graphene complex can be used as the nano functional additive of rubber (particularly rubber for tire), the agent of Resins, epoxy gluing and polymer matrix composites, owing to reduced the content of the more expensive nano silicon oxide of price in the mixture, the lime carbonate lower with price replaces, nanometer additive strengthened and the function of conduction so this additive had both had, and also had the outstanding ratio of performance to price.

Embodiment 78: the method that the present embodiment high-level efficiency prepares graphene complex realizes by following step: in airflow milling, with nitrogen, KCl, nano-titanium oxide Graphite Powder 99 was carried out mechanically peel 0.5 ~ 50 hour, use water dissolution KCl, filter the back and obtain graphene complex (nano-titanium oxide and Graphene composite powder), wherein nano-titanium oxide and Graphite Powder 99 mass ratio are 0.1 ~ 100:1, and KCl and Graphite Powder 99 mass ratio are 20 ~ 100:1.

Embodiment 79: the present embodiment efficient mechanical is peeled off the method for preparing Graphene and is finished by following step: in airflow milling, the silicon oxide that with nitrogen and particle diameter is 7nm carried out mechanically peel 0.5 ~ 50 hour to Graphite Powder 99, obtain the Graphene composite granule, wherein silicon oxide and Graphite Powder 99 mass ratio are 4 ~ 10:1.

Embodiment 80: the present embodiment efficient mechanical is peeled off the method for preparing graphene oxide and is finished by following step: in airflow milling, with argon gas and particle diameter is that zirconium white carried out mechanically peel 0.5 ~ 50 hour to the graphite oxide powder, obtain Graphene composite granule (zirconium white is to graphite oxide powder composite powder), wherein zirconium white and Graphite Powder 99 mass ratio are 4 ~ 10:1.

Embodiment 81: the present embodiment efficient mechanical is peeled off the method for preparing Graphene and is finished by following step: in airflow milling, with argon gas, polynite and KCl expanded graphite was carried out mechanically peel 0.5 ~ 50 hour, obtain the Graphene composite granule, wherein polynite, KCl and expanded graphite mass ratio are 1 ~ 10:50-200:1.

Embodiment 82: the present embodiment efficient mechanical is peeled off the method for preparing Graphene and is finished by following step: in airflow milling, the copper powder that with nitrogen and particle diameter is 50nm carried out mechanically peel 0.5 ~ 50 hour to expansible black lead, obtain Graphene composite granule (Graphene+copper powder), wherein copper powder and expansible black lead mass ratio are 100:1.

Embodiment 83: the method that the present embodiment high-level efficiency prepares the Graphene composite granule realizes by following step: in airflow milling, the silver powder that with nitrogen and particle diameter is 20nm carried out mechanically peel 0.5 ~ 50 hour to Graphite Powder 99, obtain Graphene composite granule (Graphene+silver powder), wherein silver powder and Graphite Powder 99 mass ratio are 50:1.

The Graphene composite granule that present embodiment is obtained adopts existing vacuum hot-pressing process promptly to prepare Graphene enhancing silver-based composite material.Specific conductivity and matrix that this material has excellence are suitable, and tensile strength improves greater than 50%, is fit to do high-grade silver contact raw material.

Embodiment 84: the method that the present embodiment high-level efficiency prepares the Graphene composite granule realizes by following step: in airflow milling, with argon gas, particle diameter is that silicon oxide and the particle diameter of 7nm is that 60nm lime carbonate carried out mechanically peel 0.5 ~ 50 hour to Graphite Powder 99, obtain Graphene composite granule (silicon oxide+lime carbonate+Graphene), wherein silicon oxide, lime carbonate and Graphite Powder 99 mass ratio are 0.1 ~ 5:0.1 ~ 50:1.

