CN104477892A

CN104477892A - Preparation method of flake graphene and flake graphene device prepared by same

Info

Publication number: CN104477892A
Application number: CN201410759741.8A
Authority: CN
Inventors: 王坚; 王叶帆
Original assignee: Yancheng City New Forms Of Energy Chemical Energy Storage And Electrical Source Of Power Research Center
Current assignee: Yancheng Teachers University
Priority date: 2014-12-12
Filing date: 2014-12-12
Publication date: 2015-04-01
Anticipated expiration: 2034-12-12
Also published as: CN104477892B

Abstract

The invention relates to a preparation method of a flake graphene and a flake graphene device prepared by the same. The preparation method is characterized in that expanded graphite flakes are obtained from flake graphite as a raw material by virtue of expanding and rolling, and then laminated on a metal sheet, the compound sheet serves as a working electrode in an electrolyte solution and is electrified to obtain a graphite interlayer compound which is relatively low in valence number and relatively high in yield, and finally, the graphite interlayer compound is stripped to obtain the flake graphene device with a matrix metal or non-metal conductor and a semiconductor. At least one side of the graphene prepared by use of the method is tightly adhered to the matrix metal or non-metal conductor and the semiconductor in the flake form; the device has excellent electrical conductivity and thermal conductivity and a huge specific surface area. The preparation method of the flake graphene has the advantages of wide raw material source, low cost, simplicity and environmental friendliness; the method is capable of directly obtaining the graphene device wide in application range, and thus is suitable for large-scale popularization, application and production.

Description

Flaky graphite alkene device prepared by a kind of preparation method of flaky graphite alkene and use the method

Technical field

The present invention relates to technical field of graphene, specifically, the preparation method that the present invention relates to a kind of flaky graphite alkene and the flaky graphite alkene device using the method to prepare.

Background technology

Graphene (Graphene) is the allotropic substance of a kind of carbon be recently familiar with for the mankind after soccerballene, carbon nanotube.Graphene is that a kind of carbon atom is with sp ²hybridized orbital Cheng Jian, the carbon material of the individual layer bi-dimensional cellular shape crystalline network formed with six-membered ring structure.The structure of this uniqueness of Graphene brings series of novel, special character to it, such as water white transparency (absorb light intensity is only 2.3%), electric conductivity high (single-layer graphene electric conductivity is close with copper), (tensile strength can reach 50 ~ 200GPa to excellent in mechanical performance, Young's modulus can reach 1TPa, and the tensile strength of single-layer graphene is 100 times of condition of equivalent thickness steel disc).Above characteristic makes Graphene have broad application prospects in many new forms of energy, field of new such as touch-screen, solar cell, aerospace materials.But Graphene is directly used in production practice also exists many limitations, therefore the preparation of graphene device and applied research thereof have become the focus in scientific research in recent years.The preparation method of Graphene is summed up, and mainly contains micromechanics stripping method, chemical Vapor deposition process (CVD), reduction-oxidation graphite method etc.Wherein, micromechanics stripping method successfully prepares the method for Graphene the earliest.The method utilizes the tear-off repeatedly of adhesive tape that graphene film is separated (K.S.Novoselov from highly oriented pyrolytic graphite, et al.Science, 306,666 (2004)), although adopt the method can prepare the Graphene of high-quality, but the method expensive starting materials, preparation process is seriously consuming time, cannot realize scale operation.Chemical Vapor deposition process is under pyrocarbon hydrogen compound (as methane) atmosphere, make the carbon laydown in hydrocarbon polymer to transition metal substrate thus obtained Graphene (Jessica Campos-Delgado, et al.Nano Letters, 8,9 (2008)).The method can obtain larger-size grapheme material, but manufacturing cost is too high and the graphene product number of plies of gained is difficult to control, and then limits the application of product.Reduction-oxidation graphite method prepares the main method of Graphene at present in a large number.The method, first by graphite oxidation, then obtains graphene oxide by stripping, finally the graphene oxide obtained is obtained Graphene by reduction.Although this method can prepare Graphene (Vincent C. in a large number, et al.Nat Nanotech, 4,25 (2008)), but, because this method relates to oxidation, reduction process, final gained Graphene still can contain partial oxidation group, and these oxide groups destroy the sp of Graphene ²structure, can cause the performance of Graphene, particularly conductivity and have a strong impact on.For solving above-mentioned preparation method's Problems existing, the Patents PART of current domestic existence is as follows.Chinese Patent Application No.: 200910084879.1, patent name: the preparation method of Graphene.This inventive method is reacted in ionic liquid by carbon nanotube and oxygenant and obtained Graphene.The method step is simple, easy handling, is applicable to large-scale commercial production.Chinese Patent Application No.: 200880112966.7, patent name: a kind of preparation method of two-dimension single layer plumbago alkene.The catalyzer of single-layer graphene is first prepared in this invention, passes into carbon source Pintsch process in an inert atmosphere afterwards and obtain two-dimension single layer plumbago alkene in the container that catalyzer is housed.In sum, the technology preparing Graphene at present can't meet that preparation method is simple, with low cost, product performance stablize the industrialization basic demands such as controlled, especially directly graphene device can not be obtained, yield is lower, acquisition be mostly mixed system containing Graphene, be difficult to be separated, purity is not high, even if acquisition grapheme material, be also difficult to obtained more practical graphene device, this just significantly limit Graphene in application that is wider, more wide field.

Summary of the invention

The object of the invention is to overcome the deficiencies in the prior art, the flaky graphite alkene device a kind of preparation method of flaky graphite alkene being provided and using the method to prepare.The object of the invention is to be achieved through the following technical solutions: with flexible expansion crystalline flake graphite for raw material, exfoliated graphite sheet is made by calendering, again with metallic conductor, non-metal conductor or semi-conductor obtain the composite sheet of expanded graphite by compound, then be energized the composite sheet of obtained expanded graphite composite sheet in the electrolytic solution that generate between obtained graphite flake layer and have the flakey expanded graphite of compound, finally use microwave, ultrasonic, the composite sheet of high temperature or electrolysis treatment flakey expanded graphite thus realize the flaky graphite alkene device that flakey expanded graphite lamella peels off obtained flaky graphite alkene and correspondence.

The selection of described graphite there is no particular restriction, can comprise natural graphite, synthetic graphite, specifically, comprises natural flake graphite, highly oriented pyrolytic graphite or special spherical graphite etc.Therefore raw material sources object extensive, with low cost can be reached.Further: the calendering described in (1) flexible expanded graphite is passed through repeatedly roll-in progressively obtain exfoliated graphite sheet;

(2) compound described in is by conductive binder, galvanic deposit, electroless plating, vacuum spraying or hot pressing thus the composite sheet of obtained metallic conductor, non-metal conductor or semi-conductor and exfoliated graphite sheet on exfoliated graphite sheet surface;

(3) energising described in obtains to generate between graphite flake layer the flakey expanded graphite of compound, be using the composite sheet of metallic conductor, non-metal conductor or semi-conductor and exfoliated graphite sheet as working electrode and choose compound between graphite layers is obtained to the electrode electrolysis that is energized in electrolyte solution;

(4) described supersound process flakey expanded graphite thus realize limellar stripping and obtain flaky graphite alkene and refer to: ultrasonic vibration and cavitation are carried out to flakey expanded graphite, described microwave treatment flakey expanded graphite thus realize limellar stripping and obtain flaky graphite alkene and refer to: dry by generating the composite sheet having the flakey expanded graphite of compound between obtained for energising graphite flake layer, be placed in microwave reaction chamber, microwave reaction chamber is vacuumized and passes into protective gas, with microwave, heat treated is carried out to reaction chamber, then close the flaky graphite alkene device of the obtained flaky graphite alkene of microwave cooling and correspondence, described electrolysis treatment flakey expanded graphite thus realize limellar stripping and obtain flaky graphite alkene and refer to: with the flakey expanded graphite of noble electrode or the obtained compound between graphite layers of energising for electrode, with the flakey expanded graphite of the obtained compound between graphite layers that is energized for working electrode, with organic ion liquor or the inorganic electrolyte aqueous solution for electrolytic solution, direct current or AC power, under constant voltage or continuous current, carry out negative electrode or anodic polarization electrolytic stripping compound between graphite layers or flakey expanded graphite, the flaky graphite alkene device of obtained flaky graphite alkene and correspondence, described pyroprocessing flakey expanded graphite thus realize limellar stripping and obtain flaky graphite alkene and refer to: the graphite layers that energising is obtained had the flakey expanded graphite washing of compound dry, under protective atmosphere protection, carry out high temperature 300 ~ 600 DEG C activation peel off, then lower the temperature, wash, the dry flaky graphite alkene device obtaining flaky graphite alkene and correspondence.

