CN103318878B - A kind of oversized shape is than the preparation method and its usage of graphene microchip - Google Patents
A kind of oversized shape is than the preparation method and its usage of graphene microchip Download PDFInfo
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Abstract
The present invention relates to the preparation method and its usage of a kind of oversized shape than graphene microchip.Graphene oxide paper or the mixing material containing partial impurities are placed in silica tube, pass into the H of certain air pressure
2, with high-rate laser, line scanning heating is focused into sample, under given conditions, can obtain in room temperature environment and be less than that 10 atomic shells, electric conductivity are high, the complete graphene microchip of good uniformity, and retrofit can be carried out to the impurity in material.The average atom number of plies of obtained Graphene is at 6-8 layer, and between 2.0-3.0nm, microplate shape ratio can close to 10000.Its optics and conductivity are significantly better than graphene microchip prepared by traditional chemical method of reducing; Regulated by the segmentation of Laser Scanning Parameters, the method has that target processibility is strong, the microplate number of plies and size is controlled, equipment simple, clean and effective, flexible operation, can repeatedly carry out the advantage such as sample preparation and patterning processing, has excellent industrial application value.
Description
Technical field
The present invention relates to a kind of preparation method of graphene microchip, particularly a kind of oversized shape is than the preparation method and its usage of graphene microchip.
Background technology
Graphene microchip refers generally to carbon-coating number more than 10 layers, the ultra-thin Graphene stratiform accumulation body of thickness in 5-100 nanometer range.In the document had, graphite original planar carbon six-ring conjugation crystalline structure is maintained also referred to as GrapheneNanosheets. graphene microchip, there is excellent physical strength, conduction, heat conductivility, and good lubrication, high temperature resistant and anticorrosion properties.Relative to common graphite, the thickness of graphene microchip is within the scope of nanoscale, but its radial width can reach several to dozens of micron, has the shape ratio (diameter/thickness ratio) of super large.Graphene microchip, be multi-layer graphene structure, but the characteristic of Graphene, such as conduction, heat conduction, printing opacity, flexibility etc. are kept very well, can add to widely in existing various base mateiral as a kind of industrial raw materials, the performance of current material is improved.The good characteristic that graphene microchip has due to it, its Application Areas is boundless, such as improves the heat conduction of plastic cement and heat dispersion, plastic cement conduction and antistatic modified, strengthens the intensity of plastic cement, and improves wear-resisting, the lubricity of plastic cement and erosion resistance etc.Owing to having nano thickness, easily and other material compound as even in polymer materials, and form good compound interface, the high strength of Graphene, lubrication, high temperature resistant and conductive characteristic can take in the middle of matrix material by graphene microchip, thus can design, prepare high performance composite.It is all good application that graphene composite material, Graphene plastics, Graphene rubber, Graphene conductive ink, Graphene coating, Graphene inhale ripple hidden function plate, Graphene radiating element, Graphene power cell, Graphene functional coating, ultracapacitor, seawater desalination desalting device etc.
Current, graphene microchip is applied to matrix material three features: the gauffer of (1) graphenic surface and defect enhance the combination with polymeric substrates, are beneficial to dynamic changes process between interface; (2) Graphene has high-specific surface area, and upper and lower surface can be fully utilized; (3) unique two-dirnentional structure of Graphene can effectively hinder crackle to spread, thus the fracture toughness property of reinforced composite.Therefore, study the controlled synthesis of large shape than the Graphene of (large size and few atomic shell) for the application of its matrix material, the especially improvement of macromechanical property, has positive effect.