Claims

Translated fromChinese

1.高效率制备石墨烯复合物或氧化石墨烯复合物的方法，其特征在于高效率制备石墨烯复合物或氧化石墨烯复合物的方法是按下述步骤进行的：一、将碳素材料粉、固体颗粒和液体工作介质混合后进行机械剥离；二、去除非目标复合物的物质：去除液体工作介质，而固体颗粒至少保留一种，即获得石墨烯复合物或氧化石墨烯复合物；其中，所述固体颗粒的平均粒径在1nm~100μm，所述碳素材料粉为石墨粉、膨胀石墨、可膨胀石墨、插层石墨或氧化石墨粉，所述液体工作介质在机械剥离的工作温度下表面张力为10~73mN/m且粘度为1×10⁹mPa·s，在机械剥离过程中加入分散剂，分散剂用量为液体工作介质的0~20%。1. The method for preparing graphene composite or graphene oxide composite with high efficiency is characterized in that the method for preparing graphene composite or graphene oxide composite with high efficiency is carried out according to the following steps: one, carbon material Powder, solid particles and liquid working medium are mixed and then mechanically peeled off; 2. Removal of non-target compound substances: remove the liquid working medium, and keep at least one of the solid particles, that is, obtain graphene composites or graphene oxide composites; Wherein, the average particle diameter of the solid particles is between 1 nm and 100 μm, the carbon material powder is graphite powder, expanded graphite, expandable graphite, intercalated graphite or graphite oxide powder, and the liquid working medium is The surface tension at temperature is 10~73mN/m and the viscosity is 1×10⁹ mPa·s. A dispersant is added during the mechanical peeling process, and the amount of dispersant is 0~20% of the liquid working medium.

2.根据权利要求1所述的高效率制备石墨烯复合物或氧化石墨烯复合物的方法，其特征在于所述碳素材料粉与固体颗粒的重量比1：0.1~10000，所述固体颗粒与液体工作介质的重量比1：0.1~10000。2. The method for preparing graphene composites or graphene oxide composites with high efficiency according to claim 1, wherein the weight ratio of the carbon material powder to solid particles is 1:0.1~10000, and the solid particles The weight ratio to the liquid working medium is 1:0.1~10000.

