CN103318878A - Preparation method and application of large size and shape ratio graphene microsheet - Google Patents
Preparation method and application of large size and shape ratio graphene microsheet Download PDFInfo
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Abstract
The invention relates to a preparation method and application of a large size and shape ratio graphene microsheet. The method comprises the following steps: arranging oxidized graphene paper or a mixed material containing partial impurities in a quartz tube, introducing H2 at a certain air pressure, and focusing a sample for performing scanning heating by using high-speed laser, wherein a complete graphene microsheet with less than ten atomic layers and high electric conductivity and high uniformity can be prepared in a room temperature environment under certain conditions, and the impurities in the material can be finely processed. The average atomic layer number of the prepared graphene is 6-8, the particle size is between 2.0 and 3.0nm, and the shape ratio of the microsheet can be close to 10,000. The optical and conductive performances are obviously superior to those of the graphene microsheet prepared by the traditional chemical reducing method; according to fine regulation of the laser scanning parameters, the method has the advantages of repeatedly performing sample treatment and pattern processing, along with high target processability, controllable layer number and size of the microsheet, simple equipment, cleanliness, high efficiency and flexible operation, and has excellent industrial application value.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene microplate, particularly a kind of oversized shape is than the preparation method and its usage of Graphene microplate.
Background technology
The Graphene microplate refers generally to the carbon-coating number more than 10 layers, the ultra-thin Graphene stratiform accumulation body of thickness in the 5-100 nanometer range.In the document that has, be also referred to as GrapheneNanosheets. Graphene microplate and kept the original planar carbon six-ring of graphite conjugation crystalline structure, have excellent physical strength, conduction, heat conductivility, and good lubricated, high temperature resistant and anticorrosion properties.With respect to common graphite, the thickness of Graphene microplate is in the nanoscale scope, but its radial width can reach several to the dozens of micron, has the shape of super large than (diameter/thickness ratio).The Graphene microplate, be the multi-layer graphene structure, but the characteristic of Graphene obtains fine maintenance such as conduction, heat conduction, printing opacity, flexibility etc., can be used as a kind of industrial raw materials and add to widely in the existing various base mateiral, the performance of current material is improved.The Graphene microplate is because its good characteristic that has, and its Application Areas is boundless, for example improves heat conduction and the heat dispersion of plastic cement, and 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 have nano thickness, easily and other material such as polymer materials evenly compound, and form good compound interface, the Graphene microplate can take the high strength of Graphene, lubricated, high temperature resistant and conductive characteristic in the middle of the matrix material to, thereby can design, prepare high performance composite.It all is good application that graphene composite material, Graphene plastics, Graphene rubber, graphene conductive printing ink, Graphene coating, Graphene are inhaled ripple hidden function plate, Graphene radiating element, Graphene power cell, Graphene functional coating, ultracapacitor, seawater desalination desalting device etc.
Current, the Graphene microplate is applied to matrix material three characteristics: the gauffer on (1) Graphene surface and defective have strengthened the combination with polymeric substrates, are beneficial to load transmission between the 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 the crackle diffusion, thus the fracture toughness property of reinforced composite.Therefore, study big shape than the controlled preparation of the Graphene of (large size and lack atomic shell) application, the especially improvement of macromechanics character for its matrix material, positive effect is arranged.
The manufacturer of present domestic sale Graphene microplate mainly contains hexa-atomic limit company, Nanjing Ji Cang nanosecond science and technology Science and Technology Ltd., the Ningbo of Zhejiang Mo Xi Science and Technology Ltd. etc. of have in Changzhou, and its preparation method comprises thermal reduction oxidation style and solvent method etc.Main products has powder and two kinds of forms of slurry, can be applicable to medicine, detection, catalyzer, conduction and heat conduction field etc.The current production line of producing 300 tons of Graphene microplates per year of having extended 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 but can't accurately carry out microcosmic thickness or size control between 5-10um.U.S. XG technology company limited is the different Graphene microplates of two kinds of series of volume production diameter 15 and 25um accurately, but thickness is bigger, are distributed in 6-8nm (M rank) or 15nm (H series) respectively.The controlled preparation of the Graphene microplate below 10 layers of super large shape ratio does not still have maturation method at present at home.