Described applying method has: conductive binder method, galvanic deposit composite algorithm, electroless plating composite algorithm, spraying method, pressure sintering.

Wherein, conductive binder in described complex method is that one of exfoliated graphite sheet expanded graphite calendering obtained uniformly coats electroconductive binder, then cover upper metallic conductor, non-metal conductor or wafer, form expanded graphite and metallic conductor, non-metal conductor or semiconductors coupling thin slice through pressing.

Wherein, described galvanic deposit composite algorithm: the one side of exfoliated graphite sheet expanded graphite calendering obtained is as negative electrode, metal or metal alloy to be deposited does antianode, direct current is led in containing corresponding metal or nonmetallic ion electrolyte solution, carry out galvanic deposit, form expanded graphite and matrix metal or non-metal conductor and semiconductors coupling thin slice.

Wherein, described electroless plating composite algorithm: be immersed in the one side of exfoliated graphite sheet that expanded graphite calendering obtains containing in corresponding metal or nonmetallic ion electrolyte solution, carries out electroless plating and forms expanded graphite and matrix metal or non-metal conductor or semiconductors coupling thin slice.

Wherein, described spraying method comprises: metal thermal spraying, vacuum evaporating, Vacuum Magnetic sputtering plating.

Wherein, described spraying method relate to metal thermal spraying method be exactly utilize high-temperature liquid metal by high-pressure inert gas be atomized and jet deposition to calendering obtain graphite flake on, little pressure layer-by-layer rolling is carried out close to the high temperature of fusing point and fabulous rheological when molten metal has just touched graphite flake, thus obtain fine and close metal cover, the form and dimensional precision of unlikely destruction graphite flake again, obtained expanded graphite and matrix metal conductor compound foil.

Wherein, it is exactly wire or metal and non-metal powder are melted in special spray converges room or spray gun that described spraying method relates to vacuum evaporating, one of exfoliated graphite sheet is ejected into again on the surface, obtained expanded graphite and metal or non-metal conductor or semiconductors coupling thin slice by pressurized air or inert gas atomizer.

Wherein, described spraying method relates to vacuum evaporating and utilizes Vacuum Magnetic to sputter plating machine exactly, with matrix metal or non-metal conductor or semiconductor material for target material, Vacuum Magnetic sputtering plating is carried out on a surface to exfoliated graphite sheet, obtains expanded graphite and metal or non-metal conductor or semiconductors coupling thin slice.

Wherein, described pressure sintering: the graphite flake that calendering obtains is posted in the metal support of foil-like, forms overlapping preform; In a vacuum or in nonoxidizing atmosphere thermo-compressed is added to preform duplexer, thus the composite sheet of obtained expanded graphite and matrix metal conductor.

Described matrix metal or non-metal conductor or wafer are one or more element combinations of Pb, Au, Ag, Pt, Ca, Sn, Zn, Ti, Ni, Al, Cu, Cr, In, Pd, Zn, Na, Li, K, Mg, Fe, Mn and C, Si.

Described electrolyte solution is inorganic salt solution, inorganic acid solution, inorganic alkali solution, organic ion solution.

It is described that to choose electrode be that metal electrode comprises: one or more element combinations of Pb, Au, Ag, Pt, Ca, Sn, Zn, Ti, Ni, Al, Cu, Cr, In, Pd and Graphite Electrodes.

Described energising obtain compound between graphite layers or flakey expanded graphite be pass into direct current, alternating-current carries out the obtained compound between graphite layers of electrolysis or flakey expanded graphite.

The method of described stripping compound between graphite layers is selected from a kind of, two or more combination in following method: supersonic method, microwave method, pyroprocess, electrolytic process.Wherein, described supersound process flakey expanded graphite thus realize limellar stripping and obtain flaky graphite alkene and refer to: ultrasonic vibration and cavitation are carried out to flakey expanded graphite, temperature is 10 ~ 50 DEG C, and ultrasonic splitting time is 5 ~ 120 minutes, and power is 1mW-1000 W.

Wherein, described microwave method is by the obtained compound between graphite layers of energising or the drying of flakey expanded graphite, is placed in microwave reaction chamber; Microwave reaction chamber is vacuumized and passes into protective gas; With microwave heating reaction chamber to 300 ~ 600 DEG C, heating 2 ~ 180s, close microwave, whole reactive system is cooled to 100 DEG C in a nitrogen atmosphere, obtained flaky graphite alkene.

Wherein, described pyroprocess be by compound between graphite layers obtained for energising or the washing of flakey expanded graphite dry, under protective atmosphere protection, carry out high temperature 300 ~ 600 DEG C activation peel off, then lower the temperature, wash, dryly obtain flaky graphite alkene.

Wherein, described electrolytic process be with noble electrode be to electrode, be energized obtained compound between graphite layers or flakey expanded graphite for working electrode, with organic ion liquor or the inorganic electrolyte aqueous solution for electrolytic solution, direct current or AC power, under constant voltage or continuous current, carry out negative electrode or anodic polarization electrolytic stripping compound between graphite layers or flakey expanded graphite, obtained flaky graphite alkene.

Preferred several technical scheme is as follows:

preferred technical scheme one:

(1) get one piece of flexible expansion crystalline flake graphite washing, dry; utilize roll squeezer to regulate gap repeatedly to roll gradually, in calender line, carry out boosting simultaneously, increase the flexibility of graphite; calendering, until graphite flake thickness is 0.05mm, namely obtains exfoliated graphite sheet;

(2) by acetylene black 96.85%, Xylo-Mucine 1.55%, styrene-butadiene rubber(SBR) 1.60%, stir, furnishing pasty slurry; Overlay on aluminium foil by this pasty slurry uniform spreading, paving is covered thickness and is 0.01mm; To spread in the pasty slurry covered exfoliated graphite sheet on uniform fold again, paving is covered thickness and is 0.08mm, then will spread the expanded graphite-aluminium compound foil vacuum-drying at normal temperatures 1 hour of the humidity covered, obtained expanded graphite-aluminium compound foil;

(3) expanded graphite-aluminium compound foil is done anode, do electrolytic solution with 10M aqueous sulfuric acid, another expanded graphite-metal composite thin slice does negative electrode, and electrolytic condition is: voltage is 2.3V, and the time is 20 minutes; Flakey expanded graphite is obtained after process;

(4) the flakey expanded graphite more than after process was through washing dry 3 hours in an oven; dried sample is placed in microwave reaction chamber; microwave reaction chamber is vacuumized and passes into protective gas; be 800W with microwave heating power, reaction chamber 600 DEG C, continuous heating 60 s; close microwave; whole reactive system is cooled to 100 DEG C in a nitrogen atmosphere, and obtaining the flaky graphite alkene device with aluminium base, is flaky graphite alkene above aluminium base.

preferred technical scheme two:

(1) get one piece of flexible expansion crystalline flake graphite washing, dry, utilize roll squeezer to regulate gap repeatedly to roll gradually, in calender line, carry out boosting simultaneously, increase the flexibility of graphite, calendering, until graphite flake thickness is 0.05mm, namely obtains exfoliated graphite sheet.

