CN101857221A - Method for preparing graphene compounds and graphene oxide compounds with high efficiency - Google Patents

Method for preparing graphene compounds and graphene oxide compounds with high efficiency Download PDF

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CN101857221A
CN101857221A CN 201010179118 CN201010179118A CN101857221A CN 101857221 A CN101857221 A CN 101857221A CN 201010179118 CN201010179118 CN 201010179118 CN 201010179118 A CN201010179118 A CN 201010179118A CN 101857221 A CN101857221 A CN 101857221A
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graphene
oxide
powder
working
graphite
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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 relates to a method for preparing graphene compounds and graphene oxide compounds with high efficiency, relating to the method for preparing the graphene compounds and the graphene oxide compounds. The invention solves the problems of easy composition of graphene or graphene oxide per se and many process steps, higher cost and difficult dispersedness for preparing the graphene compounds and the graphene oxide compounds by the traditional method at the same time. The invention adopts a mechanical stripping method to obtain the graphene compounds and the graphene oxide compounds. In the invention, an automatic machine is utilized, solid particles are used for assisting stripping, the contact area and the stripping number of the stripping process are greatly increased, and carbon material powder experiences a lot of stripping processes through the action of shear and impact, thereby obviously improving the stripping efficiency and achieving the purpose of uniform dispersedness to the composites. The method is suitable for industrial mass production of the graphene compounds and the graphene oxide compounds.

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 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 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 area 2) 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 peel 9MPas 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 peel 9MPas, 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) 2NH 3, kaolinite, dickite, agalmatolite, hydrotalcite (LDHs,
Figure 550530DEST_PATH_IMAGE001
M IIIBe ionic radius and the approaching trivalent metal ion of magnesium ion; A N-Be negatively charged ion), houghite (
Figure 117908DEST_PATH_IMAGE002
, 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, NaTiO 2, NaVO 2, NaCrO 2, NaMnO 2, NaFeO 2, NaCoO 2, NaNiO 2, KTiO 2, KVO 2, KCrO 2, KMnO 2, KFeO 2, KCoO 2, KNiO 2, 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 NaCrS 2, NaVS 2, KCrS 2, KVS 2, ACuFeS 2, NaCuFeS 2, KCuFeS 2, Li 2FeS 2Or K 2Pt 4S 6, 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 1mm 2, 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 peel 9MPas 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 1mm 2, 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 peel 9MPas, 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.
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 1mm 2, 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 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) 2NH 3, kaolinite, dickite, agalmatolite, hydrotalcite (LDHs,
Figure 917237DEST_PATH_IMAGE001
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, NaTiO 2, NaVO 2, NaCrO 2, NaMnO 2, NaFeO 2, NaCoO 2, NaNiO 2, KTiO 2, KVO 2, KCrO 2, KMnO 2, KFeO 2, KCoO 2, KNiO 2, 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 NaCrS 2, NaVS 2, KCrS 2, KVS 2, ACuFeS 2, NaCuFeS 2, KCuFeS 2, Li 2FeS 2Or K 2Pt 4S 6, 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, 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., (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 filtration 2The 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-SiO 2The 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-SiO 2The 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 SiO 2Strengthen 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 filtration 2The 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-SiO 2The 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.
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 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.
The graphene oxide composite granule that present embodiment obtains is the raw material of antimicrobial composite material material.
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 filtration 2The 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.
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 1mm 2, 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 65: what present embodiment and embodiment 64 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, 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) 2NH 3, kaolinite, dickite, agalmatolite, hydrotalcite (LDHs,
Figure 683516DEST_PATH_IMAGE001
M IIIBe ionic radius and the approaching trivalent metal ion of magnesium ion; A N-Be negatively charged ion), houghite (
Figure 987458DEST_PATH_IMAGE002
, 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, NaTiO 2, NaVO 2, NaCrO 2, NaMnO 2, NaFeO 2, NaCoO 2, NaNiO 2, KTiO 2, KVO 2, KCrO 2, KMnO 2, KFeO 2, KCoO 2, KNiO 2, 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 NaCrS 2, NaVS 2, KCrS 2, KVS 2, ACuFeS 2, NaCuFeS 2, KCuFeS 2, Li 2FeS 2Or K 2Pt 4S 6, 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.
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, 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., (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 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, Fe 2O 3With 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 Fe 2O 3, obtain graphene complex (Graphene+silver powder), wherein silver powder and Graphite Powder 99 mass ratio are 50:1, Fe 2O 3With 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 (11)

