CN104477892B

CN104477892B - Flaky graphite alkene device prepared by the preparation method of a kind of flaky graphite alkene and use the method

Info

Publication number: CN104477892B
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: 2016-08-24
Anticipated expiration: 2034-12-12
Also published as: CN104477892A

Abstract

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.It is characterized in that, the present invention is with crystalline flake graphite as raw material, exfoliated graphite sheet is obtained by expanding calendering, then fit on foil, in electrolyte solution, this composite sheet prepares, as working electrode energising, the compound between graphite layers that valence mumber is relatively low, yield is higher, is finally peeled away described compound between graphite layers and prepares the flaky graphite alkene device with parent metal or non-metal conductor and quasiconductor.The Graphene at least a part of which that the method prepares has while being close to be combined on a kind of parent metal or non-metal conductor and quasiconductor in flakey, and this device has excellent electric conductivity, heat conductivity and huge specific surface area.The advantage of this invention is: raw material sources are extensive, with low cost, the simple and direct environmental protection of preparation method；The method directly obtains the graphene device having wide range of applications, and is suitable for large-scale promotion application and production.

Description

Flakey stone prepared by the preparation method of a kind of flaky graphite alkene and use the method Ink alkene device

Technical field

The present invention relates to technical field of graphene, specifically, the present invention relates to the preparation side of a kind of flaky graphite alkene Flaky graphite alkene device prepared by method and use the method.

Background technology

Graphene (Graphene) is the carbon that fullerene, the latter of CNT recognized by the mankind recently that continues Allotrope.Graphene is that a kind of carbon atom is with sp²Hybrid orbital bonding, the monolayer two dimension formed with six-membered ring structure The material with carbon element of honeycomb crystal lattice structure.The structure of this uniqueness of Graphene brings series of novel, special character to it, Such as water white transparency (absorbing light intensity is only 2.3%), conductivity high (single-layer graphene conductivity is close with copper), (up to 50～200GPa, elastic modelling quantity is up to 1TPa, and the tension of single-layer graphene is strong for tensile strength for excellent in mechanical performance Degree is 100 times of condition of equivalent thickness steel disc).Above characteristic makes Graphene at touch screen, solaode, Aero-Space material Many new forms of energy, the field of new such as material have broad application prospects.But, Graphene is directly used in production practices and also deposits Limiting in many, therefore preparation and the applied research thereof of graphene device has become the focus in scientific research in recent years.Graphite The preparation method of alkene is summed up, and mainly has micromechanics stripping method, chemical vapour deposition technique (CVD), reduction-oxidation graphite method Deng.Wherein, micromechanics stripping method is the method the most successfully preparing Graphene.The method is to utilize the tear-off handle repeatedly of adhesive tape Graphene film separate from highly oriented pyrolytic graphite (K.S.Novoselov, et al.Science, 306,666 (2004)), although use the method can prepare the Graphene of high-quality, but the method expensive starting materials, preparation process is time-consuming Seriously, it is impossible to realize large-scale production.Chemical vapour deposition technique is under pyrocarbon hydrogen compound (such as methane) atmosphere, makes Carbon laydown in Hydrocarbon on transition metal substrate thus prepare Graphene (Jessica Campos-Delgado, et Al.Nano Letters, 8,9 (2008)).The method can prepare larger-size grapheme material, but, manufacturing cost mistake High and gained the graphene product number of plies is difficult to control to, and then limits the application of product.Reduction-oxidation graphite method is the biggest Amount prepares the main method of Graphene.The method, first by graphite oxidation, then obtains graphene oxide by stripping, finally incites somebody to action To graphene oxide obtain Graphene by reduction.Although this method can prepare Graphene (Vincent C., et in a large number Al.Nat Nanotech, 4,25 (2008)), but, owing to this method relates to oxidation, reduction process, final gained Graphene still can Containing partial oxidation group, these oxide groups destroy the sp of Graphene²Structure, particularly can lead the performance of Graphene Electrical property causes and has a strong impact on.For solving the problem that above-mentioned preparation method exists, the Patents part of current domestic existence is lifted Under such as.Chinese Patent Application No.: 200910084879.1, patent name: the preparation method of Graphene.This inventive method is Reacted in ionic liquid by CNT and oxidant and prepare Graphene.The method step is simple, it is easy to operation, is suitable for Large-scale industrial production.Chinese Patent Application No.: 200880112966.7, patent name: a kind of two-dimension single layer plumbago alkene Preparation method.The catalyst of single-layer graphene is first prepared in this invention, the most in an inert atmosphere to equipped with catalyst Container is passed through carbon source Pintsch process and prepares two-dimension single layer plumbago alkene.In sum, the technology preparing Graphene at present can't Meet that preparation method is simple, with low cost, properties of product stablize the industrialization basic demands such as controlled, especially can not directly prepare stone Ink alkene device, yield is relatively low, it is thus achieved that be mostly the mixed system containing Graphene, it is difficult to separate, purity is the highest, even if obtain Grapheme material, it is also difficult to preparing more practical graphene device, this just significantly limit Graphene wider, wider The application in wealthy field.

Summary of the invention

It is an object of the invention to overcome the deficiencies in the prior art, it is provided that the preparation method of a kind of flaky graphite alkene and making The flaky graphite alkene device prepared by the method.It is an object of the invention to be achieved through the following technical solutions: with flexibility Expansion crystalline flake graphite is raw material, makes exfoliated graphite sheet by calendering, then with metallic conductor, non-metal conductor or quasiconductor By the compound composite sheet preparing expanded graphite, then by the composite sheet of prepared expanded graphite at electrolyte Middle energising prepares the composite sheet generating the flakey expanded graphite having compound between graphite flake layer, finally uses microwave, surpasses Sound, high temperature or electrolysis process the composite sheet of flakey expanded graphite thus realize flakey expanded graphite lamella and peel off Prepare flaky graphite alkene and the flaky graphite alkene device of correspondence.

The selection of described graphite there is no particular restriction, it may include native graphite, Delanium, specifically, including sky So crystalline flake graphite, highly oriented pyrolytic graphite or special spherical graphite etc..Therefore can reach the mesh that raw material sources are extensive, with low cost 's.Further: the calendering described in (1) is that by repeatedly roll-in, flexible expanded graphite is progressively obtained exfoliated graphite sheet；

(2) compound described in be on exfoliated graphite sheet surface by conductive binder, electro-deposition, chemical deposition, Airless spraying or hot pressing thus prepare the composite of metallic conductor, non-metal conductor or quasiconductor and exfoliated graphite sheet Thin slice;

(3) energising described in prepares to generate between graphite flake layer the flakey expanded graphite of compound, be by metallic conductor, Electrode is existed with choose by the composite sheet of non-metal conductor or quasiconductor and exfoliated graphite sheet as working electrode In electrolyte solution, energising electrolysis prepares compound between graphite layers;

(4) described supersound process flakey expanded graphite thus realize limellar stripping and prepare flaky graphite alkene and refer to: Flakey expanded graphite is carried out ultrasonic vibration and cavitation;Described microwave treatment flakey expanded graphite thus realize lamella Peel off prepared flaky graphite alkene to refer to: energising prepares generation between graphite flake layer answering of the flakey expanded graphite of compound Material web is dried, and is placed in microwave reaction chamber, by microwave reaction chamber evacuation and be passed through protective gas, uses microwave Reaction chamber is carried out heat treated, is then shut off microwave cooling and prepares flaky graphite alkene and the flaky graphite alkene device of correspondence Part；Described electrolysis processes flakey expanded graphite thus realizes limellar stripping and prepare flaky graphite alkene and refer to: with inertia electricity The flakey expanded graphite of the compound between graphite layers that pole or energising prepare is to electrode, the graphite layers prepared with energising The flakey expanded graphite of compound is working electrode, with organic ion liquid solution or inorganic electrolyte aqueous solution as electrolyte, Direct current or alternating current power supply, under constant voltage or constant current, carry out negative electrode or anode polarization electrolysis stripping compound between graphite layers or Flakey expanded graphite, prepares flaky graphite alkene and the flaky graphite alkene device of correspondence；Described high-temperature process scale Shape expanded graphite thus realize limellar stripping and prepare flaky graphite alkene and refer to: the graphite layers that energising prepares is had compound The washing of flakey expanded graphite is dried, and carries out high temperature 300～600 DEG C of activation are peeled off under protective atmosphere is protected, then cooling, Washing, dry prepared flaky graphite alkene and the flaky graphite alkene device of correspondence.