The manufacturer of current domestic sale graphene microchip mainly contains the hexa-atomic plain company limited in Changzhou, Nanjing Ji Cang nanosecond science and technology Science and Technology Ltd., Ningbo of Zhejiang Mo Xi Science and Technology Ltd. etc., and its preparation method comprises thermal reduction oxidation style and solvent method etc.Main products has powder and slurry two kinds of forms, can be applicable to medicine, detection, catalyzer, conduction and heat conduction field etc.The current production line having extended annual output 300 tons of graphene microchip of Ningbo of Zhejiang Mo Xi Science and Technology Ltd., price drops to 3 yuan/gram; Their Morsh-P2 product comprises the Graphene (mean thickness 3.5nm) of the less number of plies, and diameter between 5-10um, but accurately cannot carry out microcosmic thickness or size control.XG Technology Co., Ltd. of the U.S. can accurately volume production diameter 15 and the serial different graphene microchip of 25um two kinds, but thickness is comparatively large, is distributed in 6-8nm (M rank) or 15nm (H series) respectively.The controlled synthesis of less than 10 layers graphene microchip of super large shape ratio there is no maturation method at present at home.
LASER HEATING redox graphene solution (or spin coating liquid) and the preparation of patterning is on this basis utilized once repeatedly to be reported, but method therefor needs the graphene oxide that disperses in laser direct irradiation solvent before, Graphene not only after reduction is easily reunited, and in solution, the weak acid material of self impurity or generation may stop the part carboxyl reduction at graphene oxide edge, thus larger sized graphene microchip cannot be obtained.In fact, traditional solution irradiation redox graphene is utilized to be quite difficult for the controllable precise of the product atom number of plies or size.
On the other hand, graphene composite material is especially based on the preparation of the polymer composites of Graphene, and the technology needing some new gets involved.For the Graphene of chemical reduction, pile up because stratiform easily occurs for its plane pattern and Interaction between layers; Current a kind of effective solution route is by adding tensio-active agent or mixing the combination avoided between Graphene with polymkeric substance in advance before reduction.Because Graphene has sp2 hybrid structure in face, usually the non covalent bond between polymkeric substance is combined very weak, thus chemically modified Graphene or graphene oxide are more suitable for as wild phase than pure grapheme material, but in chemically modified and graphene oxide face, the reduction of character proposes new requirement for composite structure design itself.
Summary of the invention
The object of the invention is to solve above-mentioned deficiency, propose a kind ofly to prepare the method for large shape than graphene microchip, and the new route of doped graphene and graphene composite material is prepared in development on this basis.Its feature is to transfer the controllable parameter of Laser focus to affect final dimension and thickness key variables, utilize the advantage of the rapid heating of modern laser and localization modification to segment and regulate Graphene micro-raman spectra, performance and size, and in conjunction with the corresponding doping of multi-component preparation of target materials or composite structure.
The technical scheme realizing the object of the invention is: a kind of oversized shape is than the preparation method of graphene microchip; Be specially following steps: graphene oxide paper or its matrix material are positioned in vitreosil pipe by (1); Laser apparatus is adopted to carry out rapid scanning heat reduction to sample; (2) test product.
Above-mentioned oversized shape is than the preparation method of graphene microchip, and described step (1), for be bonded on support by graphene oxide paper or its matrix material, puts into silica tube, and extracting vacuum also passes into high-purity hydrogen immediately; Open laser apparatus, and allow laser focusing at graphene oxide paper or its composite material surface, utilize numerical control software to carry out rapid scanning and patterned process to sample.
Above-mentioned oversized shape is than the preparation method of graphene microchip, described step (2) becomes Dark grey from black for patterned surfaces graphene oxide paper after laser marking to be seen or its matrix material, take out finished product, observe respectively with four-point probe, Raman spectrum and microscope.
Above-mentioned oversized shape is than the preparation method of graphene microchip, and preferred described graphene oxide paper composites is a kind of in the graphene oxide paper of metal or semiconductor doping, graphene oxide-ceramic composite, graphene oxide-polymer composites.
Above-mentioned oversized shape is than the preparation method of graphene microchip, and preferred described high-purity hydrogen purity is 99.999%, when passing into high-purity hydrogen, when passing into high-purity hydrogen, when pressure relative in silica tube passes into for stopping during-0.05Pa.
Above-mentioned oversized shape is than the preparation method of graphene microchip, and the pulse laser frequency range of preferred described laser apparatus is 10-50ns; Laser scanning speed is 1000-5000mm/s; Laser output power is 5-6W.