3.根据权利要求2所述的高效率制备石墨烯复合物或氧化石墨烯复合物的方法，其特征在于所述固体颗粒是锂、铍、硼、钠、镁、铝、硅、磷、硫、钙、钪、钛、钒、铬、锰、铁、钴、镍、铜、锌、镓、锗、砷、硒、溴、铷、锶、钇、锆、铌、钼、锝、钌、铑、钯、银、镉、铟、锡、锑、碲、碘、镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥、锕、钍、镤、铀、镎、钚、镅、锔、锫、锎、锿、镄、钔、锘、铹、钽、钨、铼、铱、铂、金、铅、铋、氧化硼、氧化硅、氧化锆、氧化铝、碳酸钙、五氧化二钒、氧化镁、二氧化钛、氧化锌、氧化锡、三氧化二铁、四氧化三铁、硼化锆、硼化镧、硼化钛、硼化钽、硼化铬、硼化钨、碳化硅、碳化硼、氮化铝、氮化镁、氮化钛、氟化钠、氟化铵、硫化镉、磷化铟、碳酸氢铵、溴化铵、铬酸铵、磷酸二氢铵、甲酸铵、磷酸一氢铵、碘化铵、硝酸铵、草酸铵、高氯酸铵、硫酸铵、亚硫酸铵、酒石酸铵、硫氰酸铵、氯酸钡、醋酸铵、氯化钡、氢氧化钡、碘化钡、硝酸钡、高氯酸钡、硫化钡、溴化钙、碘化钙、硝酸钙、亚硝酸钙、溴化钴、氯酸钴、氯化钴、乙酸钾、溴酸钾、溴化钾、碳酸钾、氯酸钾、氯化钾、铬酸钾、重铬酸钾、磷酸二氢钾、铁氰化钾、亚铁氰化钾、氟化钾、甲酸钾、硫酸氢钾、氢氧化钾、碘酸钾、碘化钾、硝酸钾、草酸钾、高锰酸钾、硫酸钾、硫代硫酸钾、乙酸锂、溴化锂、氯化钠、氯化锂、甲酸锂、碘化锂、硝酸铝、硫酸铝、乙酸镁、溴化镁、碘化镁、硫酸镁、溴化锰、氯化锰、乙酸钠、溴酸钠、碳酸钠、氯酸钠、磷酸二氢钠、甲酸钠、碘酸钠、硝酸钠、磷酸钠、硫酸钠、氯化镍、硝酸镍、氯化亚铁、硫酸亚铁、氯化铁、氯化铜、硝酸铜、硫酸铜、硫酸锌、蔗糖、尿素、三氧化钼、氢氧化镁铝、硅酸铝、硅酸铁、硅酸钙、硅酸镁、硅酸钾、硅酸钠、钛酸铁、钛酸钙、钛酸铅、锆钛酸铅、铁酸铋、氧化钪、氧化铬、二氧化锰、氧化钴、氧化镍、氧化铜、氧化锌、氧化钇、二氧化锆、五氧化二铌、三氧化钼、七氧化二锝、二氧化钌、氧化铑、氧化钯、氧化银、氧化镉、氧化镥、二氧化铪、五氧化二钽、三氧化钨、四氧化铼、四氧化锇、二氧化铱、二氧化铂、氧化金、氧化铹、五氧化二钒、三氧化钼、六方氮化硼、金属二硫化物、金属硒化物、金属碲化物、Hofmann型化合物：Ni(CN)₂NH₃、高岭石、地开石、叶腊石、水滑石、类水滑石、多元硫化物、过渡金属氧化物、NaTiO₂、NaVO₂、NaCrO₂、NaMnO₂、NaFeO₂、NaCoO₂、NaNiO₂、KTiO₂、KVO₂、KCrO₂、KMnO₂、KFeO₂、KCoO₂、KNiO₂、碱金属的钛酸盐、碱金属的铌酸盐、碱金属的铌钛酸盐、铀酰钒酸盐、氧化石墨、石墨插层化合物、蒙脱石、皂石、蛭石、白云石、层状磷酸铁、碲化镉、砷化铟、锑化镓、铜铟镓硒、硫化镉、纳米碳管、富勒烯、活性炭颗粒、中间相炭微球、高分子微球、玻璃粉中的一种或其中几种的组成；所述多元硫化物为NaCrS₂、NaVS₂、KCrS₂、KVS₂、ACuFeS₂、NaCuFeS₂、KCuFeS₂、Li₂FeS₂或K₂Pt₄S₆，所述金属二硫化物、金属硒化物和金属碲化物中的金属为Sn、Ti、Zr、Hf、V、Nb、Ta、Mo或W。3. the method for preparing graphene composite or graphene oxide composite with high efficiency according to claim 2, is characterized in that said solid particle is lithium, beryllium, boron, sodium, magnesium, aluminum, silicon, phosphorus, sulfur , calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, bromine, rubidium, strontium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium , palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium , protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, ferm, 钔, 鼎, 铹, tantalum, tungsten, rhenium, iridium, platinum, gold, lead, bismuth, boron oxide, silicon oxide, oxide Zirconium, alumina, calcium carbonate, vanadium pentoxide, magnesium oxide, titanium dioxide, zinc oxide, tin oxide, ferric oxide, ferric oxide, zirconium boride, lanthanum boride, titanium boride, tantalum boride, Chromium boride, tungsten boride, silicon carbide, boron carbide, aluminum nitride, magnesium nitride, titanium nitride, sodium fluoride, ammonium fluoride, cadmium sulfide, indium phosphide, ammonium bicarbonate, ammonium bromide, chromium Ammonium acid, ammonium dihydrogen phosphate, ammonium formate, ammonium monohydrogen phosphate, ammonium iodide, ammonium nitrate, ammonium oxalate, ammonium perchlorate, ammonium sulfate, ammonium sulfite, ammonium tartrate, ammonium thiocyanate, barium chlorate, Ammonium acetate, barium chloride, barium hydroxide, barium iodide, barium nitrate, barium perchlorate, barium sulfide, calcium bromide, calcium iodide, calcium nitrate, calcium nitrite, cobalt