Described applying method has: conductive binder method, electro-deposition composite algorithm, chemical deposition composite algorithm, spraying process, Pressure sintering.

Wherein, the described conductive binder in complex method is that expanded graphite expanded graphite calendering obtained is thin The one of sheet uniformly coats electroconductive binder, is then covered by metallic conductor, non-metal conductor or wafer, warp Pressing forms expanded graphite and metallic conductor, non-metal conductor or semiconductors coupling thin slice.

Wherein, described electro-deposition composite algorithm: the one side of exfoliated graphite sheet expanded graphite calendering obtained is as the moon Pole, metal or metal alloy to be deposited does anode, logical in containing corresponding metal or nonmetallic ion electrolyte solution Unidirectional current, carries out electro-deposition, forms expanded graphite and parent metal or non-metal conductor and semiconductors coupling thin slice.

Wherein, described chemical deposition composite algorithm: the one side dipping of the exfoliated graphite sheet that expanded graphite calendering is obtained Containing in corresponding metal or nonmetallic ion electrolyte solution, carry out chemical plating and form expanded graphite and parent metal or non- Metallic conductor or semiconductors coupling thin slice.

Wherein, described spraying process includes: metal thermal spraying, vacuum evaporating, Vacuum Magnetic sputtering plating.

Wherein, described spraying process relates to metal thermal spraying method and utilizes high-temperature liquid metal to be atomized by high-pressure inert gas exactly And on the graphite flake that obtains to calendering of jet deposition, close to the high temperature of fusing point and fabulous when molten metal has just touched graphite flake Rheological characteristic carry out little pressure layer-by-layer rolling, thus obtain the metal coating of densification, will not destroy again graphite flake shape and Dimensional accuracy, prepares expanded graphite and parent metal conductor compound foil.

Wherein, it is exactly in special spray by tinsel or metal and non-metal powder that described spraying process relates to vacuum evaporating Remittance room or spray gun are melted, is reinjected on a surface of exfoliated graphite sheet by compressed air or inert gas atomizer, system Obtain expanded graphite and metal or non-metal conductor or semiconductors coupling thin slice.

Wherein, described spraying process relate to vacuum evaporating utilize exactly Vacuum Magnetic sputter plating machine, with parent metal or non-gold Belong to conductor or semi-conducting material is target material, carry out Vacuum Magnetic sputtering plating to a surface of exfoliated graphite sheet, it is thus achieved that expand stone Ink 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, form overlap Preform；In a vacuum or add thermo-compressed in nonoxidizing atmosphere to preform duplexer, thus prepare expanded graphite Composite sheet with parent metal conductor.

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

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

Described choosing electrode is that metal electrode includes: Pb, Au, Ag, Pt, Ca, Sn, Zn, Ti, Ni, Al, Cu, Cr, One or more element combinations of In, Pd and graphite electrode.

Described energising prepare compound between graphite layers or flakey expanded graphite for being passed through unidirectional current, alternating current carries out electricity Solve the compound between graphite layers or flakey expanded graphite prepared.

The described method peeling off compound between graphite layers is selected from the one in following method, two or more group Close: supercritical ultrasonics technology, microwave method, high temperature method, electrolysis.Wherein, described supersound process flakey expanded graphite thus realize sheet Layer is peeled off prepared flaky graphite alkene and is referred to: flakey expanded graphite is carried out ultrasonic vibration and cavitation, and temperature is 10～50 DEG C, Ultrasonic splitting time is 5～120 minutes, and power is 1mW-1000 W.

Wherein, described microwave method is compound between graphite layers prepared for energising or flakey expanded graphite to be dried, will It is placed in microwave reaction chamber；By microwave reaction chamber evacuation and be passed through protective gas；With microwave heating reaction chamber to 300 ～600 DEG C, heating 2～180s, close microwave, whole response system is cooled to 100 DEG C in a nitrogen atmosphere, prepares flakey stone Ink alkene.

Wherein, described high temperature method is by dry to compound between graphite layers prepared for energising or the washing of flakey expanded graphite Dry, under protective atmosphere is protected, carry out high temperature 300～600 DEG C of activation are peeled off, then lower the temperature, wash, be dried prepared flakey Graphene.

Wherein, described electrolysis be with inert electrode be to electrode, with energising prepare compound between graphite layers or squama Lamellar expanded graphite is working electrode, with organic ion liquid solution or inorganic electrolyte aqueous solution as electrolyte, and direct current or friendship Stream power supply, under constant voltage or constant current, carries out negative electrode or anode polarization electrolysis stripping compound between graphite layers or flakey is swollen Swollen graphite, prepares flaky graphite alkene.

Preferred several technical scheme is as follows:

Preferably technical scheme one:

(1) take one piece of flexible expansion crystalline flake graphite washing, dry, utilize roll squeezer gradually to regulate gap and repeatedly press Prolonging, carry out auxiliary heating in calender line simultaneously, increase the flexibility of graphite, calendering, until graphite flake thickness is 0.05mm, to obtain final product To exfoliated graphite sheet;

(2) by acetylene black 96.85%, sodium carboxymethyl cellulose 1.55%, butadiene-styrene rubber 1.60%, stir, furnishing Pasty slurry；Overlaying on aluminium foil by this pasty slurry uniform spreading, being coated with thickness is 0.01mm；Again in the pasty slurry being coated with all Exfoliated graphite sheet in even covering, being coated with thickness is 0.08mm, the moist expanded graphite-aluminum compound foil being then coated with Vacuum drying 1 hour at normal temperatures, prepares expanded graphite-aluminum compound foil；

(3) expanded graphite-aluminum compound foil is done anode, do electrolyte 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；Obtain flakey after process and expand stone Ink；

(4) the flakey expanded graphite after processing more than is dried 3 hours in an oven through washing, is put by dried sample In microwave reaction chamber, by microwave reaction chamber evacuation and be passed through protective gas, it is 800W with microwave heating power, reaction 600 DEG C of chamber, continuous heating 60 s, close microwave, whole response system is cooled to 100 DEG C in a nitrogen atmosphere, it is thus achieved that with aluminum The flaky graphite alkene device of substrate, is flaky graphite alkene above aluminium base.

Preferably technical scheme two:

(1) take one piece of flexible expansion crystalline flake graphite washing, dry, utilize roll squeezer gradually to regulate gap and repeatedly press Prolonging, carry out auxiliary heating in calender line simultaneously, increase the flexibility of graphite, calendering, until graphite flake thickness is 0.05mm, to obtain final product To exfoliated graphite sheet.

(2) by acetylene black 96.85%, sodium carboxymethyl cellulose 1.55%, butadiene-styrene rubber 1.60%, it is sufficiently stirred for all Even, furnishing pasty slurry;Overlaying on aluminium foil by this pasty slurry uniform spreading, being coated with thickness is 0.01mm;Again at the pasty state being coated with Exfoliated graphite sheet on uniform fold on slurry, being coated with thickness is 0.08mm, the moist expanded graphite-aluminum being then coated with Compound foil is vacuum dried 1 hour at normal temperatures, prepares expanded graphite-aluminum compound foil;

(3) expanded graphite-aluminum compound foil is done anode, do electrolyte with 10M aqueous sulfuric acid, another expanded graphite- Metal composite thin slice does negative electrode, and constant voltage 2.1V condition is electrolysed 30 minutes, obtains flakey expanded graphite-aluminum THIN COMPOSITE after process Sheet；

(4) contain 100mL dehydrated alcohol with beaker, prepared flakey expanded graphite-aluminum compound foil is submerged in anhydrous In ethanol, stand 1 hour；Then by above-mentioned flooded flakey expanded graphite-aluminum compound foil equipped with the anhydrous second of 100mL The beaker of alcohol is placed in tank so that in tank, the liquid level of water is equal with the ethanol liquid level within beaker；Take and can produce The ultrasonic output probe of 100kHz and 400kHz ultrasound wave, adjusts their power to 100W, then by ultrasonic output probe It is placed in the bottom of beaker outer wall, uses above two frequency to filling dehydrated alcohol and flakey expanded graphite-aluminum is combined simultaneously Thin slice ultrasonication 2 hours；Notice that the water temperature controlled in circulating water chennel is 10 DEG C, after ultrasonic end, it is thus achieved that with aluminum base therebetween The flaky graphite alkene device of plate and flaky graphite alkene.