The large shape prepared of aforesaid method than the purposes of graphene microchip, preferably in the application in functional paint, property-modifying additive, electrically conductive ink, ultracapacitor, lithium-ion-power cell field.
The principle of the invention belongs to the chemical reduction Graphene method of solid phase, because main process occurs in solid-state environment, not only effectively prevent may reuniting of graphene molecules under solvent environment, the various environmentally harmful chemical substance because dissolving agent process brings can also be removed from.Experiment proves, compared with traditional solution reduction, the present invention has the remarkable advantages such as laser controllability is good, experimental implementation simple, graphene microchip finished product area is large, the number of plies is few, growth substrate is diversified; In addition, can further genralrlization on present method basis, as the graphene microchip of metal or semiconductor doping is prepared in experiment, or the matrix material (utilizing laser to process mixing raw material) such as graphene oxide-pottery, graphene oxide-polymkeric substance, can also easily for pattern structure.
Graphene oxide paper described in the present invention is a kind of matrix material of stratiform, by graphene oxide by being formed with the physics of interlayer or chemically crosslinked in face.The cost of this stacked structure is very low, but mechanical stretch intensity and Young's modulus are all better than other paper-like material, therefore can prepare high performance composite with Material claddings such as polymkeric substance, glass, pottery, metals.Graphene oxide paper in the present invention derives from the hexa-atomic plain Science and Technology Ltd. in Changzhou and Nanjing Ji Cang nanosecond science and technology company limited respectively.
The present invention has positive effect: (1) utilizes fast laser to scan heating and patterning processing, and the redox graphene microplate that diameter 10-20um size is controlled, thickness is less than 10 atomic shells, electric conductivity is high can be prepared by present method; (2) direct graphene oxide paper or composite system are as laser treatment object, and preparation process does not relate to the complex reaction in solution, thus simplify preparation process, and can production control environment more accurately; (3) utilize laser rapid scanning, not only make the spatial resolution of local reduction more accurate, and establish feasible ways for the large shape of preparation than graphene microchip, finished product shows high conductivity and intrinsic graphite Raman spectral signature; Microplate pattern is more smooth, and large shape is more more than structure distribution; The microplate number of plies and size regulate by laser parameter segmentation; (4) creationary use LASER HEATING redox graphene and laser modified graphene composite material system, makes optimized fabrication doped graphene structure and heterogeneous heterogeneous graphene composite material become possibility.
Accompanying drawing explanation
In order to make content of the present invention more easily be clearly understood, below according to specific embodiment also by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
The graphene oxide target schematic diagram of Fig. 1 a different structure and composition; Modified graphene microplate light path schematic diagram is prepared in Fig. 1 b fast laser scanning reduction.
The burnt micro Raman spectra of Fig. 2 copolymerization, corresponding (a) is without the graphene oxide paper of laser treatment; (b) fast laser scanning heat reduction graphene oxide.
Fig. 3 atomic force microscope shape appearance figure (tapping-mode), the large shape of corresponding diagram 3 (a) fast laser scanning reduction compares graphene microchip; The graphene microchip structure of Fig. 3 (b) metallic particles doping.
The scanning electron microscope (SEM) photograph of Fig. 4 LASER HEATING redox graphene.
Embodiment
(embodiment 1)
1. by substrate of glass or independently graphene oxide paper vertically stick on support, put into silica tube.Sample apart from the distance of quartzy pipe end window about about 150mm.By mechanical pump and molecular pump extracting vacuum, be down to 10 to intraductal pressure
-2pa; Close evacuating valve, pass into a little high pure nitrogen 2-5 minute and treat that it is full of boiler tube, then close nitrogen valve, reopen extraction valve, treat that intraductal pressure is down to 10 again
-2pa, passes into nitrogen again, so repeatedly after 2-3 time, vacuumizes 2-3 hour continuously, until pressure drops to the limit be about 1x10
-4pa.Pass into high-purity hydrogen (99.999%), until negative relative rises to-0.05Pa in pipe.
