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.
(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, 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:
(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) 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;
(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) 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:
(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) 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;
(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) 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:
(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) 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;
(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) 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;
(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) 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:
(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;
(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:
(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;
(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.
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.
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 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.)。
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.
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
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.
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.
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 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.
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.)。
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.
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
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.
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
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.
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.
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 10 galvanic deposit 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 0.025mm, technological process as
fig. 2shown in, namely obtain exfoliated graphite sheet.
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
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.)。
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.
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
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.
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; 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
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.
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; 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
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.
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, 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
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.
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 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
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.
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.)。
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.
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.