(3) expanded graphite-aluminium compound foil is done anode, do electrolytic solution with 10M aqueous sulfuric acid, another expanded graphite-metal composite thin slice does negative electrode, constant voltage 2.1V condition electrolysis 30 minutes, obtains flakey expanded graphite-aluminium compound foil after process;

(4) contain 100mL dehydrated alcohol with beaker, obtained flakey expanded graphite-aluminium compound foil is submerged in dehydrated alcohol, leave standstill 1 hour; Then the above-mentioned beaker that 100mL dehydrated alcohol is housed having flooded flakey expanded graphite-aluminium compound foil is placed in tank, makes the liquid level of water in tank equal with the ethanol liquid level of beaker inside; Get and can produce the hyperacoustic ultrasonic output probe of 100kHz and 400kHz, their power is adjusted to 100W, then exporting ultrasonic the bottom that probe is placed in beaker outer wall, using above-mentioned two kinds of frequencies to filling dehydrated alcohol and flakey expanded graphite-aluminium compound foil ultrasonication 2 hours simultaneously; Water temperature therebetween in attentional manipulation circulating water channel is 10 DEG C, after ultrasonic end, obtains the flaky graphite alkene device with aluminium base and flaky graphite alkene.

preferred technical scheme three:

(2) get silico-aluminate high-temperature electric conduction glue, stir, furnishing pasty slurry, overlay on aluminium foil by this pasty slurry uniform spreading, paving is covered thickness and is 0.01mm; To spread in the pasty slurry covered exfoliated graphite sheet on uniform fold again, paving is covered thickness and is 0.08mm, then will spread the expanded graphite-aluminium compound foil vacuum-drying at normal temperatures 1 hour of the humidity covered, obtained expanded graphite-aluminium compound foil;

(4) obtained flakey expanded graphite-aluminium compound foil is placed in high temperature reaction stove, described high temperature reaction stove is vacuum tube furnace, after pumping furnace air, in high temperature reaction stove, pass into protective gas argon gas protect, be warming up to 600 DEG C, continue to pass into protective gas, 600 DEG C of more than constant temperature 30min; Then room temperature is dropped in protective gas protection, washing, drying, the obtained flaky graphite alkene device with aluminium base.

preferred technical scheme four:

(1) get one piece of flexible expansion crystalline flake graphite washing, dry; utilize roll squeezer to regulate gap repeatedly to roll gradually, in calender line, carry out boosting simultaneously, increase the flexibility of graphite; calendering, until graphite flake thickness is 0.025mm, namely obtains exfoliated graphite sheet;

(2) one side of exfoliated graphite sheet expanded graphite calendering obtained, as negative electrode, is got the pure stereotype that one piece of area is greater than negative electrode and is done antianode, lead to direct current, carry out continuous current 25mA/cm in containing plumbic acetate electrolyte solution ²galvanic deposit 5 hours, forms expanded graphite-metallic lead composite sheet;

(3) antianode is done in the graphite face of expanded graphite-metallic lead composite sheet; electrolytic solution is done with 5M aqueous sulfuric acid; anticathode is done in the graphite face of another expanded graphite-metallic lead composite sheet; constant voltage 2.3V condition electrolysis 20 minutes, the flakey expanded graphite anode after process and negative electrode were through washing dry 3 hours in an oven; Dried sample is carried out above-mentioned energising again and process 5 minutes, obtain the flaky graphite alkene device flaky graphite alkene with lead substrate.

preferred technical scheme five:

(1) get one piece of flexible expansion crystalline flake graphite washing, dry; roll squeezer is utilized to regulate gap repeatedly to roll gradually; carry out boosting in calender line simultaneously, increase the flexibility of graphite, calendering is until graphite flake thickness is 0.015mm namely obtain exfoliated graphite sheet;

(2) one side of exfoliated graphite sheet expanded graphite calendering obtained is immersed in electroless lead plating solution, and constant temperature 50 DEG C reaction 5 hours, forms expanded graphite-metallic lead composite sheet;

(3) antianode is done in the graphite face of expanded graphite-metallic lead composite sheet; electrolytic solution is done with 5M aqueous sulfuric acid; anticathode is done in the graphite face of another expanded graphite-metallic lead composite sheet; constant voltage 2.1V condition electrolysis 20 minutes, the flakey expanded graphite anode after process and negative electrode were through washing dry 3 hours in an oven; Dried sample is carried out above-mentioned energising again and process 2 minutes, obtain the flaky graphite alkene with lead substrate and flaky graphite alkene device.

preferred technical scheme six:

(2) electric arc spraying aluminium lamination is carried out to Expandable graphite sheet obtained after calendering; the pressurized air of spraying should clean, drying; pressure must not be less than 0.4MPa; spray distance is 250mm; spray gun is at a right angle with Expandable graphite sheet surface as far as possible; 45 ° are less than to cannot do without; spray gun translational speed reaches 50 μm with a coating thickness; the width of 1/3 should be had overlapping between each spraying band; thickness requirement is even as far as possible, and the spray gun trend between each sprayed coating is mutually vertical, alternate covering; until metal layer thickness reaches 60 μm, obtained expanded graphite-aluminium compound foil;

(4) the flakey expanded graphite-aluminium compound foil more than after process was through washing dry 3 hours in an oven; dried sample is placed in microwave reaction chamber; microwave reaction chamber is vacuumized and passes into protective gas; be 800W with microwave heating power; reaction chamber 300 DEG C; continuous heating 60 s; close microwave; whole reactive system is cooled to 100 DEG C in a nitrogen atmosphere; obtain the flaky graphite alkene device with aluminium base, obtain the flaky graphite alkene device with aluminium base and flaky graphite alkene.

preferred technical scheme seven:

(1) get the synthetic graphite flake that one piece of thickness is 0.1mm, washing, oven dry, utilize roll squeezer to regulate gap repeatedly to roll gradually, carry out boosting in calender line simultaneously, increase the flexibility of graphite, calendering, until graphite flake thickness is 0.025mm, namely obtains graphite flake;

(2) electric arc spraying aluminium lamination is carried out to graphite flake obtained after calendering, the pressurized air of spraying should clean, drying, pressure must not be less than 0.4MPa, spray distance is 250mm, spray gun is at a right angle with Expandable graphite sheet surface as far as possible, 45 ° are less than to cannot do without, spray gun translational speed reaches 50 μm with a coating thickness, the width of 1/3 should be had overlapping between each spraying band, thickness requirement is even as far as possible, and the spray gun trend between each sprayed coating is mutually vertical, alternate covering, until metal layer thickness reaches 60 μm, obtained graphite-aluminium compound foil;

(3) graphite-aluminium compound foil is done anode, do electrolytic solution with 5M aqueous sulfuric acid, another expanded graphite-metal composite thin slice does negative electrode, constant voltage 2.3V condition electrolysis 100 minutes, obtains flakey expanded graphite-aluminium compound foil after process;

(4) contain 100mL dehydrated alcohol with beaker, obtained expanded graphite-aluminium compound foil is submerged in dehydrated alcohol, leave standstill 1 hour; Then the above-mentioned beaker that 100mL dehydrated alcohol is housed having flooded expanded graphite-aluminium compound foil is placed in tank, makes the liquid level of water in tank equal with the ethanol liquid level of beaker inside; Get and can produce the hyperacoustic ultrasonic output probe of 100kHz and 400kHz, their power is adjusted to 1000W, then ultrasonic output probe being amplexiformed the bottom being placed on beaker outer wall, using above-mentioned two kinds of frequencies to filling dehydrated alcohol and flakey expanded graphite system is ultrasonic simultaneously; Water temperature therebetween in attentional manipulation circulating water channel is 50 DEG C, and ultrasonic splitting time is 5 minutes, after ultrasonic end, obtains the flaky graphite alkene device with aluminium base and flaky graphite alkene.