Preferably technical scheme three:

(2) taking aluminosilicate high-temperature electric conduction glue, stir, furnishing pasty slurry, by this pasty slurry uniform spreading Overlaying on aluminium foil, being coated with thickness is 0.01mm；Exfoliated graphite sheet on uniform fold in the pasty slurry being coated with, is coated with thickness again Degree is 0.08mm, is then vacuum dried at normal temperatures 1 hour by the moist expanded graphite-aluminum compound foil being coated with, prepares Expanded graphite-aluminum compound foil；

(4) being placed in high temperature reaction stove by prepared flakey expanded graphite-aluminum compound foil, described high temperature reaction stove is Vacuum tube furnace, after pumping furnace air, is passed through protective gas argon in high temperature reaction stove and protects, be warming up to 600 DEG C, it is continually fed into protective gas, 600 DEG C of more than constant temperature 30min；Then room temperature is dropped in protective gas protection, wash, It is dried, prepares the flaky graphite alkene device with aluminium base.

Preferably technical scheme four:

(1) take one piece of flexible expansion crystalline flake graphite washing, dry, utilize roll squeezer gradually to regulate gap and repeatedly press Prolonging, carry out auxiliary heating in calender line simultaneously, increase the flexibility of graphite, calendering, until graphite flake thickness is 0.025mm, to obtain final product To exfoliated graphite sheet;

(2) one side of exfoliated graphite sheet expanded graphite calendering obtained is as negative electrode, takes one piece of area more than negative electrode Pure stereotype do anode, in containing lead acetate electrolyte solution, logical unidirectional current, carries out constant current 25mA/cm²Electro-deposition 5 is little Time, form expanded graphite-metallic lead composite sheet;

(3) the graphite face of expanded graphite-metallic lead composite sheet is done anode, be electrolysed with 5M aqueous sulfuric acid Liquid, the graphite face of another expanded graphite-metallic lead composite sheet is done negative electrode, and constant voltage 2.3V condition is electrolysed 20 minutes, Flakey expanded graphite anode and negative electrode after process are dried 3 hours in an oven through washing;Dried sample is carried out again Above-mentioned energising processes 5 minutes, it is thus achieved that with the flaky graphite alkene device flaky graphite alkene of lead substrate.

Preferably technical scheme five:

(1) take one piece of flexible expansion crystalline flake graphite washing, dry, utilize roll squeezer gradually to regulate gap and repeatedly press Prolonging, carry out auxiliary heating in calender line simultaneously, increase the flexibility of graphite, calendering is until graphite flake thickness is 0.015mm and get final product To exfoliated graphite sheet;

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

(3) the graphite face of expanded graphite-metallic lead composite sheet is done anode, be electrolysed with 5M aqueous sulfuric acid Liquid, the graphite face of another expanded graphite-metallic lead composite sheet is done negative electrode, and constant voltage 2.1V condition is electrolysed 20 minutes, Flakey expanded graphite anode and negative electrode after process are dried 3 hours in an oven through washing;Dried sample is carried out again Above-mentioned energising processes 2 minutes, it is thus achieved that with flaky graphite alkene and the flaky graphite alkene device of lead substrate.

Preferably technical scheme six:

(2) Expandable graphite sheet prepared after calendering carrying out electric arc spraying aluminium lamination, the compressed air of spraying should clean, do Dry, pressure cannot be less than 0.4MPa, and spray distance is 250mm, and spray gun is at a right angle with Expandable graphite sheet surface as far as possible, the most not Must be less than 45 °, spray gun translational speed reaches 50 μm with a coating thickness, should have the width overlap of 1/3 between each spraying band, thick Degree requires uniform as far as possible, and the spray gun trend between each sprayed coating is mutually perpendicular to, alternate covering, until metal layer thickness reaches 60 μm, prepares expanded graphite-aluminum compound foil;

(3) expanded graphite-aluminum compound foil is done anode, do electrolyte with 10M aqueous sulfuric acid, another expanded graphite- Metal composite thin slice does negative electrode, and constant voltage 2.1V condition is electrolysed 30 minutes, obtains flakey expanded graphite-aluminum THIN COMPOSITE after process Sheet;

(4) the flakey expanded graphite-aluminum compound foil after processing more than is dried 3 hours in an oven through washing, will be dry Sample after dry is placed in microwave reaction chamber, by microwave reaction chamber evacuation and be passed through protective gas, uses microwave heating power For 800W, reaction chamber 300 DEG C, continuous heating 60 s, closing microwave, whole response system is cooled to 100 in a nitrogen atmosphere DEG C, it is thus achieved that with the flaky graphite alkene device of aluminium base, it is thus achieved that with flaky graphite alkene device and the flakey of aluminium base Graphene.

Preferably technical scheme seven:

(1) take the synthetic graphite flake that one piece of thickness is 0.1mm, wash, dry, utilize roll squeezer gradually to regulate gap Repeatedly rolling, carry out auxiliary heating in calender line simultaneously, increase the flexibility of graphite, calendering is until graphite flake thickness is 0.025mm, i.e. obtains graphite flake；

(2) graphite flake prepared after calendering carrying out electric arc spraying aluminium lamination, the compressed air of spraying should clean, do Dry, pressure cannot be less than 0.4MPa, and spray distance is 250mm, and spray gun is at a right angle with Expandable graphite sheet surface as far as possible, the most not Must be less than 45 °, spray gun translational speed reaches 50 μm with a coating thickness, should have the width overlap of 1/3 between each spraying band, thick Degree requires uniform as far as possible, and the spray gun trend between each sprayed coating is mutually perpendicular to, alternate covering, until metal layer thickness reaches 60 μm, prepares graphite-aluminum compound foil；

(3) graphite-aluminum compound foil being done anode, do electrolyte with 5M aqueous sulfuric acid, another expanded graphite-metal is multiple Closing thin slice and do negative electrode, constant voltage 2.3V condition is electrolysed 100 minutes, obtains flakey expanded graphite-aluminum compound foil after process；

(4) contain 100mL dehydrated alcohol with beaker, prepared expanded graphite-aluminum compound foil is submerged in dehydrated alcohol In, stand 1 hour；Then the above-mentioned beaker equipped with 100mL dehydrated alcohol having flooded expanded graphite-aluminum compound foil is put In tank so that in tank, the liquid level of water is equal with the ethanol liquid level within beaker；Take and can produce 100kHz and 400kHz The ultrasonic output probe of ultrasound wave, adjusts their power to 1000W, is then amplexiformed by ultrasonic output probe and be placed on beaker The bottom of outer wall, uses above two frequency to filling dehydrated alcohol and flakey expanded graphite system is ultrasonic simultaneously；Note therebetween The water temperature that meaning controls in circulating water chennel is 50 DEG C, and ultrasonic splitting time is 5 minutes, after ultrasonic end, it is thus achieved that with aluminium base Flaky graphite alkene device and flaky graphite alkene.

Preferably technical scheme eight:

(4) being placed in high temperature reaction stove by prepared flakey expanded graphite-aluminum compound foil, described high temperature reaction stove is Vacuum tube furnace or calcining furnace, after pumping furnace air, be passed through protective gas argon in high temperature reaction stove and protect, and rises Temperature, to 600 DEG C, is continually fed into protective gas, 600 DEG C of more than constant temperature 30min；Then room is dropped in protective gas protection Temperature, washs, is dried, prepare the flaky graphite alkene device with aluminium base.

Preferably technical scheme nine:

(1) take one piece of flexible expansion crystalline flake graphite washing, dry, utilize roll squeezer gradually to regulate gap and repeatedly press Prolonging, carry out auxiliary heating in calender line simultaneously, increase the flexibility of graphite, calendering, until graphite flake thickness is 0.05mm, to obtain final product To exfoliated graphite sheet；

(2) exfoliated graphite sheet prepared after calendering carries out adding thermo-compressed, heating temperature with aluminum slice when contacting Spending 650 DEG C, pressurization 5MPa makes aluminum slice generation plastic deformation, to fit in Expandable graphite sheet, prepares expanded graphite-aluminum and is combined Thin slice；

(4) the flakey expanded graphite-aluminum compound foil after processing more than is dried 3 hours in an oven through washing, will be dry Sample after dry is placed in microwave reaction chamber, by microwave reaction chamber evacuation and be passed through protective gas, uses microwave heating power For 800W, reaction chamber 600 DEG C, continuous heating 60 s, closing microwave, whole response system is cooled to 100 in a nitrogen atmosphere DEG C, it is thus achieved that with flaky graphite alkene device and the flaky graphite alkene device of aluminium base.