bromide, cobalt chlorate, chlorine Cobalt oxide, potassium acetate, potassium bromate, potassium bromide, potassium carbonate, potassium chlorate, potassium chloride, potassium chromate, potassium dichromate, potassium dihydrogen phosphate, potassium ferricyanide, potassium ferrocyanide, potassium fluoride, Potassium formate, potassium hydrogen sulfate, potassium hydroxide, potassium iodate, potassium iodide, potassium nitrate, potassium oxalate, potassium permanganate, potassium sulfate, potassium thiosulfate, lithium acetate, lithium bromide, sodium chloride, lithium chloride, formic acid Lithium, lithium iodide, aluminum nitrate, aluminum sulfate, magnesium acetate, magnesium bromide, magnesium iodide, magnesium sulfate, manganese bromide, manganese chloride, sodium acetate, sodium bromate, sodium carbonate, sodium chlorate, diphosphate Sodium hydrogen, sodium formate, sodium iodate, sodium nitrate, sodium phosphate, sodium sulfate, nickel chloride, nickel nitrate, ferrous chloride, ferrous sulfate, ferric chloride, copper chloride, copper nitrate, copper sulfate, zinc sulfate , sucrose, urea, molybdenum trioxide, magnesium aluminum hydroxide, aluminum silicate, iron silicate, calcium silicate, magnesium silicate, potassium silicate, sodium silicate, iron titanate, calcium titanate, lead titanate, Lead zirconate titanate, bismuth ferrite, scandium oxide, chromium oxide, manganese dioxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, yttrium oxide, zirconium dioxide, niobium pentoxide, molybdenum trioxide, heptoxide Technetium, ruthenium dioxide, rhodium oxide, palladium oxide, silver oxide, cadmium oxide, lutetium oxide, hafnium dioxide, tantalum pentoxide, tungsten trioxide, rhenium tetroxide, osmium tetroxide, iridium dioxide, platinum dioxide, Gold oxide, cerbium oxide, vanadium pentoxide, molybdenum trioxide, hexagonal boron nitride, metal disulfides, metal selenides, metal tellurides, Hofmann-type compounds: Ni(CN)₂ NH₃ , kaolinite, earth Calcite, pyrophyllite, hydrotalcite, hydrotalcite-like, polysulfides, transition metal oxides, NaTiO₂ , NaVO₂ , NaCrO₂ , NaMn O₂ ,_NaFeO₂ , NaCoO₂ , NaNiO₂ , KTiO₂ , KVO₂ , KCrO 2 , KMnO₂ , KFeO₂ , KCoO₂ , KNiO₂ , alkali metal titanate, alkali metal niobate, alkali metal Niobate titanate, uranyl vanadate, graphite oxide, graphite intercalation compound, montmorillonite, saponite, vermiculite, dolomite, layered iron phosphate, cadmium telluride, indium arsenide, gallium antimonide, copper One or more of indium gallium selenide, cadmium sulfide, carbon nanotubes, fullerenes, activated carbon particles, mesophase carbon microspheres, polymer microspheres, and glass powder; the polysulfide is NaCrS₂ , NaVS₂ , KCrS₂ , KVS₂ , ACuFeS₂ , NaCuFeS₂ , KCuFeS₂ , Li₂ FeS₂ or K₂ Pt₄ S₆ , the metal in the metal disulfide, metal selenide and metal telluride is Sn , Ti, Zr, Hf, V, Nb, Ta, Mo or W.