preferred technical scheme eight:

(4) obtained flakey expanded graphite-aluminium compound foil is placed in high temperature reaction stove, described high temperature reaction stove is vacuum tube furnace or calcining furnace, after pumping furnace air, in high temperature reaction stove, pass into protective gas argon gas protect, be warming up to 600 DEG C, continue to pass into protective gas, 600 DEG C of more than constant temperature 30min; Then room temperature is dropped in protective gas protection, washing, drying, the obtained flaky graphite alkene device with aluminium base.

preferred technical scheme nine:

(1) get one piece of flexible expansion crystalline flake graphite washing, dry, utilize roll squeezer to regulate gap repeatedly to roll gradually, in calender line, carry out boosting simultaneously, increase the flexibility of graphite, calendering, until graphite flake thickness is 0.05mm, namely obtains exfoliated graphite sheet;

(2) carry out adding thermo-compressed under the state that the exfoliated graphite sheet obtained afterwards in calendering contacts with aluminum slice, Heating temperature 650 DEG C, pressurization 5MPa makes aluminum slice generation viscous deformation, to fit in Expandable graphite sheet, and obtained expanded graphite-aluminium compound foil;

(4) the flakey expanded graphite-aluminium compound foil more than after process was through washing dry 3 hours in an oven; dried sample is placed in microwave reaction chamber; microwave reaction chamber is vacuumized and passes into protective gas; be 800W with microwave heating power; reaction chamber 600 DEG C, continuous heating 60 s, closes microwave; whole reactive system is cooled to 100 DEG C in a nitrogen atmosphere, obtains the flaky graphite alkene device with aluminium base and flaky graphite alkene device.

preferred technical scheme ten:

(3) expanded graphite-aluminium compound foil is done anode, do electrolytic solution with 5M aqueous sulfuric acid, another expanded graphite-metal composite thin slice does negative electrode, constant voltage 20.0 V condition electrolysis 1 second, obtains flakey expanded graphite-aluminium compound foil after process;

(4) contain 100mL dehydrated alcohol with beaker, obtained expanded graphite-aluminium compound foil is submerged in dehydrated alcohol, leave standstill 1 hour; Then the above-mentioned beaker that 100mL dehydrated alcohol is housed having flooded expanded graphite-aluminium compound foil is placed in tank, makes the liquid level of water in tank equal with the ethanol liquid level of beaker inside; Get and can produce the hyperacoustic ultrasonic output probe of 100kHz and 400kHz, their power is adjusted to 100W, then the ultrasonic probe that exports being placed in the bottom of beaker outer wall, using above-mentioned two kinds of frequencies to filling dehydrated alcohol and flakey expanded graphite system ultrasonication 2 hours simultaneously; Water temperature therebetween in attentional manipulation circulating water channel is 40 DEG C, after ultrasonic end, obtains the flaky graphite alkene device with aluminium base and flaky graphite alkene.

preferred technical scheme 11:

(3) expanded graphite-aluminium compound foil is done anode, do electrolytic solution with 5M aqueous sulfuric acid, another expanded graphite-metal composite thin slice does negative electrode, constant voltage 1 mV condition electrolysis 10 hours, the flakey expanded graphite-aluminium compound foil after process;

(4) obtained flakey expanded graphite-aluminium compound foil is placed in high temperature reaction stove, described high temperature reaction stove is vacuum tube furnace or calcining furnace, after pumping furnace air, in high temperature reaction stove, pass into protective gas argon gas protect, be warming up to 600 DEG C, continue to pass into protective gas, 600 DEG C of more than constant temperature 30min; Then room temperature is dropped in protective gas protection, washing, drying, the obtained flaky graphite alkene device with aluminium base and flaky graphite alkene.

Compared with prior art, positively effect of the present invention is: (1) directly obtains flaky graphite alkene device, yield is high, without the need to being separated, be easy to preparation various types of electrodes material, heat-transfer matcrial, electro-conductive material, sensor material, energy storage material, hydrogen-absorbing material, catalyzer and sorbing material etc.;

(2) raw material sources are extensive, with low cost, and various types of graphite all can be used for preparation, prepares subsidiary material energy-conserving and environment-protective, cheap for manufacturing cost;

(3) easy, the product performance of preparation method are stablized controlled, are applicable to suitability for industrialized production.

accompanying drawing explanationfig. 1 is the method process flow diagram that the present invention prepares Graphene.

Fig. 2 rolls expanded graphite process schematic representation.Wherein 1 be expressed as pressure roller, 2 are expressed as the rear graphite flake of calendering.

Fig. 3 exfoliated graphite sheet and metal or non-metal conductor or semiconductors coupling lamellar structure schematic diagram.

Fig. 4 compound between graphite layers or flakey intumesced graphite structure schematic diagram.

Fig. 5 flaky graphite alkene device architecture schematic diagram.

Fig. 6 flaky graphite alkene device architecture SEM schemes.

embodimentthe embodiment of the preparation method of a kind of flaky graphite alkene of the present invention is below provided.

embodiment 1 bonds electrolysis microwave method and prepares flaky graphite alkeneget the washing of one piece of flexible expansion crystalline flake graphite, dry, utilize roll squeezer to regulate gap repeatedly to roll gradually, in calender line, carry out boosting simultaneously, increase the flexibility of graphite, calendering until graphite flake thickness is 0.05mm, technological process as fig. 1 and Fig. 2shown in, namely obtain exfoliated graphite sheet.

By acetylene black (conductive agent, particle diameter: about 10nm) 96.85%, CMC(Xylo-Mucine) 1.55%, SBR(styrene-butadiene rubber(SBR)) 1.60%, stir, furnishing pasty slurry.Overlay on aluminium foil by this pasty slurry uniform spreading, paving is covered thickness and is 0.01mm.To spread in the pasty slurry covered exfoliated graphite sheet on uniform fold again, paving is covered thickness and is 0.08mm, then will spread the expanded graphite-aluminium compound foil vacuum-drying at normal temperatures 1 hour of humidity covered, obtain expanded graphite-aluminium compound foil (technique as fig. 1shown in, as shown in Figure 3, wherein 1 be expressed as the rear exfoliated graphite sheet of calendering, 2 represent aluminium compound foils to expanded graphite-aluminium compound foil structure.）。Expanded graphite-aluminium compound foil is done anode, does electrolytic solution with 10M aqueous sulfuric acid, another expanded graphite-metal composite thin slice does negative electrode, and electrolytic condition is: voltage is 2.3V, and the time is 20 minutes.Flakey expanded graphite after process, as shown in Fig. 4 flaky graphite structural representation, wherein 1 is expressed as flakey expanded graphite; 2 are expressed as aluminium compound foil.

Flakey expanded graphite more than after process was through washing dry 3 hours in an oven; dried sample is placed in microwave reaction chamber; microwave reaction chamber is vacuumized and passes into protective gas; be 800W with microwave heating power, reaction chamber 600 DEG C, continuous heating 60 s; close microwave; whole reactive system is cooled to 100 DEG C in a nitrogen atmosphere, obtains the flaky graphite alkene device with aluminium base, and the graphene sheet layer that this embodiment obtains is thin.The tulle shape that the present embodiment obtained product is transparent, there is fold at edge, there is obvious Graphene feature, the number of plies scope of the flaky graphite alkene that this embodiment obtains mainly concentrates on 1-8 layer, direct acquisition flaky graphite alkene device, as shown in Fig. 5 flaky graphite alkene device architecture schematic diagram, wherein 1 be expressed as flaky graphite alkene; 2 are expressed as sheet metal.As shown in Fig. 6 flaky graphite alkene device SEM phenogram.

embodiment 2 sprays electrolysis microwave method and prepares flaky graphite alkene

Get the washing of one piece of flexible expansion crystalline flake graphite, dry, utilize roll squeezer to regulate gap repeatedly to roll gradually, in calender line, carry out boosting simultaneously, increase the flexibility of graphite, calendering until graphite flake thickness is 0.025mm, technological process as fig. 2shown in, namely obtain exfoliated graphite sheet.