Preferably technical scheme ten:

(3) expanded graphite-aluminum compound foil is done anode, do electrolyte with 5M aqueous sulfuric acid, another expanded graphite-gold Belonging to compound foil and do negative electrode, constant voltage 20.0 V condition is electrolysed 1 second, obtains flakey expanded graphite-aluminum compound foil after process；

(4) contain 100mL dehydrated alcohol with beaker, prepared expanded graphite-aluminum compound foil is submerged in dehydrated alcohol In, stand 1 hour；Then the above-mentioned beaker equipped with 100mL dehydrated alcohol having flooded expanded graphite-aluminum compound foil is put In tank so that in tank, the liquid level of water is equal with the ethanol liquid level within beaker；Take and can produce 100kHz and 400kHz The ultrasonic output probe of ultrasound wave, adjusts their power to 100W, then ultrasonic output probe is placed in beaker outer wall Bottom, uses above two frequency to filling dehydrated alcohol and flakey expanded graphite system ultrasonication 2 hours simultaneously；Therebetween Notice that the water temperature controlled in circulating water chennel is 40 DEG C, after ultrasonic end, it is thus achieved that with aluminium base flaky graphite alkene device and Flaky graphite alkene.

Preferably technical scheme 11:

(2) exfoliated graphite sheet prepared after calendering carries out adding thermo-compressed, heating temperature with aluminum slice when contacting Spending 650 DEG C, pressurization 5MPa makes aluminum slice generation plastic deformation, to fit in Expandable graphite sheet, prepares expanded graphite-aluminum and is combined Thin slice;

(3) expanded graphite-aluminum compound foil is done anode, do electrolyte with 5M aqueous sulfuric acid, another expanded graphite-gold Belonging to compound foil and do negative electrode, constant voltage 1 mV condition is electrolysed 10 hours, the flakey expanded graphite-aluminum compound foil after process;

(4) being placed in high temperature reaction stove by prepared flakey expanded graphite-aluminum compound foil, described high temperature reaction stove is Vacuum tube furnace or calcining furnace, after pumping furnace air, be passed through protective gas argon in high temperature reaction stove and protect, and rises Temperature, to 600 DEG C, is continually fed into protective gas, 600 DEG C of more than constant temperature 30min；Then room is dropped in protective gas protection Temperature, washs, is dried, and prepares the flaky graphite alkene device with aluminium base and flaky graphite alkene.

Compared with prior art, the positive effect of the present invention is: (1) directly obtains flaky graphite alkene device, yield High, it is not necessary to separate, it is easy to preparation various types of electrodes material, heat-transfer matcrial, conductive material, sensor material, energy storage material, suction hydrogen material Material, catalyst and adsorbing material etc.；

(2) raw material sources are extensive, with low cost, and various types of graphite all can be used for preparing, preparation auxiliary material energy-saving Environmental protection, cheap for manufacturing cost；

(3) preparation method simplicity, properties of product are stablized controlled, are suitable for industrialized production.

Description of drawings 1 prepares the method process flow diagram of Graphene for the present invention.

Fig. 2 rolls expanded graphite process schematic representation.Wherein 1 being expressed as pressure roller, 2 are expressed as graphite flake after calendering.

Fig. 3 exfoliated graphite sheet and metal or non-metal conductor or semiconductors coupling flake 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.

The detailed description of the invention of the preparation method of the detailed description of the invention present invention presented below a kind of flaky graphite alkene.

Embodiment 1 bonding electrolysis microwave method is prepared flaky graphite alkene and is taken one piece of flexible expansion crystalline flake graphite washing, dries Dry, utilize roll squeezer gradually to regulate gap and repeatedly roll, calender line carries out auxiliary heating simultaneously, increases the soft of graphite Property, calendering is until graphite flake thickness is 0.05mm, and technical process as depicted in figs. 1 and 2, i.e. obtains exfoliated graphite sheet.

By acetylene black (conductive agent, particle diameter: about 10nm) 96.85%, CMC(sodium carboxymethyl cellulose) 1.55%, SBR(butylbenzene Rubber) 1.60%, stir, furnishing pasty slurry.Overlaying on aluminium foil by this pasty slurry uniform spreading, being coated with thickness is 0.01mm.Exfoliated graphite sheet on uniform fold in the pasty slurry being coated with again, being coated with thickness is 0.08mm, then will be coated with Good moist expanded graphite-aluminum compound foil is vacuum dried 1 hour at normal temperatures, prepares expanded graphite-aluminum compound foil (work Skill as it is shown in figure 1, expanded graphite-aluminum compound foil structure as it is shown on figure 3, wherein 1 be expressed as calendering after exfoliated graphite sheet, 2 Represent aluminum compound foil.).Expanded graphite-aluminum compound foil being done anode, does electrolyte with 10M aqueous sulfuric acid, another expands Graphite-metal compound foil does negative electrode, and electrolytic condition is: voltage is 2.3V, and the time is 20 minutes.Flakey after process is swollen Swollen graphite, as shown in Fig. 4 flaky graphite structural representation, wherein 1 is expressed as flakey expanded graphite；2 are expressed as aluminum again Close thin slice.

Flakey expanded graphite after more than processing is dried 3 hours in an oven through washing, is placed in by dried sample In microwave reaction chamber, by microwave reaction chamber evacuation and be passed through protective gas, it is 800W with microwave heating power, reaction chamber 600 DEG C, continuous heating 60 s, close microwave, whole response system is cooled to 100 DEG C in a nitrogen atmosphere, it is thus achieved that with aluminum base The flaky graphite alkene device of plate, the graphene sheet layer that this embodiment obtains is thin.The tulle that the present embodiment obtained product is transparent Shape, there is fold at edge, has obvious Graphene feature, and the number of plies scope of the flaky graphite alkene that this embodiment prepares mainly is concentrated At 1-8 layer, directly obtain flaky graphite alkene device, as shown in Fig. 5 flaky graphite alkene device architecture schematic diagram, wherein 1 It is expressed as flaky graphite alkene；2 are expressed as foil.As shown in Fig. 6 flaky graphite alkene device SEM phenogram.

Embodiment 2 spraying electrolysis microwave method prepares flaky graphite alkene

Take one piece of flexible expansion crystalline flake graphite washing, dry, utilize roll squeezer gradually to regulate gap and repeatedly roll, pressure Carrying out auxiliary heating during prolonging simultaneously, increase the flexibility of graphite, calendering is 0.025mm until graphite flake thickness, technical process As in figure 2 it is shown, i.e. obtain exfoliated graphite sheet.

The Expandable graphite sheet prepared after calendering carries out electric arc spraying aluminium lamination, and the compressed air of spraying should clean, be dried, Pressure cannot be less than 0.4MPa, and spray distance is 250mm, and spray gun is at a right angle with Expandable graphite sheet surface as far as possible, to cannot do without Less than 45 °, spray gun translational speed reaches 50 μm with a coating thickness, should have the width overlap of 1/3, thickness between each spraying band Requiring uniform as far as possible, the spray gun trend between each sprayed coating is mutually perpendicular to, alternate covering, until metal layer thickness reaches 60 μ M, prepares expanded graphite-aluminum compound foil,.

Expanded graphite-aluminum compound foil is done anode, does electrolyte with 10M aqueous sulfuric acid, another expanded graphite-metal Compound foil does negative electrode, and constant voltage 2.1V condition is electrolysed 30 minutes, and the flakey expanded graphite after process, such as Fig. 4 flakey Shown in graphite-structure schematic diagram, wherein 1 it is expressed as flakey expanded graphite；2 are expressed as aluminum compound foil.

Flakey expanded graphite after more than processing is dried 3 hours in an oven through washing, is placed in by dried sample In microwave reaction chamber, by microwave reaction chamber evacuation and be passed through protective gas, it is 800W with microwave heating power, reaction chamber 300 DEG C, continuous heating 60 s, close microwave, whole response system is cooled to 100 DEG C in a nitrogen atmosphere, it is thus achieved that with aluminum base The flaky graphite alkene device of plate, obtains the flaky graphite alkene device with aluminium base, the graphene film that this embodiment obtains Layer is thin.The gauze-like that the present embodiment obtained product is transparent, there is fold at edge, has obvious Graphene feature, this embodiment system The number of plies scope of the flaky graphite alkene obtained is concentrated mainly on 1-8 layer, directly obtains flaky graphite alkene device.