4.根据权利要求3所述的高效率制备石墨烯复合物或氧化石墨烯复合物的方法，其特征在于所述液体工作介质在机械剥离的工作温度下表面张力为40~50mN/m。4. The method for preparing graphene composites or graphene oxide composites with high efficiency according to claim 3, wherein the surface tension of the liquid working medium is 40 ~ 50mN/m at the working temperature of mechanical stripping.

5.根据权利要求4所述的高效率制备石墨烯复合物或氧化石墨烯复合物的方法，其特征在于所述液体工作介质在机械剥离的工作温度下粘度为100~500000mPa·s。5. The method for preparing graphene composites or graphene oxide composites with high efficiency according to claim 4, wherein the liquid working medium has a viscosity of 100 to 500,000 mPa·s at the working temperature of mechanical stripping.

6.根据权利要求1-5任一项权利要求所述的高效率制备石墨烯复合物或氧化石墨烯复合物的方法，其特征在于所述的液体工作介质为水、醇类、芳香族化合物、酮类、胺类、离子液体、烷类、杂环化合物、二硫化碳、四氯化碳、汽油、植物油、柴油、蜡、醇的水溶液、烷类的醇溶液、酮的醇溶液、胺的水溶液、芳香族化合物的烷溶液或高分子化合物，其中所述高分子化合物为聚丙烯酸酯、聚乙烯醇、聚乙二醇、聚醋酸乙烯、淀粉、聚丁二烯、聚丁苯二烯、环氧树脂、煤焦油或沥青。6. according to the method for preparing graphene composite or graphene oxide composite with high efficiency according to any one of claims 1-5, it is characterized in that described liquid working medium is water, alcohols, aromatic compounds , ketones, amines, ionic liquids, alkanes, heterocyclic compounds, carbon disulfide, carbon tetrachloride, gasoline, vegetable oils, diesel oil, waxes, aqueous solutions of alcohols, alcohol solutions of alkanes, alcohol solutions of ketones, and aqueous solutions of amines , an alkane solution of an aromatic compound or a polymer compound, wherein the polymer compound is polyacrylate, polyvinyl alcohol, polyethylene glycol, polyvinyl acetate, starch, polybutadiene, polybutadiene, cyclic epoxy resin, coal tar or pitch.

7.根据权利要求6所述的高效率制备石墨烯复合物或氧化石墨烯复合物的方法，其特征在于所述醇类为乙醇、正丙醇、正丁醇、乙二醇、丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、丙三醇及异丙醇中的一种或其中几种的混合；所述芳香族化合物为苯、甲苯、萘或蒽；所述酮类为丙酮或Ν-甲基吡咯烷酮；所述胺类为N-甲基甲酰胺、N，N-二甲基甲酰胺或N，N-二乙基甲酰胺；所述离子液体为1-丁基-3-甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑六氟磷酸盐或1-羟乙基-3-甲基六氟磷酸盐；所述烷类为正己烷、辛烷或癸烷；所述杂环化合物为呋喃或吡啶；所述醇的水溶液中醇为甲醇、乙醇、丙三醇、丁二醇或异丙醇；所述烷类的醇溶液为正己烷的辛醇溶液、正己烷的癸醇溶液或十八烷的癸醇溶液；所述酮的醇溶液为丙酮的丁二醇溶液或丙酮的乙醇溶液；所述胺的水溶液中的胺为N-甲基甲酰胺溶液或N，N-二甲基甲酰胺溶液；所述芳香族化合物的烷溶液为苯的正己烷溶液或甲苯的正己烷溶液。7. the method for preparing graphene composite or graphene oxide composite with high efficiency according to claim 6, is characterized in that described alcohols are ethanol, n-propanol, n-butanol, ethylene glycol, propylene glycol, 1 , one or a mixture of 2-butanediol, 1,3-butanediol, 1,4-butanediol, glycerol and isopropanol; the aromatic compound is benzene, toluene , naphthalene or anthracene; the ketones are acetone or N-methylpyrrolidone; the amines are N-methylformamide, N, N-dimethylformamide or N, N-diethylformamide; The ionic liquid is 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate or 1-hydroxyethyl-3-methylhexafluorophosphate The alkane is n-hexane, octane or decane; the heterocyclic compound is furan or pyridine; the alcohol in the aqueous solution of alcohol is methanol, ethanol, glycerol, butanediol or isopropanol; The alcohol solution of the alkanes is an octanol solution of n-hexane, a decanol solution of n-hexane or a decanol solution of octadecane; the alcohol solution of the ketone is a butanediol solution of acetone or an ethanol solution of acetone; The amine in the amine aqueous solution is N-methylformamide solution or N,N-dimethylformamide solution; the alkane solution of the aromatic compound is benzene n-hexane solution or toluene n-hexane solution.