Electric arc spraying aluminium lamination is carried out to Expandable graphite sheet obtained after calendering, the pressurized air of spraying should clean, drying, pressure must not be less than 0.4MPa, spray distance is 250mm, spray gun is at a right angle with Expandable graphite sheet surface as far as possible, 45 ° are less than to cannot do without, spray gun translational speed reaches 50 μm with a coating thickness, the width of 1/3 should be had overlapping between each spraying band, thickness requirement is even as far as possible, and the spray gun trend between each sprayed coating is mutually vertical, alternate covering, until metal layer thickness reaches 60 μm, obtained expanded graphite-aluminium compound foil.

Expanded graphite-aluminium compound foil is done anode, electrolytic solution is done with 10M aqueous sulfuric acid, another expanded graphite-metal composite thin slice does negative electrode, constant voltage 2.1V condition electrolysis 30 minutes, flakey expanded graphite after process, as shown in Fig. 4 flaky graphite structural representation, wherein 1 be expressed as flakey expanded graphite; 2 are expressed as aluminium compound foil.

Flakey expanded graphite more than after process was through washing dry 3 hours in an oven; dried sample is placed in microwave reaction chamber; microwave reaction chamber is vacuumized and passes into protective gas; be 800W with microwave heating power; reaction chamber 300 DEG C; continuous heating 60 s; close microwave; whole reactive system is cooled to 100 DEG C in a nitrogen atmosphere; obtain the flaky graphite alkene device with aluminium base; obtain the flaky graphite alkene device with aluminium base, the graphene sheet layer that this embodiment obtains is thin.The tulle shape that the present embodiment obtained product is transparent, there is fold at edge, has obvious Graphene feature, and the number of plies scope of the flaky graphite alkene that this embodiment obtains mainly concentrates on 1-8 layer, directly obtains flaky graphite alkene device.

embodiment 3 hot pressing electrolysis microwave method prepares flaky graphite alkene

Get the washing of one piece of flexible expansion crystalline flake graphite, dry, utilize roll squeezer to regulate gap repeatedly to roll gradually, in calender line, carry out boosting simultaneously, increase the flexibility of graphite, calendering until graphite flake thickness is 0.05mm, technological process as fig. 1 and Fig. 2shown in, namely obtain exfoliated graphite sheet.

Carry out adding thermo-compressed under the state that the exfoliated graphite sheet obtained afterwards in calendering contacts with aluminum slice, Heating temperature 650 DEG C, pressurization 5MPa makes aluminum slice generation viscous deformation, to fit in Expandable graphite sheet, and obtained expanded graphite-aluminium compound foil.

Flakey expanded graphite more than after process was through washing dry 3 hours in an oven; dried sample is placed in microwave reaction chamber; microwave reaction chamber is vacuumized and passes into protective gas; be 800W with microwave heating power, reaction chamber 600 DEG C, continuous heating 60 s; close microwave; whole reactive system is cooled to 100 DEG C in a nitrogen atmosphere, obtains the flaky graphite alkene device with aluminium base, and the graphene sheet layer that this embodiment obtains is thin.The tulle shape that the present embodiment obtained product is transparent, there is fold at edge, has obvious Graphene feature, and the number of plies scope of the flaky graphite alkene that this embodiment obtains mainly concentrates on 1-8 layer, directly obtains flaky graphite alkene device.

embodiment 4 bonds electrolysis supersonic method and prepares flaky graphite alkene

get the washing of one piece of flexible expansion crystalline flake graphite, dry, utilize roll squeezer to regulate gap repeatedly to roll gradually, in calender line, carry out boosting simultaneously, increase the flexibility of graphite, calendering until graphite flake thickness is 0.05mm, technological process as fig. 2shown in, namely obtain exfoliated graphite sheet.

By acetylene black (conductive agent, particle diameter: about 10nm) 96.85%, CMC(Xylo-Mucine) 1.55%, SBR(styrene-butadiene rubber(SBR)) 1.60%, stir, furnishing pasty slurry.Overlay on aluminium foil by this pasty slurry uniform spreading, paving is covered thickness and is 0.01mm.To spread in the pasty slurry covered exfoliated graphite sheet on uniform fold again, paving is covered thickness and is 0.08mm, then will spread the expanded graphite-aluminium compound foil vacuum-drying at normal temperatures 1 hour of humidity covered, obtain expanded graphite-aluminium compound foil (technique as fig. 3shown in, wherein 1 be expressed as the rear exfoliated graphite sheet of calendering, 2 represent aluminium compound foils.）。

Contain 100mL dehydrated alcohol with beaker, obtained flakey expanded graphite-aluminium compound foil is submerged in dehydrated alcohol, leave standstill 1 hour.Then the above-mentioned beaker that 100mL dehydrated alcohol is housed having flooded flakey expanded graphite-aluminium compound foil is placed in tank, makes the liquid level of water in tank equal with the ethanol liquid level of beaker inside.Get and can produce the hyperacoustic ultrasonic output probe of 100kHz and 400kHz, their power is adjusted to 100W, then exporting ultrasonic the bottom that probe is placed in beaker outer wall, using above-mentioned two kinds of frequencies to filling dehydrated alcohol and flakey expanded graphite-aluminium compound foil ultrasonication 2 hours simultaneously.Water temperature therebetween in attentional manipulation circulating water channel is 10 DEG C, after ultrasonic end, obtain the flaky graphite alkene device with aluminium base, the graphene sheet layer that this embodiment obtains is thin, there is fold at edge, there is obvious Graphene feature, the number of plies average out to of the flaky graphite alkene that this embodiment obtains 3 ~ 5 layers, directly obtain the flaky graphite alkene device with aluminium base.

embodiment 5 sprays electrolysis supersonic method and prepares flaky graphite alkene

Get the synthetic graphite flake that one piece of thickness is 0.1mm, washing, oven dry, utilize roll squeezer to regulate gap repeatedly to roll gradually, carry out boosting in calender line simultaneously, increase the flexibility of graphite, calendering until graphite flake thickness is 0.025mm, technological process as Fig. 1 and fig. 2shown in, namely obtain graphite flake.

Electric arc spraying aluminium lamination is carried out to graphite flake obtained after calendering, the pressurized air of spraying should clean, drying, pressure must not be less than 0.4MPa, spray distance is 250mm, spray gun is at a right angle with Expandable graphite sheet surface as far as possible, 45 ° are less than to cannot do without, spray gun translational speed reaches 50 μm with a coating thickness, the width of 1/3 should be had overlapping between each spraying band, thickness requirement is even as far as possible, and the spray gun trend between each sprayed coating is mutually vertical, alternate covering, until metal layer thickness reaches 60 μm, obtained graphite-aluminium compound foil.

Graphite-aluminium compound foil is done anode, electrolytic solution is done with 10M aqueous sulfuric acid, another expanded graphite-metal composite thin slice does negative electrode, constant voltage 2.3V condition electrolysis 100 minutes, flakey expanded graphite after process, as shown in Fig. 4 flaky graphite structural representation, wherein 1 be expressed as flakey expanded graphite; 2 are expressed as aluminium compound foil.