Embodiment 3 hot pressing electrolysis microwave method prepares flaky graphite alkene

Take one piece of flexible expansion crystalline flake graphite washing, dry, utilize roll squeezer gradually to regulate gap and repeatedly roll, pressure Carrying out auxiliary heating during prolonging simultaneously, increase the flexibility of graphite, calendering is until graphite flake thickness is 0.05mm, and technical process is such as Shown in Fig. 1 and Fig. 2, i.e. obtain exfoliated graphite sheet.

The exfoliated graphite sheet prepared after calendering carries out adding thermo-compressed, heating-up temperature when contacting with aluminum slice 650 DEG C, pressurization 5MPa makes aluminum slice generation plastic deformation, to fit in Expandable graphite sheet, prepares expanded graphite-aluminum THIN COMPOSITE Sheet.

Flakey expanded graphite after more than processing is dried 3 hours in an oven through washing, is placed in by dried sample In microwave reaction chamber, by microwave reaction chamber evacuation and be passed through protective gas, it is 800W with microwave heating power, reaction chamber 600 DEG C, continuous heating 60 s, close microwave, whole response system is cooled to 100 DEG C in a nitrogen atmosphere, it is thus achieved that with aluminum base The flaky graphite alkene device of plate, the graphene sheet layer that this embodiment obtains is thin.The tulle that the present embodiment obtained product is transparent Shape, there is fold at edge, has obvious Graphene feature, and the number of plies scope of the flaky graphite alkene that this embodiment prepares mainly is concentrated At 1-8 layer, directly obtain flaky graphite alkene device.

Embodiment 4 bonding electrolysis supercritical ultrasonics technology prepares flaky graphite alkene

Take one piece of flexible expansion crystalline flake graphite washing, dry, utilize roll squeezer gradually to regulate gap and repeatedly roll, pressure Carrying out auxiliary heating during prolonging simultaneously, increase the flexibility of graphite, calendering is until graphite flake thickness is 0.05mm, and technical process is such as Shown in Fig. 2, i.e. obtain exfoliated graphite sheet.

By acetylene black (conductive agent, particle diameter: about 10nm) 96.85%, CMC(sodium carboxymethyl cellulose) 1.55%, SBR(butylbenzene Rubber) 1.60%, stir, furnishing pasty slurry.Overlaying on aluminium foil by this pasty slurry uniform spreading, being coated with thickness is 0.01mm.Exfoliated graphite sheet on uniform fold in the pasty slurry being coated with again, being coated with thickness is 0.08mm, then will be coated with Good moist expanded graphite-aluminum compound foil is vacuum dried 1 hour at normal temperatures, prepares expanded graphite-aluminum compound foil (work Skill is as it is shown on figure 3, wherein 1 be expressed as exfoliated graphite sheet after calendering, and 2 represent aluminum compound foil.).

Contain 100mL dehydrated alcohol with beaker, prepared flakey expanded graphite-aluminum compound foil is submerged in anhydrous second In alcohol, stand 1 hour.Then by above-mentioned flooded flakey expanded graphite-aluminum compound foil equipped with 100mL dehydrated alcohol Beaker be placed in tank so that in tank, the liquid level of water is equal with the ethanol liquid level within beaker.Take and can produce 100kHz With the ultrasonic output probe of 400kHz ultrasound wave, their power is adjusted to 100W, then ultrasonic output probe is placed in burning The bottom of cup outer wall, uses above two frequency to surpass filling dehydrated alcohol and flakey expanded graphite-aluminum compound foil simultaneously Sound effect 2 hours.Notice that the water temperature controlled in circulating water chennel is 10 DEG C, after ultrasonic end, it is thus achieved that with the squama of aluminium base therebetween Flake graphite alkene device, the graphene sheet layer that this embodiment obtains is thin, and there is fold at edge, has obvious Graphene feature, and this is real Execute the number of plies average out to 3 of flaky graphite alkene～5 layers that example prepares, directly obtain the flaky graphite alkene device with aluminium base Part.

Embodiment 5 spraying electrolysis supercritical ultrasonics technology prepares flaky graphite alkene

Take the synthetic graphite flake that one piece of thickness is 0.1mm, wash, dry, utilize roll squeezer gradually to regulate gap and enter Row rolls repeatedly, carries out auxiliary heating in calender line simultaneously, increases the flexibility of graphite, and calendering is until graphite flake thickness is 0.025mm, technical process as depicted in figs. 1 and 2, i.e. obtains graphite flake.

The graphite flake prepared after calendering carries out electric arc spraying aluminium lamination, and the compressed air of spraying should clean, be dried, pressure Power cannot be less than 0.4MPa, and spray distance is 250mm, and spray gun is at a right angle with Expandable graphite sheet surface as far as possible, little to cannot do without In 45 °, spray gun translational speed reaches 50 μm with a coating thickness, should have the width overlap of 1/3 between each spraying band, and thickness is wanted Asking uniform as far as possible, the spray gun trend between each sprayed coating is mutually perpendicular to, alternate covering, until metal layer thickness reaches 60 μm, Prepare graphite-aluminum compound foil.

Graphite-aluminum compound foil is done anode, does electrolyte with 10M aqueous sulfuric acid, another expanded graphite-metal composite Thin slice does negative electrode, and constant voltage 2.3V condition is electrolysed 100 minutes, and the flakey expanded graphite after process, such as Fig. 4 flakey stone Shown in ink structure schematic diagram, wherein 1 it is expressed as flakey expanded graphite；2 are expressed as aluminum compound foil.

Contain 100mL dehydrated alcohol with beaker, prepared expanded graphite-aluminum compound foil is submerged in dehydrated alcohol, quiet Put 1 hour.Then the above-mentioned beaker equipped with 100mL dehydrated alcohol having flooded expanded graphite-aluminum compound foil is placed in tank In so that in tank, the liquid level of water is equal with the ethanol liquid level within beaker.Take and can produce 100kHz and 400kHz ultrasound wave Ultrasonic output probe, their power is adjusted to 1000W, then ultrasonic output probe is amplexiformed and is placed on beaker outer wall Bottom, uses above two frequency to filling dehydrated alcohol and flakey expanded graphite system is ultrasonic simultaneously.Note therebetween controlling Water temperature in circulating water chennel is 50 DEG C, and ultrasonic splitting time is 5 minutes, after ultrasonic end, it is thus achieved that with the flakey of aluminium base Graphene device, the graphene sheet layer that this embodiment obtains is thin, and there is fold at edge, has obvious Graphene feature, this embodiment The number of plies average out to 3 of flaky graphite alkene prepared～5 layers, directly obtain the flaky graphite alkene device with aluminium base.

Embodiment 6 hot pressing electrolysis supercritical ultrasonics technology prepares flaky graphite alkene

Expanded graphite-aluminum compound foil is done anode, does electrolyte with 5M aqueous sulfuric acid, another expanded graphite-metal Compound foil does negative electrode, and constant voltage 20.0 V condition is electrolysed 1 second, and the flakey expanded graphite after process, such as Fig. 4 flakey Shown in graphite-structure schematic diagram, wherein 1 it is expressed as flakey expanded graphite；2 are expressed as aluminum compound foil.

Contain 100mL dehydrated alcohol with beaker, prepared expanded graphite-aluminum compound foil is submerged in dehydrated alcohol, quiet Put 1 hour.Then the above-mentioned beaker equipped with 100mL dehydrated alcohol having flooded expanded graphite-aluminum compound foil is placed in tank In so that in tank, the liquid level of water is equal with the ethanol liquid level within beaker.Take and can produce 100kHz and 400kHz ultrasound wave Ultrasonic output probe, their power is adjusted to 100W, then ultrasonic output probe is placed in the bottom of beaker outer wall, with Time use above two frequency to filling dehydrated alcohol and flakey expanded graphite system ultrasonication 2 hours.Note control therebetween Water temperature in circulating water chennel processed is 40 DEG C, after ultrasonic end, it is thus achieved that with the flaky graphite alkene device of aluminium base, this embodiment The graphene sheet layer obtained is thin, and there is fold at edge, has obvious Graphene feature, the flaky graphite alkene that this embodiment prepares Number of plies average out to 3～5 layers, directly obtain the flaky graphite alkene device with aluminium base.

Embodiment 7 bonding electrolysis high temperature method prepares flaky graphite alkene

Take aluminosilicate high-temperature electric conduction glue, stir, furnishing pasty slurry, this pasty slurry uniform spreading is overlayed on On aluminium foil, being coated with thickness is 0.01mm.Exfoliated graphite sheet on uniform fold in the pasty slurry being coated with again, being coated with thickness is 0.08mm, is then vacuum dried the moist expanded graphite-aluminum compound foil being coated with at normal temperatures 1 hour, prepares and expand Graphite-aluminum compound foil (technique such as Fig. 1 and expanded graphite-aluminum compound foil as shown in Figure 3, wherein 1 be expressed as calendering after swollen Swollen graphite flake, 2 represent aluminum compound foil.).