2. install optical fiber laser, regulate its vertical height and level attitude, make injection laser beam focus exactly on sample surfaces.Guarantee that sample is placed within the scope of beam flying by the ruddiness pre-determined bit of system.Setting graphene pattern (as structures such as square, circular, ring-types) is drawn with system mapping software or AutoCAD.Open laser apparatus and function software.Sweep velocity is arranged on 1200mm/s, frequency 25kHz, power 5W, tests respectively and compares.The 5 minutes working lipe of laser reduction reaction.After having tested, close hydrogen, open pressure lock.After pipe inside and outside air pressure balance, open quartz tube furnace, take out sample, be placed in drying receptacle and preserve.
3. Laser Experiments complete after Graphene (Dark grey) can as the sample of four point probe resistance test, the spacing of four point probe probe is 5mm; Survey surperficial square resistance result and be followed successively by: non-conductive (before laser treatment sample), 35-50 Ω/mouth (laser reduction multilayer graphene oxide), 10-13 Ω/ (laser reduction single-layer graphene oxide).In addition, utilize micro Raman spectra to test preferred microcell, carry out spectroscopic acquisition; In measuring process, setting spectral range is from 800 to 3500cm
-1.In atomic force microscope test, need the Graphene of sampling trace to put into dehydrated alcohol and dilute, then process with ultrasonic, until naked eyes almost do not see; The drop that takes a morsel drops on clean quartz or mica substrate, allows its diffusion come, is heated to liquid and volatilizees completely under being placed on infrared lamp.Atomic force microscope pattern is collected and is taked tapping-mode, first can scan and be convenient on a large scale find sample, then carry out detail scans for single graphene microchip, obtains height and phase corner characteristics.The test of scanning electronic microscope needs to be dispersed in by graphene powder on the conductive resin of load sample base, then puts into Electronic Speculum chamber and carry out secondary electron imaging.
The property-modifying additive that graphene microchip prepared by the present embodiment can be used as speciality coating uses.
(embodiment 2)
1. will be mixed with impurity (as SiO
2powder, metallic particles, carbon nanotube etc.) graphene oxide paper vertically stick on support, put into silica tube.Sample apart from the distance of quartzy pipe end window about about 150mm.By mechanical pump and molecular pump extracting vacuum, be down to 10 to intraductal pressure
-2pa; Close evacuating valve, pass into a little high pure nitrogen 2-5 minute and treat that it is full of boiler tube, then close nitrogen valve, reopen extraction valve, treat that intraductal pressure is down to 10 again
-2pa, passes into nitrogen again, so repeatedly after 2-3 time, vacuumizes 2-3 hour continuously, until pressure drops to the limit be about 1x10
-4pa.Pass into high-purity hydrogen (99.999%), until negative relative rises to-0.05Pa in pipe.
2. install optical fiber laser, regulate its vertical height and level attitude, make injection laser beam focus exactly on sample surfaces.Guarantee that sample is placed within the scope of beam flying by the ruddiness pre-determined bit of system.Setting graphene pattern (as structures such as square, circular, ring-types) is drawn with system mapping software or AutoCAD.Open laser apparatus and function software.Sweep velocity be arranged between 2000-5000mm/s, frequency 30kHz, power 6W, tests respectively and compares.The working lipe of laser reduction reaction was between 20 minutes.After having tested, close hydrogen, open pressure lock.After pipe inside and outside air pressure balance, open quartz tube furnace, take out sample, be placed in drying receptacle and preserve.