Contain 100mL dehydrated alcohol with beaker, obtained expanded graphite-aluminium compound foil is submerged in dehydrated alcohol, leave standstill 1 hour.Then the above-mentioned beaker that 100mL dehydrated alcohol is housed having flooded expanded graphite-aluminium compound foil is placed in tank, makes the liquid level of water in tank equal with the ethanol liquid level of beaker inside.Get and can produce the hyperacoustic ultrasonic output probe of 100kHz and 400kHz, their power is adjusted to 1000W, then ultrasonic output probe being amplexiformed the bottom being placed on beaker outer wall, using above-mentioned two kinds of frequencies to filling dehydrated alcohol and flakey expanded graphite system is ultrasonic simultaneously.Water temperature therebetween in attentional manipulation circulating water channel is 50 DEG C, ultrasonic splitting time is 5 minutes, after ultrasonic end, obtain the flaky graphite alkene device with aluminium base, the graphene sheet layer that this embodiment obtains is thin, and there is fold at edge, has obvious Graphene feature, the number of plies average out to of the flaky graphite alkene that this embodiment obtains 3 ~ 5 layers, directly obtains the flaky graphite alkene device with aluminium base.

embodiment 6 hot pressing electrolysis supersonic method prepares flaky graphite alkene

Expanded graphite-aluminium compound foil is done anode, electrolytic solution is done with 5M aqueous sulfuric acid, another expanded graphite-metal composite thin slice does negative electrode, constant voltage 20.0 V condition electrolysis 1 second, flakey expanded graphite after process, as shown in Fig. 4 flaky graphite structural representation, wherein 1 be expressed as flakey expanded graphite; 2 are expressed as aluminium compound foil.

Contain 100mL dehydrated alcohol with beaker, obtained expanded graphite-aluminium compound foil is submerged in dehydrated alcohol, leave standstill 1 hour.Then the above-mentioned beaker that 100mL dehydrated alcohol is housed having flooded expanded graphite-aluminium compound foil is placed in tank, makes the liquid level of water in tank equal with the ethanol liquid level of beaker inside.Get and can produce the hyperacoustic ultrasonic output probe of 100kHz and 400kHz, their power is adjusted to 100W, then the ultrasonic probe that exports being placed in the bottom of beaker outer wall, using above-mentioned two kinds of frequencies to filling dehydrated alcohol and flakey expanded graphite system ultrasonication 2 hours simultaneously.Water temperature therebetween in attentional manipulation circulating water channel is 40 DEG C, after ultrasonic end, obtain the flaky graphite alkene device with aluminium base, the graphene sheet layer that this embodiment obtains is thin, there is fold at edge, there is obvious Graphene feature, the number of plies average out to of the flaky graphite alkene that this embodiment obtains 3 ~ 5 layers, directly obtain the flaky graphite alkene device with aluminium base.

embodiment 7 bonds electrolysis pyroprocess and prepares flaky graphite alkene

Get silico-aluminate high-temperature electric conduction glue, stir, furnishing pasty slurry, overlay on aluminium foil by this pasty slurry uniform spreading, paving is covered thickness and is 0.01mm.To spread in the pasty slurry covered exfoliated graphite sheet on uniform fold again, paving is covered thickness and is 0.08mm, then will spread the expanded graphite-aluminium compound foil vacuum-drying at normal temperatures 1 hour of humidity covered, obtain expanded graphite-aluminium compound foil (technique as Fig. 1 and expanded graphite-aluminium compound foil as fig. 3shown in, wherein 1 be expressed as the rear exfoliated graphite sheet of calendering, 2 represent aluminium compound foils.）。

Obtained flakey expanded graphite is placed in high temperature reaction stove, and described high temperature reaction stove is vacuum tube furnace, after pumping furnace air, in high temperature reaction stove, pass into protective gas argon gas protect, be warming up to 600 DEG C, continue to pass into protective gas, 600 DEG C of more than constant temperature 30min; Then room temperature is dropped in protective gas protection, washing, drying, the obtained flaky graphite alkene device with aluminium base.

embodiment 8 sprays electrolysis pyroprocess and prepares flaky graphite alkene

Obtained flakey expanded graphite is placed in high temperature reaction stove, described high temperature reaction stove is vacuum tube furnace or calcining furnace, after pumping furnace air, in high temperature reaction stove, pass into protective gas argon gas protect, be warming up to 600 DEG C, continue to pass into protective gas, 600 DEG C of more than constant temperature 30min; Then room temperature is dropped in protective gas protection, washing, drying, the obtained flaky graphite alkene device with aluminium base.

embodiment 9 hot pressing electrolysis pyroprocess prepares flaky graphite alkene

Expanded graphite-aluminium compound foil is done anode, electrolytic solution is done with 5M aqueous sulfuric acid, another expanded graphite-metal composite thin slice does negative electrode, constant voltage 1 mV condition electrolysis 10 hours, flakey expanded graphite after process, as shown in Fig. 4 flaky graphite structural representation, wherein 1 be expressed as flakey expanded graphite; 2 are expressed as aluminium compound foil.

embodiment 10 galvanic deposit electrolytic process prepares flaky graphite alkene

The one side of exfoliated graphite sheet expanded graphite calendering obtained, as negative electrode, is got the pure stereotype that one piece of area is greater than negative electrode and is done antianode, lead to direct current, carry out continuous current 25mA/cm in containing plumbic acetate electrolyte solution ²galvanic deposit 5 hours, forms expanded graphite-metallic lead composite sheet.

Antianode is done in the graphite face of expanded graphite-metallic lead composite sheet, electrolytic solution is done with 5M aqueous sulfuric acid, anticathode is done in the graphite face of another expanded graphite-metallic lead composite sheet, constant voltage 2.3V condition electrolysis 20 minutes, the flakey expanded graphite anode after process and negative electrode were through washing dry 3 hours in an oven.Dried sample is carried out above-mentioned energising again and process 5 minutes, obtain the flaky graphite alkene device with lead substrate, the graphene sheet layer that this embodiment obtains is thin.The tulle shape that the present embodiment obtained product is transparent, there is fold at edge, there is obvious Graphene feature, the number of plies scope of the flaky graphite alkene that this embodiment obtains mainly concentrates on 1-8 layer, direct acquisition flaky graphite alkene device, as Fig. 5 flaky graphite alkene device architecture schematic diagram, wherein 1 be expressed as flaky graphite alkene; 2 are expressed as lead metal thin slice.

embodiment 11 electroless plating electrolytic process prepares flaky graphite alkene

Get the washing of one piece of flexible expansion crystalline flake graphite, dry, utilize roll squeezer to regulate gap repeatedly to roll gradually, in calender line, carry out boosting simultaneously, increase the flexibility of graphite, calendering until graphite flake thickness is 0.015mm, technological process as fig. 2shown in, namely obtain exfoliated graphite sheet.

The one side of exfoliated graphite sheet expanded graphite calendering obtained is immersed in electroless lead plating solution, and constant temperature 50 DEG C reaction 5 hours, forms expanded graphite-metallic lead composite sheet.

Antianode is done in the graphite face of expanded graphite-metallic lead composite sheet, electrolytic solution is done with 5M aqueous sulfuric acid, anticathode is done in the graphite face of another expanded graphite-metallic lead composite sheet, constant voltage 2.1V condition electrolysis 20 minutes, the flakey expanded graphite anode after process and negative electrode were through washing dry 3 hours in an oven.Dried sample is carried out above-mentioned energising again and process 2 minutes, obtain the flaky graphite alkene device with lead substrate, the graphene sheet layer that this embodiment obtains is thin.The tulle shape that the present embodiment obtained product is transparent, there is fold at edge, there is obvious Graphene feature, the number of plies scope of the flaky graphite alkene that this embodiment obtains mainly concentrates on 1-8 layer, direct acquisition flaky graphite alkene device, as Fig. 5 flaky graphite alkene device architecture schematic diagram, wherein 1 be expressed as flaky graphite alkene; 2 are expressed as lead metal thin slice.

embodiment 12 bonds electrolysis supersonic method and prepares flaky graphite alkene