Being placed in high temperature reaction stove by prepared flakey expanded graphite, described high temperature reaction stove is vacuum tube furnace, takes out After removing furnace air, in high temperature reaction stove, it is passed through protective gas argon protects, be warming up to 600 DEG C, be continually fed into guarantor Protecting property gas, 600 DEG C of more than constant temperature 30min；Then protective gas protection drop to room temperature, wash, be dried, prepare with The flaky graphite alkene device of aluminium base.

Embodiment 8 spraying electrolysis high temperature method prepares flaky graphite alkene

The Expandable graphite sheet prepared after calendering carries out electric arc spraying aluminium lamination, and the compressed air of spraying should clean, be dried, Pressure cannot be less than 0.4MPa, and spray distance is 250mm, and spray gun is at a right angle with Expandable graphite sheet surface as far as possible, to cannot do without Less than 45 °, spray gun translational speed reaches 50 μm with a coating thickness, should have the width overlap of 1/3, thickness between each spraying band Requiring uniform as far as possible, the spray gun trend between each sprayed coating is mutually perpendicular to, alternate covering, until metal layer thickness reaches 60 μ M, prepares expanded graphite-aluminum compound foil.

Being placed in high temperature reaction stove by prepared flakey expanded graphite, described high temperature reaction stove is vacuum tube furnace or forges Burn stove, after pumping furnace air, in high temperature reaction stove, be passed through protective gas argon protect, be warming up to 600 DEG C, continue It is passed through protective gas, 600 DEG C of more than constant temperature 30min；Then drop to room temperature in protective gas protection, wash, be dried, system Must be with the flaky graphite alkene device of aluminium base.

Embodiment 9 hot pressing electrolysis high temperature method prepares flaky graphite alkene

Expanded graphite-aluminum compound foil is done anode, does electrolyte with 5M aqueous sulfuric acid, another expanded graphite-metal Compound foil does negative electrode, and constant voltage 1 mV condition is electrolysed 10 hours, and the flakey expanded graphite after process, such as Fig. 4 flakey Shown in graphite-structure schematic diagram, wherein 1 it is expressed as flakey expanded graphite；2 are expressed as aluminum compound foil.

Embodiment 10 electro-deposition electrolysis prepares flaky graphite alkene

The one side of exfoliated graphite sheet expanded graphite calendering obtained, as negative electrode, takes one piece of area and is more than the pure of negative electrode Stereotype does anode, and in containing lead acetate electrolyte solution, logical unidirectional current, carries out constant current 25mA/cm²Electro-deposition 5 hours, Form expanded graphite-metallic lead composite sheet.

The graphite face of expanded graphite-metallic lead composite sheet is done anode, does electrolyte with 5M aqueous sulfuric acid, The graphite face of another expanded graphite-metallic lead composite sheet is done negative electrode, and constant voltage 2.3V condition is electrolysed 20 minutes, place Flakey expanded graphite anode and negative electrode after reason are dried 3 hours in an oven through washing.On dried sample is carried out again State energising to process 5 minutes, it is thus achieved that with the flaky graphite alkene device of lead substrate, the graphene sheet layer that this embodiment obtains is thin. The gauze-like that the present embodiment obtained product is transparent, there is fold at edge, has obvious Graphene feature, the squama that this embodiment prepares The number of plies scope of flake graphite alkene is concentrated mainly on 1-8 layer, directly obtains flaky graphite alkene device, such as Fig. 5 flakey stone Ink alkene device architecture schematic diagram, wherein 1 is expressed as flaky graphite alkene；2 are expressed as lead metal thin slice.

Embodiment 11 chemical deposition electrolysis prepares flaky graphite alkene

Take one piece of flexible expansion crystalline flake graphite washing, dry, utilize roll squeezer gradually to regulate gap and repeatedly roll, pressure Carrying out auxiliary heating during prolonging simultaneously, increase the flexibility of graphite, calendering is 0.015mm until graphite flake thickness, technical process As in figure 2 it is shown, i.e. 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 is anti- Answer 5 hours, form expanded graphite-metallic lead composite sheet.

The graphite face of expanded graphite-metallic lead composite sheet is done anode, does electrolyte with 5M aqueous sulfuric acid, The graphite face of another expanded graphite-metallic lead composite sheet is done negative electrode, and constant voltage 2.1V condition is electrolysed 20 minutes, place Flakey expanded graphite anode and negative electrode after reason are dried 3 hours in an oven through washing.On dried sample is carried out again State energising to process 2 minutes, it is thus achieved that with the flaky graphite alkene device of lead substrate, the graphene sheet layer that this embodiment obtains is thin. The gauze-like that the present embodiment obtained product is transparent, there is fold at edge, has obvious Graphene feature, the squama that this embodiment prepares The number of plies scope of flake graphite alkene is concentrated mainly on 1-8 layer, directly obtains flaky graphite alkene device, such as Fig. 5 flakey stone Ink alkene device architecture schematic diagram, wherein 1 is expressed as flaky graphite alkene；2 are expressed as lead metal thin slice.

Embodiment 12 bonding electrolysis supercritical ultrasonics technology prepares flaky graphite alkene

Contain 100mL dehydrated alcohol with beaker, prepared flakey expanded graphite-aluminum compound foil is submerged in anhydrous second In alcohol, stand 1 hour.Then by above-mentioned flooded flakey expanded graphite-aluminum compound foil equipped with 100mL dehydrated alcohol Beaker be placed in tank so that in tank, the liquid level of water is equal with the ethanol liquid level within beaker.Take and can produce 100kHz The ultrasonic output probe of ultrasound wave, adjusts their power to 1 W, then ultrasonic output probe is placed in the end of beaker outer wall Portion, uses above two frequency to filling dehydrated alcohol and flakey expanded graphite-aluminum compound foil ultrasonication 2 is little simultaneously Time.Notice that the water temperature controlled in circulating water chennel is 10 DEG C, after ultrasonic end, it is thus achieved that with the flaky graphite alkene of aluminium base therebetween Device, the graphene sheet layer that this embodiment obtains is thin, and there is fold at edge, has obvious Graphene feature, and this embodiment prepares The number of plies average out to of flaky graphite alkene 12 layers, directly obtains the flaky graphite alkene device with aluminium base.

Embodiment 13 hot pressing electrolysis microwave method prepares flaky graphite alkene

Flakey expanded graphite after more than processing is dried 3 hours in an oven through washing, is placed in by dried sample In microwave reaction chamber, by microwave reaction chamber evacuation and be passed through protective gas, power is 10 W, uses microwave heating reaction chamber To 300 DEG C, continuous heating 180s, close microwave, whole response system is cooled to 100 DEG C in a nitrogen atmosphere, prepares flakey Graphene, it is thus achieved that with the flaky graphite alkene device of aluminium base, the graphene sheet layer that this embodiment obtains is thin.The present embodiment institute Obtaining the gauze-like that product is transparent, there is fold at edge, has obvious Graphene feature, the flaky graphite alkene that this embodiment prepares Number of plies scope be concentrated mainly on 1-8 layer, directly obtain flaky graphite alkene device.

Embodiment 14 hot pressing electrolysis microwave method prepares flaky graphite alkene

Flakey expanded graphite after more than processing is dried 3 hours in an oven through washing, is placed in by dried sample In microwave reaction chamber, power is 1000 W, by microwave reaction chamber evacuation and be passed through protective gas, reacts with microwave heating Chamber is to 600 DEG C, and continuous heating 2 s, closedown microwave, whole response system is cooled to 100 DEG C in a nitrogen atmosphere, prepares scale Shape Graphene, it is thus achieved that with the flaky graphite alkene device of aluminium base, the graphene sheet layer that this embodiment obtains is thin.The present embodiment The gauze-like that obtained product is transparent, there is fold at edge, has obvious Graphene feature, the flaky graphite that this embodiment prepares The number of plies scope of alkene is concentrated mainly on 1-8 layer, directly obtains flaky graphite alkene device.