8.高效率制备石墨烯复合物或氧化石墨烯复合物的方法，其特征在于高效率制备石墨烯复合物或氧化石墨烯复合物的方法是按下述步骤进行的：一、将碳素材料粉、固体颗粒和液体工作介质混合后进行机械剥离；二、去除非目标复合物的物质：固体颗粒全部去除或者至少保留一种；即获得石墨烯复合物或氧化石墨烯复合物；其中，所述碳素材料粉为石墨粉、膨胀石墨、可膨胀石墨、插层石墨或氧化石墨粉，液体工作介质在机械剥离的工作温度下表面张力为10~73mN/m且粘度为1×10⁹mPa·s，所述固体颗粒的平均粒径在1nm~100μm，在机械剥离过程中加入分散剂，分散剂用量为液体工作介质的0~20%，液体工作介质为高分子化合物。8. The method for preparing graphene composites or graphene oxide composites with high efficiency is characterized in that the method for preparing graphene composites or graphene oxide composites with high efficiency is carried out according to the following steps: one, the carbon material Powder, solid particles and liquid working medium are mixed and then mechanically peeled off; 2. Removal of non-target composite substances: all solid particles are removed or at least one is retained; that is, graphene composites or graphene oxide composites are obtained; wherein, the The carbon material powder is graphite powder, expanded graphite, expandable graphite, intercalated graphite or graphite oxide powder, and the liquid working medium has a surface tension of 10~73mN/m and a viscosity of 1×10⁹ mPa at the working temperature of mechanical exfoliation ·s, the average particle size of the solid particles is between 1 nm and 100 μm, and a dispersant is added during the mechanical stripping process, the amount of the dispersant is 0 to 20% of the liquid working medium, and the liquid working medium is a polymer compound.

9.根据权利要求8所述高效率制备石墨烯复合物或氧化石墨烯复合物的方法，其特征在于所述高分子化合物为聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯、ABS树脂、聚丙烯酸酯、聚丙烯腈、聚乙烯醇、聚乙二醇、聚醋酸乙烯、淀粉、聚丁二烯、聚丁苯二烯、聚苯胺、聚对苯乙炔、环氧树脂、聚四氟乙烯、尼龙、聚酰亚胺、聚酯、酚醛树脂、聚联苯、聚苯并噁嗪、聚芴、聚吡咯、聚噻吩、橡胶、煤焦油、沥青、液晶高分子、木质素、有机氟树脂及有机硅树脂中的一种或其中几种的组合。9. according to the method for preparing graphene compound or graphene oxide compound with high efficiency described in claim 8, it is characterized in that described polymer compound is polyethylene, polypropylene, polyvinyl chloride, polystyrene, ABS resin, Polyacrylate, polyacrylonitrile, polyvinyl alcohol, polyethylene glycol, polyvinyl acetate, starch, polybutadiene, polybutadiene, polyaniline, polyphenylene vinylene, epoxy resin, polytetrafluoroethylene , nylon, polyimide, polyester, phenolic resin, polybiphenyl, polybenzoxazine, polyfluorene, polypyrrole, polythiophene, rubber, coal tar, pitch, liquid crystal polymer, lignin, organic fluorine resin And one or a combination of several silicone resins.

10.高效率制备石墨烯复合物或氧化石墨烯复合物的方法，其特征在于高效率制备石墨烯复合物或氧化石墨烯复合物的方法是按下述步骤进行的：一、在气流粉碎机内，用气体工作介质和粒径为1nm~100μm的固体颗粒对碳素材料粉进行机械剥离，剥离时间在5分钟以上；二、去除非目标复合物的物质：固体颗粒至少保留一种；即获得石墨烯复合物或氧化石墨烯复合物；所述碳素材料粉为石墨粉、膨胀石墨、可膨胀石墨、插层石墨或氧化石墨粉。10. The method for preparing graphene composites or graphene oxide composites with high efficiency is characterized in that the method for preparing graphene composites or graphene oxide composites with high efficiency is carried out according to the following steps: one. Inside, the carbon material powder is mechanically stripped with a gas working medium and solid particles with a particle size of 1nm~100μm, and the stripping time is more than 5 minutes; 2. Removal of non-target compound substances: at least one solid particle is retained; that is A graphene composite or a graphene oxide composite is obtained; the carbon material powder is graphite powder, expanded graphite, expandable graphite, intercalated graphite or graphite oxide powder.

11.根据权利要求10所述高效率制备石墨烯复合物或氧化石墨烯复合物的方法，其特征在于所述气体工作介质为空气、He、Ne、Ar、N₂、H₂、Cl₂、Br₂、CO、CO₂、CH₄、NH₃、水蒸气、苯蒸气中的一种或其中几种的混合。11. The method for preparing graphene composites or graphene oxide composites with high efficiency according to claim 10, characterized in that the gas working medium is air, He, Ne, Ar, N₂ , H₂ , Cl₂ , One of Br₂ , CO, CO₂ , CH₄ , NH₃ , water vapor, benzene vapor or a mixture of several of them.