Contain 100mL dehydrated alcohol with beaker, obtained flakey expanded graphite-aluminium compound foil is submerged in dehydrated alcohol, leave standstill 1 hour.Then the above-mentioned beaker that 100mL dehydrated alcohol is housed having flooded flakey expanded graphite-aluminium compound foil is placed in tank, makes the liquid level of water in tank equal with the ethanol liquid level of beaker inside.Get and can produce the hyperacoustic ultrasonic output probe of 100kHz, their power is adjusted to 1 W, then exporting ultrasonic the bottom that probe is placed in beaker outer wall, using above-mentioned two kinds of frequencies to filling dehydrated alcohol and flakey expanded graphite-aluminium compound foil ultrasonication 2 hours simultaneously.Water temperature therebetween in attentional manipulation circulating water channel is 10 DEG C, after ultrasonic end, obtain the flaky graphite alkene device with aluminium base, the graphene sheet layer that this embodiment obtains is thin, there is fold at edge, there is obvious Graphene feature, the number of plies average out to of the flaky graphite alkene that this embodiment obtains 12 layers, directly obtain the flaky graphite alkene device with aluminium base.

embodiment 13 hot pressing electrolysis microwave method prepares flaky graphite alkene

Flakey expanded graphite more than after process was through washing dry 3 hours in an oven; dried sample is placed in microwave reaction chamber; vacuumized in microwave reaction chamber and pass into protective gas, power is 10 W, with microwave heating reaction chamber to 300 DEG C; continuous heating 180s; close microwave, whole reactive system is cooled to 100 DEG C in a nitrogen atmosphere, obtained flaky graphite alkene; obtain the flaky graphite alkene device with aluminium base, the graphene sheet layer that this embodiment obtains is thin.The tulle shape that the present embodiment obtained product is transparent, there is fold at edge, has obvious Graphene feature, and the number of plies scope of the flaky graphite alkene that this embodiment obtains mainly concentrates on 1-8 layer, directly obtains flaky graphite alkene device.

embodiment 14 hot pressing electrolysis microwave method prepares flaky graphite alkene

Flakey expanded graphite more than after process was through washing dry 3 hours in an oven; dried sample is placed in microwave reaction chamber; power is 1000 W, is vacuumized in microwave reaction chamber and passes into protective gas, with microwave heating reaction chamber to 600 DEG C; continuous heating 2 s; close microwave, whole reactive system is cooled to 100 DEG C in a nitrogen atmosphere, obtained flaky graphite alkene; obtain the flaky graphite alkene device with aluminium base, the graphene sheet layer that this embodiment obtains is thin.The tulle shape that the present embodiment obtained product is transparent, there is fold at edge, has obvious Graphene feature, and the number of plies scope of the flaky graphite alkene that this embodiment obtains mainly concentrates on 1-8 layer, directly obtains flaky graphite alkene device.

embodiment 15 galvanic deposit electrolytic process prepares flaky graphite alkene

Antianode is done in the graphite face of expanded graphite-metallic lead composite sheet, electrolytic solution is done with 5M aqueous sulfuric acid, lead electrode does anticathode, constant voltage 2.3V condition DC electrolysis 20 minutes, and the flakey expanded graphite anode after process and negative electrode were through washing dry 3 hours in an oven.Dried sample is carried out above-mentioned energising again and process 5 minutes, obtain the flaky graphite alkene device with lead substrate, the graphene sheet layer that this embodiment obtains is thin.The tulle shape that the present embodiment obtained product is transparent, there is fold at edge, there is obvious Graphene feature, the number of plies scope of the flaky graphite alkene that this embodiment obtains mainly concentrates on 20 layers, direct acquisition flaky graphite alkene device, as Fig. 5 flaky graphite alkene device architecture schematic diagram, wherein 1 be expressed as flaky graphite alkene; 2 are expressed as lead metal thin slice.

embodiment 16 galvanic deposit electrolytic process prepares flaky graphite alkene

Antianode is done in the graphite face of expanded graphite-metallic lead composite sheet, electrolytic solution is done with 5M glycine solution, the graphite layers that energising obtains has the flakey expanded graphite of compound to be to electrode, continuous current 1A condition DC electrolysis 20 minutes, the flakey expanded graphite anode after process and negative electrode were through washing dry 3 hours in an oven.Dried sample is carried out above-mentioned energising again and process 5 minutes, obtain the flaky graphite alkene device with lead substrate, the graphene sheet layer that this embodiment obtains is thin.The tulle shape that the present embodiment obtained product is transparent, there is fold at edge, there is obvious Graphene feature, the number of plies scope of the flaky graphite alkene that this embodiment obtains mainly concentrates on 1-8 layer, direct acquisition flaky graphite alkene device, as Fig. 5 flaky graphite alkene device architecture schematic diagram, wherein 1 be expressed as flaky graphite alkene; 2 are expressed as lead metal thin slice.

embodiment 17 bonds electrolysis pyroprocess and prepares flaky graphite alkene

Obtained flakey expanded graphite is placed in high temperature reaction stove, described high temperature reaction stove is vacuum tube furnace or calcining furnace, after pumping furnace air, in high temperature reaction stove, pass into protective gas argon gas protect, be warming up to 300 DEG C, continue to pass into protective gas, 600 DEG C of more than constant temperature 30min; Then room temperature is dropped in protective gas protection, washing, drying, the obtained flaky graphite alkene device with aluminium base.

The above is only the preferred embodiment of the present invention, it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise, can also make some improvement, and these improvement also should be considered as in protection scope of the present invention.

Claims

1. the preparation method of a flaky graphite alkene, it is characterized in that, with flexible expansion crystalline flake graphite for raw material, exfoliated graphite sheet is made by calendering, again with metallic conductor, non-metal conductor or semi-conductor obtain the composite sheet of expanded graphite by compound, then be energized the composite sheet of obtained expanded graphite composite sheet in the electrolytic solution that generate between obtained graphite flake layer and have the flakey expanded graphite of compound, finally use microwave, ultrasonic, the composite sheet of high temperature or electrolysis treatment flakey expanded graphite thus realize the flaky graphite alkene device that flakey expanded graphite lamella peels off obtained flaky graphite alkene and correspondence.

2. the preparation method of flaky graphite alkene according to claim 1, is characterized in that:

(1) calendering described in flexible expanded graphite is passed through repeatedly roll-in progressively obtain exfoliated graphite sheet;

(4) described supersound process flakey expanded graphite thus realize limellar stripping and obtain flaky graphite alkene and refer to: ultrasonic vibration and cavitation are carried out to flakey expanded graphite, described microwave treatment flakey expanded graphite thus realize limellar stripping and obtain flaky graphite alkene and refer to: dry by generating the composite sheet having the flakey expanded graphite of compound between obtained for energising graphite flake layer, be placed in microwave reaction chamber, microwave reaction chamber is vacuumized and passes into protective gas, with microwave, heat treated is carried out to reaction chamber, then close the flaky graphite alkene device of the obtained flaky graphite alkene of microwave cooling and correspondence, described electrolysis treatment flakey expanded graphite thus realize limellar stripping and obtain flaky graphite alkene and refer to: have the flakey expanded graphite of compound for electrode with noble electrode or the obtained graphite layers of energising, the flakey expanded graphite of compound is had for working electrode with the obtained graphite layers that is energized, with organic ion liquor or the inorganic electrolyte aqueous solution for electrolytic solution, direct current or AC power, under constant voltage or continuous current, carry out negative electrode or anodic polarization electrolytic stripping compound between graphite layers or flakey expanded graphite, the flaky graphite alkene device of obtained flaky graphite alkene and correspondence, described pyroprocessing flakey expanded graphite thus realize limellar stripping and obtain flaky graphite alkene and refer to: the graphite layers that energising is obtained had the flakey expanded graphite washing of compound dry, under protective atmosphere protection, carry out high temperature 300 ~ 600 DEG C activation peel off, then lower the temperature, wash, the dry flaky graphite alkene device obtaining flaky graphite alkene and correspondence.