Embodiment 15 electro-deposition electrolysis prepares flaky graphite alkene

The graphite face of expanded graphite-metallic lead composite sheet is done anode, does electrolyte with 5M aqueous sulfuric acid, Lead electrode does negative electrode, constant voltage 2.3V condition DC electrolysis 20 minutes, the flakey expanded graphite anode after process and negative electrode 3 hours it are dried in an oven through washing.Dried sample carries out above-mentioned energising again process 5 minutes, it is thus achieved that with lead substrate Flaky graphite alkene device, this embodiment obtain graphene sheet layer thin.The gauze-like 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 prepares is concentrated mainly on 20 layers, directly obtain flaky graphite alkene device, such as Fig. 5 flaky graphite alkene device architecture schematic diagram, wherein 1 be expressed as squama Flake graphite alkene；2 are expressed as lead metal thin slice.

Embodiment 16 electro-deposition electrolysis prepares flaky graphite alkene

The graphite face of expanded graphite-metallic lead composite sheet is done anode, does electrolyte with 5M glycine solution, The graphite layers that energising prepares has the flakey expanded graphite of compound for electrode, constant current 1A condition DC electrolysis 20 points Clock, flakey expanded graphite anode and negative electrode after process are dried 3 hours in an oven through washing.Dried sample is entered again The above-mentioned energising of row processes 5 minutes, it is thus achieved that with the flaky graphite alkene device of lead substrate, the graphene sheet layer that this embodiment obtains Thin.The gauze-like that the present embodiment obtained product is transparent, there is fold at edge, has obvious Graphene feature, and this embodiment prepares The number of plies scope of flaky graphite alkene be concentrated mainly on 1-8 layer, directly obtain flaky graphite alkene device, such as Fig. 5 scale Shape graphene device structural representation, wherein 1 is expressed as flaky graphite alkene；2 are expressed as lead metal thin slice.

Embodiment 17 bonding electrolysis high temperature method prepares flaky graphite alkene

Being placed in high temperature reaction stove by prepared flakey expanded graphite, described high temperature reaction stove is vacuum tube furnace or forges Burn stove, after pumping furnace air, in high temperature reaction stove, be passed through protective gas argon protect, be warming up to 300 DEG C, continue It is passed through protective gas, 600 DEG C of more than constant temperature 30min；Then drop to room temperature in protective gas protection, wash, be dried, system Must be with the flaky graphite alkene device of aluminium base.

The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art Member, without departing from the inventive concept of the premise, it is also possible to make some improvement, these improvement also should be regarded as the guarantor in the present invention In the range of protecting.

Claims

1. the preparation method of a flaky graphite alkene, it is characterised in that step is as follows:

(1) take one piece of flexible expansion crystalline flake graphite washing, dry, utilize roll squeezer gradually to regulate gap and repeatedly roll, pressure Carrying out auxiliary heating during prolonging simultaneously, increase the flexibility of graphite, calendering, until graphite flake thickness is 0.05mm, is i.e. expanded Graphite flake;

(2) by acetylene black 96.85%, sodium carboxymethyl cellulose 1.55%, butadiene-styrene rubber 1.60%, stir, furnishing pasty state Slurry；Overlaying on aluminium foil by this pasty slurry uniform spreading, being coated with thickness is 0.01mm；Uniformly cover in the pasty slurry being coated with again Covering exfoliated graphite sheet, being coated with thickness is 0.08mm, then by moist expanded graphite-aluminum compound foil of being coated with often The lower vacuum drying of temperature 1 hour, prepares expanded graphite-aluminum compound foil；

(3) expanded graphite-aluminum compound foil is done anode, do electrolyte with 10M aqueous sulfuric acid, another expanded graphite-metal Compound foil 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 after processing more than is dried 3 hours in an oven through washing, is placed in micro-by dried sample In ripple reaction chamber, by microwave reaction chamber evacuation and be passed through protective gas, it is 800W with microwave heating power, reaction chamber 600 DEG C, continuous heating 60 s, close microwave, whole response system is cooled to 100 DEG C in a nitrogen atmosphere, it is thus achieved that with aluminium base Flaky graphite alkene device, is flaky graphite alkene above aluminium base.

2. the preparation method of a flaky graphite alkene, it is characterised in that step is as follows:

(1) take one piece of flexible expansion crystalline flake graphite washing, dry, utilize roll squeezer gradually to regulate gap and repeatedly roll, pressure Carrying out auxiliary heating during prolonging simultaneously, increase the flexibility of graphite, calendering, until graphite flake thickness is 0.05mm, is i.e. expanded Graphite flake；

(2) by acetylene black 96.85%, sodium carboxymethyl cellulose 1.55%, butadiene-styrene rubber 1.60%, stir, adjust Become pasty slurry;Overlaying on aluminium foil by this pasty slurry uniform spreading, being coated with thickness is 0.01mm;Again in the pasty slurry being coated with Exfoliated graphite sheet on uniform fold, being coated with thickness is 0.08mm, the moist expanded graphite-aluminum THIN COMPOSITE being then coated with Sheet is vacuum dried 1 hour at normal temperatures, prepares expanded graphite-aluminum compound foil;

(3) expanded graphite-aluminum compound foil is done anode, do electrolyte with 10M aqueous sulfuric acid, another expanded graphite-metal Compound foil does negative electrode, and constant voltage 2.1V condition is electrolysed 30 minutes, obtains flakey expanded graphite-aluminum compound foil after process；

(4) contain 100mL dehydrated alcohol with beaker, prepared flakey expanded graphite-aluminum compound foil is submerged in dehydrated alcohol In, stand 1 hour；Then by above-mentioned flooded flakey expanded graphite-aluminum compound foil equipped with 100mL dehydrated alcohol Beaker is placed in tank so that in tank, the liquid level of water is equal with the ethanol liquid level within beaker；Take can produce 100kHz and The ultrasonic output probe of 400kHz ultrasound wave, adjusts their power to 100W, then ultrasonic output probe is placed in beaker The bottom of outer wall, uses above two frequency to filling dehydrated alcohol and flakey expanded graphite-aluminum compound foil is ultrasonic simultaneously Act on 2 hours；Notice that the water temperature controlled in circulating water chennel is 10 DEG C, after ultrasonic end, it is thus achieved that with the scale of aluminium base therebetween Shape graphene device and flaky graphite alkene.

3. the preparation method of a flaky graphite alkene, it is characterised in that step is as follows:

(2) take aluminosilicate high-temperature electric conduction glue, stir, furnishing pasty slurry, this pasty slurry uniform spreading is overlayed on On aluminium foil, being coated with thickness is 0.01mm；Exfoliated graphite sheet on uniform fold in the pasty slurry being coated with again, being coated with thickness is 0.08mm, is then vacuum dried the moist expanded graphite-aluminum compound foil being coated with at normal temperatures 1 hour, prepares and expand Graphite-aluminum compound foil；

(4) being placed in high temperature reaction stove by prepared flakey expanded graphite-aluminum compound foil, described high temperature reaction stove is vacuum Tube furnace, after pumping furnace air, is passed through protective gas argon in high temperature reaction stove and protects, be warming up to 600 DEG C, hold Continue and be passed through protective gas, 600 DEG C of more than constant temperature 30min；Then drop to room temperature in protective gas protection, wash, be dried, Prepare the flaky graphite alkene device with aluminium base.

4. the preparation method of a flaky graphite alkene, it is characterised in that step is as follows:

(1) take one piece of flexible expansion crystalline flake graphite washing, dry, utilize roll squeezer gradually to regulate gap and repeatedly roll, pressure Carrying out auxiliary heating during prolonging simultaneously, increase the flexibility of graphite, calendering, until graphite flake thickness is 0.025mm, i.e. obtains swollen Swollen graphite flake;

(2) one side of exfoliated graphite sheet expanded graphite calendering obtained is as negative electrode, takes one piece of area and is more than the pure of negative electrode Stereotype does anode, and in containing lead acetate electrolyte solution, logical unidirectional current, carries out constant current 25mA/cm2 electro-deposition 5 hours, Form expanded graphite-metallic lead composite sheet;

(3) the graphite face of expanded graphite-metallic lead composite sheet is done anode, does electrolyte with 5M aqueous sulfuric acid, The graphite face of another expanded graphite-metallic lead composite sheet is done negative electrode, and constant voltage 2.3V condition is electrolysed 20 minutes, place Flakey expanded graphite anode and negative electrode after reason are dried 3 hours in an oven through washing;On dried sample is carried out again State energising to process 5 minutes, it is thus achieved that with the flaky graphite alkene device flaky graphite alkene of lead substrate.