3. Laser Experiments complete after doped graphene structure can as the sample of four point probe resistance test, the spacing of four point probe probe is 5mm; Finished product electric conductivity after laser treatment can significantly improve, survey surperficial square resistance result (10-35 Ω/) can be slightly different with doping component and ratio.In addition, utilize micro Raman spectra to test preferred microcell, carry out spectroscopic acquisition; In measuring process, setting spectral range is from 800 to 3500cm
-1.In atomic force microscope test, need the Graphene of sampling trace to put into dehydrated alcohol and dilute, then process with ultrasonic, until naked eyes almost do not see; The drop that takes a morsel drops on clean quartz or mica substrate, allows its diffusion come, is heated to liquid and volatilizees completely under being placed on infrared lamp.Atomic force microscope pattern is collected and is taked tapping-mode, first can scan and be convenient on a large scale find sample, then carry out detail scans for single graphene microchip, obtains height and phase corner characteristics.The test of scanning electronic microscope needs to be sprinkled upon by graphene powder on the conductive resin of load sample base, then puts into Electronic Speculum chamber and carry out secondary electron imaging.
Metal prepared by the present embodiment or semiconductor doping Graphene, it is mainly used in fields such as electrode material for super capacitor, lithium ion battery electrode material, eelctro-catalyst, dye sensitization solar batterys.
(embodiment 3)
1. the graphene oxide paper comprising patterning and complex construction (as polymeric coating) is vertically sticked on support, put into silica tube.Sample apart from the distance of quartzy pipe end window about about 150mm.By mechanical pump and molecular pump extracting vacuum, be down to 10 to intraductal pressure
-2pa; Close evacuating valve, pass into a little high pure nitrogen 2-5 minute and treat that it is full of boiler tube, then close nitrogen valve, reopen extraction valve, treat that intraductal pressure is down to 10 again
-2pa, passes into nitrogen again, so repeatedly after 2-3 time, vacuumizes 2-3 hour continuously, until pressure drops to the limit be about 1x10
-4pa.Pass into high-purity hydrogen (99.999%), until negative relative rises to-0.05Pa in pipe.
2. install optical fiber laser, regulate its vertical height and level attitude, make injection laser beam focus exactly on sample surfaces.Guarantee that sample is placed within the scope of beam flying by the ruddiness pre-determined bit of system.Setting graphene pattern (as structures such as square, circular, ring-types) is drawn with system mapping software or AutoCAD.Open laser apparatus and function software.Sweep velocity be arranged between 4800mm/s, frequency 45kHz, power 6W, tests respectively and compares.The working lipe of laser reduction reaction is between 5-30 minute.After having tested, close hydrogen, open pressure lock.After pipe inside and outside air pressure balance, open quartz tube furnace, take out sample, be placed in drying receptacle and preserve.
3. Laser Experiments complete after graphene composite material body can as the sample of four point probe resistance test, the spacing of four point probe probe is 5mm; Because Graphene is occurred by laser modified by thermal reduction and other composition simultaneously, reaction is comparatively complicated, and matrix material surface square resistance result can have significant change with test zone difference.In addition, utilize micro Raman spectra to test preferred domain structure, carry out spectroscopic acquisition; In measuring process, setting spectral range is from 800 to 3500cm
-1.In atomic force microscope test, need the Graphene of sampling trace to put into dehydrated alcohol and dilute, then process with ultrasonic, until naked eyes almost do not see; The drop that takes a morsel drops on clean quartz or mica substrate, allows its diffusion come, is heated to liquid and volatilizees completely under being placed on infrared lamp.Atomic force microscope pattern is collected and is taked tapping-mode, first can scan and be convenient on a large scale find sample, then carry out detail scans for single graphene microchip, obtains height and phase corner characteristics.The test of scanning electronic microscope needs to be sprinkled upon by graphene powder on the conductive resin of load sample base, then puts into Electronic Speculum chamber and carry out secondary electron imaging.