3. the preparation method of flaky graphite alkene according to claim 2, is characterized in that:

(1) calendering described in is utilized by flexible expanded graphite roll squeezer to regulate gap to carry out roll-in repeatedly gradually, carries out boosting in nipping process simultaneously, increases the flexibility of graphite, and calendering is until graphite flake thickness is 0.015-0.05 mm;

(2) energising described in obtains to generate between graphite flake layer has the electrolytic condition of the flakey expanded graphite of compound to be: voltage is 1 mV-20 V, and the time is 1 second-10 hours;

(3) described supersound process flakey expanded graphite thus realize limellar stripping and obtain flaky graphite alkene and refer to: ultrasonic vibration and cavitation are carried out to flakey expanded graphite; temperature is 10 ~ 50 DEG C; ultrasonic splitting time is 5 ~ 120 minutes, and power is 1mW-1000 W; Described microwave treatment flakey expanded graphite thus realize limellar stripping and obtain flaky graphite alkene and refer to: dry by generating the composite sheet having the flakey expanded graphite of compound between obtained for energising graphite flake layer; be placed in microwave reaction chamber; power is 10-1000 W; microwave reaction chamber is vacuumized and passes into protective gas; with microwave heating reaction chamber to 300 ~ 600 DEG C; heating 2 ~ 180s; close microwave; whole reactive system is cooled to 100 DEG C in a nitrogen atmosphere, the flaky graphite alkene device of obtained flaky graphite alkene and correspondence.

4. the preparation method of flaky graphite alkene according to claim 3, it is characterized in that, conductive binder in described complex method is that one of exfoliated graphite sheet expanded graphite calendering obtained uniformly coats electroconductive binder, then cover upper metallic conductor, non-metal conductor or wafer, form expanded graphite and metallic conductor, non-metal conductor or semiconductors coupling thin slice through pressing.

5. the preparation method of flaky graphite alkene according to claim 3, it is characterized in that, galvanic deposit in described complex method is that the one side of exfoliated graphite sheet expanded graphite calendering obtained is as negative electrode, metal to be deposited does antianode, direct current is led in containing corresponding metal ion electrolyte solution, carry out galvanic deposit, form expanded graphite and metal or non-metal conductor and semiconductors coupling thin slice.

6. the preparation method of flaky graphite alkene according to claim 3, it is characterized in that, electroless plating in described complex method is immersed in the one side of exfoliated graphite sheet that expanded graphite calendering obtains containing in corresponding metal ion electrolyte solution, carries out electroless plating and form expanded graphite and metal or non-metal conductor and semiconductors coupling thin slice.

7. the preparation method of flaky graphite alkene according to claim 3, is characterized in that, the vacuum spraying in described complex method comprises metal thermal spraying, vacuum evaporating and Vacuum Magnetic sputtering plating.

8. the preparation method of flaky graphite alkene according to claim 7, it is characterized in that, the metal thermal spraying that vacuum spraying in described complex method relates to is exactly utilize high-temperature liquid metal to be atomized one of the exfoliated graphite sheet that also jet deposition obtains to calendering on the surface by high-pressure inert gas, little pressure layer-by-layer rolling is carried out close to the high temperature of fusing point and fabulous rheological when molten metal has just touched graphite flake, thus obtain fine and close metal cover, the form and dimensional precision of unlikely destruction graphite flake again, obtains the compound foil of expanded graphite and metallic conductor.

9. the preparation method of flaky graphite alkene according to claim 7, it is characterized in that, the vacuum evaporating that vacuum spraying in described complex method relates to is exactly wire or metal and non-metal powder are melted in special spray converges room or spray gun, one of exfoliated graphite sheet is ejected into again on the surface, obtained expanded graphite and metal or non-metal conductor and semiconductors coupling thin slice by pressurized air or inert gas atomizer.

10. the preparation method of flaky graphite alkene according to claim 7, it is characterized in that, the Vacuum Magnetic sputtering plating that vacuum spraying in described complex method relates to is exactly utilize Vacuum Magnetic to sputter plating machine, with matrix metal or non-metal conductor and semiconductor material for target material, Vacuum Magnetic sputtering plating is carried out on a surface to exfoliated graphite sheet, obtains expanded graphite and metal or non-metal conductor and semiconductors coupling thin slice.

The preparation method of 11. flaky graphite alkene according to claim 3, is characterized in that, the hot pressing in described complex method is posted in the metal support of foil-like by the graphite flake that calendering obtains, and forms overlapping preform; In a vacuum or in nonoxidizing atmosphere thermo-compressed is added to preform duplexer, the compound foil of obtained expanded graphite and metallic conductor.

The preparation method of 12. flaky graphites according to claim 3, is characterized in that, described electrolyte solution is: inorganic salt solution, inorganic acid aqueous solution, inorganic base aqueous solution, organic ion liquor.

The preparation method of 13. flaky graphite alkene according to claim 3, it is characterized in that, generating between the obtained graphite flake layer of energising described in the flakey expanded graphite process having compound is metal electrode to electrode, comprising: one or more element combinations of Pb, Au, Ag, Pt, Ca, Sn, Zn, Ti, Ni, Al, Cu, Cr, In, Pd and Graphite Electrodes.

14. 1 kinds of flaky graphite alkene devices, is characterized by the flaky graphite alkene device that this flaky graphite alkene device is preparation method's acquisition of the flaky graphite alkene used as described in claim 1-13 any one.

15. flaky graphite alkene devices according to claim 14, it is characterized in that, described flaky graphite alkene device is that 1-20 layer graphene sheet has at least while be fixed on matrix metal or non-metal conductor and semiconductor surface, other limit is in the medium beyond matrix, and matrix metal or non-metal conductor and semi-conductor and the graphene film be fixed on surface are in good electronic conduction state.

16. flaky graphite alkene devices according to claim 14, it is characterized in that, described matrix metal electrical conductor or non-metal conductor and semi-conductor comprise: one or more element combinations of Pb, Au, Ag, Pt, Ca, Sn, Zn, Ti, Ni, Al, Cu, Cr, In, Pd, Zn, Na, Li, K, Mg, Fe, Mn and C, Si.

17. flaky graphite alkene devices according to claim 15, it is characterized in that, the medium beyond described matrix metal electrical conductor or non-metal conductor and semi-conductor comprises: air, nitrogen, argon gas, hydrogen, inorganic aqueous solution, inoganic solids, organic solution, organic liquid and organic solid.

The preparation method of 18. flaky graphite alkene according to claim 4, is characterized in that step is as follows:

The preparation method of 19. flaky graphite alkene according to claim 4, is characterized in that step is as follows:

The preparation method of 20. flaky graphite alkene according to claim 4, is characterized in that step is as follows:

The preparation method of 21. flaky graphite alkene according to claim 5, is characterized in that step is as follows:

The preparation method of 22. flaky graphite alkene according to claim 6, is characterized in that step is as follows:

The preparation method of 23. flaky graphite alkene according to claim 7, is characterized in that step is as follows:

The preparation method of 24. flaky graphite alkene according to claim 7, is characterized in that step is as follows:

(3) graphite-aluminium compound foil is done anode, do electrolytic solution with 10M aqueous sulfuric acid, another expanded graphite-metal composite thin slice does negative electrode, constant voltage 2.3V condition electrolysis 100 minutes, obtains flakey expanded graphite-aluminium compound foil after process;

The preparation method of 25. flaky graphite alkene according to claim 7, is characterized in that step is as follows:

The preparation method of 26. flaky graphite alkene according to claim 3, is characterized in that step is as follows:

The preparation method of 27. flaky graphite alkene according to claim 3, is characterized in that step is as follows:

The preparation method of 28. flaky graphite alkene according to claim 3, is characterized in that step is as follows:

29. 1 kinds of flaky graphite alkene, is characterized by and use the preparation method of the flaky graphite alkene described in claim 18-28 any one to prepare.

30. 1 kinds of flaky graphite alkene devices, is characterized by the flaky graphite alkene device that this flaky graphite alkene device is preparation method's acquisition of the flaky graphite alkene used as described in claim 18-28 any one.