5. the preparation method of a flaky graphite alkene, it is characterised in that step is as follows:

(1) take one piece of flexible expansion crystalline flake graphite washing, dry, utilize roll squeezer gradually to regulate gap and repeatedly roll, pressure Carrying out auxiliary heating during prolonging simultaneously, increase the flexibility of graphite, calendering is until graphite flake thickness is that 0.015mm is i.e. expanded Graphite flake;

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

(3) the graphite face of expanded graphite-metallic lead composite sheet is done anode, does electrolyte with 5M aqueous sulfuric acid, The graphite face of another expanded graphite-metallic lead composite sheet is done negative electrode, and constant voltage 2.1V condition is electrolysed 20 minutes, place Flakey expanded graphite anode and negative electrode after reason are dried 3 hours in an oven through washing;On dried sample is carried out again State energising to process 2 minutes, it is thus achieved that with flaky graphite alkene and the flaky graphite alkene device of lead substrate.

6. the preparation method of a flaky graphite alkene, it is characterised in that step is as follows:

(2) Expandable graphite sheet prepared after calendering carrying out electric arc spraying aluminium lamination, the compressed air of spraying should clean, be dried, Pressure cannot be less than 0.4MPa, and spray distance is 250mm, and spray gun is at a right angle with Expandable graphite sheet surface as far as possible, to cannot do without Less than 45 °, spray gun translational speed reaches 50 μm with a coating thickness, should have the width overlap of 1/3, thickness between each spraying band Requiring uniform as far as possible, the spray gun trend between each sprayed coating is mutually perpendicular to, alternate covering, until metal layer thickness reaches 60 μ M, prepares expanded graphite-aluminum compound foil;

(3) expanded graphite-aluminum compound foil is done anode, do electrolyte with 10M aqueous sulfuric acid, another expanded graphite-metal Compound foil does negative electrode, and constant voltage 2.1V condition is electrolysed 30 minutes, obtains flakey expanded graphite-aluminum compound foil after process;

(4) the flakey expanded graphite-aluminum compound foil after processing more than is dried 3 hours in an oven through washing, will be dried Sample be placed in microwave reaction chamber, by microwave reaction chamber evacuation and be passed through protective gas, with microwave heating power be 800W, reaction chamber 300 DEG C, continuous heating 60 s, close microwave, whole response system is cooled to 100 DEG C in a nitrogen atmosphere, obtains The flaky graphite alkene device with aluminium base and flaky graphite must be obtained with the flaky graphite alkene device of aluminium base Alkene.

7. the preparation method of a flaky graphite alkene, it is characterised in that step is as follows:

(1) take the synthetic graphite flake that one piece of thickness is 0.1mm, wash, dry, utilize roll squeezer gradually to regulate gap and carry out Repeatedly rolling, carry out auxiliary heating in calender line simultaneously, increase the flexibility of graphite, calendering is until graphite flake thickness is 0.025mm, i.e. obtains graphite flake；

(2) graphite flake prepared after calendering carrying out electric arc spraying aluminium lamination, the compressed air of spraying should clean, be dried, pressure Power cannot be less than 0.4MPa, and spray distance is 250mm, and spray gun is at a right angle with Expandable graphite sheet surface as far as possible, little to cannot do without In 45 °, spray gun translational speed reaches 50 μm with a coating thickness, should have the width overlap of 1/3 between each spraying band, and thickness is wanted Asking uniform as far as possible, the spray gun trend between each sprayed coating is mutually perpendicular to, alternate covering, until metal layer thickness reaches 60 μm, Prepare graphite-aluminum compound foil；

(3) graphite-aluminum compound foil is done anode, do electrolyte with 10M aqueous sulfuric acid, another expanded graphite-metal composite Thin slice does negative electrode, and constant voltage 2.3V condition is electrolysed 100 minutes, obtains flakey expanded graphite-aluminum compound foil after process；

(4) contain 100mL dehydrated alcohol with beaker, prepared expanded graphite-aluminum compound foil is submerged in dehydrated alcohol, quiet Put 1 hour；Then the above-mentioned beaker equipped with 100mL dehydrated alcohol having flooded expanded graphite-aluminum compound foil is placed in tank In so that in tank, the liquid level of water is equal with the ethanol liquid level within beaker；Take and can produce 100kHz and 400kHz ultrasound wave Ultrasonic output probe, their power is adjusted to 1000W, then ultrasonic output probe is amplexiformed and is placed on beaker outer wall Bottom, uses above two frequency to filling dehydrated alcohol and flakey expanded graphite system is ultrasonic simultaneously；Note therebetween controlling Water temperature in circulating water chennel is 50 DEG C, and ultrasonic splitting time is 5 minutes, after ultrasonic end, it is thus achieved that with the flakey of aluminium base Graphene device and flaky graphite alkene.

8. the preparation method of a flaky graphite alkene, it is characterised in that step is as follows:

(4) being placed in high temperature reaction stove by prepared flakey expanded graphite-aluminum compound foil, described high temperature reaction stove is vacuum Tube furnace or calcining furnace, after pumping furnace air, be passed through protective gas argon in high temperature reaction stove and protect, be warming up to 600 DEG C, it is continually fed into protective gas, 600 DEG C of more than constant temperature 30min；Then drop to room temperature in protective gas protection, wash Wash, be dried, prepare the flaky graphite alkene device with aluminium base.

9. the preparation method of a flaky graphite alkene, it is characterised in that step is as follows:

(2) exfoliated graphite sheet prepared after calendering carries out adding thermo-compressed, heating-up temperature 650 when contacting with aluminum slice DEG C, pressurization 5MPa makes aluminum slice generation plastic deformation, to fit in Expandable graphite sheet, prepares expanded graphite-aluminum compound foil；

(4) the flakey expanded graphite-aluminum compound foil after processing more than is dried 3 hours in an oven through washing, will be dried Sample be placed in microwave reaction chamber, by microwave reaction chamber evacuation and be passed through protective gas, with microwave heating power be 800W, reaction chamber 600 DEG C, continuous heating 60 s, close microwave, whole response system is cooled to 100 DEG C in a nitrogen atmosphere, obtains Must be with the flaky graphite alkene device of aluminium base and flaky graphite alkene device.

10. the preparation method of a flaky graphite alkene, it is characterised in that step is as follows:

(3) expanded graphite-aluminum compound foil being done anode, do electrolyte with 5M aqueous sulfuric acid, another expanded graphite-metal is multiple Closing thin slice and do negative electrode, constant voltage 20.0 V condition is electrolysed 1 second, obtains flakey expanded graphite-aluminum compound foil after process；

(4) contain 100mL dehydrated alcohol with beaker, prepared expanded graphite-aluminum compound foil is submerged in dehydrated alcohol, quiet Put 1 hour；Then the above-mentioned beaker equipped with 100mL dehydrated alcohol having flooded expanded graphite-aluminum compound foil is placed in tank In so that in tank, the liquid level of water is equal with the ethanol liquid level within beaker；Take and can produce 100kHz and 400kHz ultrasound wave Ultrasonic output probe, their power is adjusted to 100W, then ultrasonic output probe is placed in the bottom of beaker outer wall, with Time use above two frequency to filling dehydrated alcohol and flakey expanded graphite system ultrasonication 2 hours；Note control therebetween Water temperature in circulating water chennel processed is 40 DEG C, after ultrasonic end, it is thus achieved that with flaky graphite alkene device and the flakey of aluminium base Graphene.

The preparation method of 11. 1 kinds of flaky graphite alkene, it is characterised in that step is as follows:

(2) exfoliated graphite sheet prepared after calendering carries out adding thermo-compressed, heating-up temperature 650 when contacting with aluminum slice DEG C, pressurization 5MPa makes aluminum slice generation plastic deformation, to fit in Expandable graphite sheet, prepares expanded graphite-aluminum compound foil;

(3) expanded graphite-aluminum compound foil being done anode, do electrolyte with 5M aqueous sulfuric acid, another expanded graphite-metal is multiple Closing thin slice and do negative electrode, constant voltage 1 mV condition is electrolysed 10 hours, the flakey expanded graphite-aluminum compound foil after process;

(4) being placed in high temperature reaction stove by prepared flakey expanded graphite-aluminum compound foil, described high temperature reaction stove is vacuum Tube furnace or calcining furnace, after pumping furnace air, be passed through protective gas argon in high temperature reaction stove and protect, be warming up to 600 DEG C, it is continually fed into protective gas, 600 DEG C of more than constant temperature 30min；Then drop to room temperature in protective gas protection, wash Wash, be dried, prepare the flaky graphite alkene device with aluminium base and flaky graphite alkene.