1. high-level efficiency prepares the method for graphene complex or graphene oxide mixture, it is characterized in that the method that high-level efficiency prepares graphene complex or graphene oxide mixture 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 peel 9MPas adds dispersion agent in the mechanically peel process, dispersant dosage is 0 ~ 20% of a liquid-working-medium.
2. high-level efficiency according to claim 1 prepares the method for graphene complex or graphene oxide mixture, 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-level efficiency according to claim 2 prepares the method for graphene complex or graphene oxide mixture, it is characterized in that 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) 2NH 3, kaolinite, dickite, agalmatolite, hydrotalcite, houghite, polynary sulfide, transition metal oxide, NaTiO 2, NaVO 2, NaCrO 2, NaMnO 2, NaFeO 2, NaCoO 2, NaNiO 2, KTiO 2, KVO 2, KCrO 2, KMnO 2, KFeO 2, KCoO 2, KNiO 2, 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 NaCrS 2, NaVS 2, KCrS 2, KVS 2, ACuFeS 2, NaCuFeS 2, KCuFeS 2, Li 2FeS 2Or K 2Pt 4S 6, the metal in described metal dithionite thing, metal selenide and the metal telluride is Sn, Ti, Zr, Hf, V, Nb, Ta, Mo or W.
4. high-level efficiency according to claim 3 prepares the method for graphene complex or graphene oxide mixture, it is characterized in that described liquid-working-medium is 40 ~ 50mN/m at the working temperature lower surface tension force of mechanically peel.
5. high-level efficiency according to claim 4 prepares the method for graphene complex or graphene oxide mixture, it is characterized in that described liquid-working-medium viscosity under the working temperature of mechanically peel is 100 ~ 500000mPas.
6. the method for preparing graphene complex or graphene oxide mixture according to the described high-level efficiency of each claim of claim 1-5, it is characterized in that 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 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.
7. high-level efficiency according to claim 6 prepares the method for graphene complex or graphene oxide mixture, 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. high-level efficiency prepares the method for graphene complex or graphene oxide mixture, it is characterized in that the method that high-level efficiency prepares graphene complex or graphene oxide mixture 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 peel 9MPas, 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.
9. described according to Claim 8 high-level efficiency prepares the method for graphene complex or graphene oxide mixture, it is characterized in that 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, a kind of or wherein several combination in organic fluorine and the silicone resin.
10. high-level efficiency prepares the method for graphene complex or graphene oxide mixture, it is characterized in that the method that high-level efficiency prepares graphene complex or graphene oxide mixture 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.
11. prepare the method for graphene complex or graphene oxide mixture according to the described high-level efficiency 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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CN115141497A (en) * 2022-09-01 2022-10-04 宜兴市国强炉业有限公司 High-thermal-conductivity wear-resistant material for circulating fluidized bed boiler and preparation method thereof
CN115417399A (en) * 2022-09-30 2022-12-02 深圳市金牌新能源科技有限责任公司 Copper-tantalum co-doped hard carbon composite material, and preparation method and application thereof
CN115417399B (en) * 2022-09-30 2024-03-26 深圳市金牌新能源科技有限责任公司 Copper-tantalum co-doped hard carbon composite material, and preparation method and application thereof
CN116656186A (en) * 2023-07-05 2023-08-29 李晶 Preparation method of graphene antibacterial water-based paint
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