Polymkeric substance described in the present embodiment comprises polyolefine, ethene, propene polymer, trevira, polymeric amide, polyurethane, epoxy resin rubber etc.The graphene composite material of preparation may be used on the fields such as microwave defense material, antistatic coating, electrically conducting coating.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. an oversized shape is than the preparation method of graphene microchip: be specially following steps: graphene oxide paper or its matrix material are positioned in vitreosil pipe by (1); Laser apparatus is adopted to carry out rapid scanning heat reduction to sample; (2) test product; Described graphene oxide paper is stratified composite, by graphene oxide by being formed with the physics of interlayer or chemically crosslinked in face; Described step (1), for be bonded on support by graphene oxide paper or its matrix material, puts into silica tube, and extracting vacuum also passes into high-purity hydrogen immediately; Open laser apparatus, and allow laser focusing at graphene oxide paper or its composite material surface, utilize numerical control software to carry out rapid scanning and patterned process to sample; The pulse laser frequency range of described laser apparatus is 10-50ns; Laser scanning speed is 1000-5000mm/s; Laser output power is 5-6W.
2. oversized shape according to claim 1 is than the preparation method of graphene microchip, it is characterized in that: described step (2) becomes Dark grey from black for patterned surfaces graphene oxide paper after laser marking to be seen or its matrix material, take out finished product, observe respectively with four-point probe, Raman spectrum and microscope, these test purposes are inspection after construction, the graphene microchip of screening high-quality or target combination product.
3. oversized shape according to claim 1 and 2 is than the preparation method of graphene microchip, it is characterized in that: described graphene oxide paper composites is a kind of in the graphene oxide paper of metal or semiconductor doping, graphene oxide-ceramic composite, graphene oxide-polymer composites.
4. oversized shape according to claim 1 is than the preparation method of graphene microchip, it is characterized in that: described high-purity hydrogen purity is 99.999%, stops passing into when passing into high-purity hydrogen when pressure relative in silica tube is-0.05Pa.
5. the oversized shape that described in any one of claim 1-4 prepared by method compares graphene microchip, it is characterized in that: the average atom number of plies of obtained graphene microchip is at 6-8 layer, thickness is between 2.0-3.0nm, microplate diameter is more than 10 μm, be 20 μm to the maximum, shape ratio and diameter and Thickness Ratio are 10000.
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| CN104810163B (en) * | 2014-07-18 | 2017-08-08 | 纳米新能源（唐山）有限责任公司 | Preparation method, graphene ultracapacitor and the energy-storage system of graphene ultracapacitor |
| CN104252974A (en) * | 2014-09-18 | 2014-12-31 | 电子科技大学 | Manufacturing method of composite film material |
| CN106531613B (en) * | 2016-04-22 | 2020-07-17 | 中国科学院微电子研究所 | Selective modification processing method and device for graphene surface |
| CN106315568B (en) * | 2016-08-23 | 2019-01-11 | 深圳智裳科技有限公司 | A kind of preparation method of graphene |
| CN106313926B (en) * | 2016-09-27 | 2019-01-29 | 清华大学 | A kind of surface modifying method changing impregnated graphite surface wettability energy |
| CN106744873B (en) * | 2016-12-02 | 2019-03-26 | 黑龙江科技大学 | A kind of method of quick preparation small size graphene |
| CN107298439B (en) * | 2017-06-14 | 2018-05-18 | 成都新柯力化工科技有限公司 | A kind of method that graphene film is prepared using femtosecond laser |
| CN107381548A (en) * | 2017-07-31 | 2017-11-24 | 江苏大学 | A kind of laser quick in situ prepares the apparatus and method with transfer large-area graphene |
| CN109401012A (en) * | 2018-10-30 | 2019-03-01 | 福州大学 | A kind of graphene microchip/high-density polyethylene composite material and preparation method thereof |
| CN111500005A (en) * | 2019-01-30 | 2020-08-07 | 家登精密工业股份有限公司 | Cycloolefin composition and semiconductor container using the same |
| CN110437509B (en) * | 2019-02-18 | 2021-06-25 | 杭州电子科技大学 | Preparation method of conductive enhanced functional rubber |
| CN113061010A (en) * | 2021-03-25 | 2021-07-02 | 中交二公局第三工程有限公司 | High-strength fiber salt corrosion resistant cement concrete |
| CN114213706A (en) * | 2021-12-02 | 2022-03-22 | 北京石墨烯技术研究院有限公司 | Graphene composite material, preparation method thereof, heat dissipation member and electronic device |
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