Utilize the preparation of LASER HEATING redox graphene solution (or spin coating liquid) and patterning on this basis once repeatedly to be reported, but method therefor needs the graphene oxide that disperses in the laser direct irradiation solvent before, not only the Graphene after the reduction is reunited easily, and the weak acid material of self impurity or generation may stop the part carboxyl reduction at graphene oxide edge in the solution, thereby can't obtain larger sized Graphene microplate.In fact, utilizing traditional solution irradiation redox graphene is quite difficult for the accurate controlled of the product atom number of plies or size.
On the other hand, graphene composite material needs some new technology to get involved especially based on the preparation of the polymer composites of Graphene.For the Graphene of chemical reduction, because of its plane pattern and interlayer interaction generation stratiform accumulation easily; Current a kind of effective solution route is by adding tensio-active agent or mixing to avoid combination between the Graphene in advance with polymkeric substance before reduction.Because Graphene has the sp2 hybrid structure in face, usually the non covalent bond between polymkeric substance is combined very weak, thereby chemically modified Graphene or graphene oxide be more suitable for as wild phase than pure grapheme material, but the reduction of character is for the new requirement of composite structure design proposition itself in chemically modified and the graphene oxide face.
Summary of the invention
The objective of the invention is to solve above-mentioned deficiency, propose a kind ofly to prepare big shape than the method for Graphene microplate, and the new route of development preparation doped graphene and graphene composite material on this basis.Its characteristics are to transfer the controllable parameter of laser retrofit to influence final dimension and thickness key variables, utilize the rapid heating of modern laser and the advantage of localization modification to segment adjusting Graphene microcell pattern, performance and size, and prepare corresponding doping or composite structure in conjunction with the multi-component target.
The technical scheme that realizes the object of the invention is: a kind of oversized shape is than the preparation method of Graphene microplate; Be specially following steps: (1) is positioned over graphene oxide paper or its matrix material in the vitreosil pipe; Adopt laser apparatus that sample is scanned fast and add thermal reduction; (2) test product.
Above-mentioned oversized shape is than the preparation method of Graphene microplate, and described step (1) is put into silica tube for graphene oxide paper or its matrix material are bonded on the support, and extracting vacuum also feeds high-purity hydrogen immediately; Open laser apparatus, and allow laser focusing at graphene oxide paper or its composite material surface, utilize numerical control software that sample is scanned and patterned process fast.
Above-mentioned oversized shape is than the preparation method of Graphene microplate, described step (2) becomes Dark grey for patterned surfaces graphene oxide paper or its matrix material behind laser marking to be seen by black, take out finished product, observe respectively with four point probe tester, Raman spectrum and microscope.
Above-mentioned oversized shape is than the preparation method of Graphene microplate, and is a kind of in the graphene oxide paper that preferred described graphene oxide paper composites is metal or semiconductor doping, graphene oxide-ceramic composite, the graphene oxide-polymer composites.
Above-mentioned oversized shape is than the preparation method of Graphene microplate, and preferred described high-purity hydrogen purity is 99.999%, when feeding high-purity hydrogen, when feeding high-purity hydrogen, stops to feed when pressure is for-0.05Pa relatively in the silica tube.
Above-mentioned oversized shape is than the preparation method of Graphene microplate, 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 big shape of method for preparing is than the purposes of Graphene microplate, preferably in the application in functional paint, property-modifying additive, electrically conductive ink, ultracapacitor, lithium-ion-power cell field.
The chemical reduction Graphene method that belongs to solid phase on the principle of the invention, because main process occurs in solid-state environment, not only effectively avoided may reuniting of graphene molecules under the solvent environment, can also remove from because the various environmentally harmful chemical substance that dissolving agent process brings.Experiment showed, with traditional solution reduction method and compare that the present invention has that the laser controllability is good, experimental implementation is simple, remarkable advantages such as Graphene microplate finished product area is big, the number of plies is few, growth substrate variation; In addition, on present method basis, can further promote, as test the Graphene microplate for preparing metal or semiconductor doping, or matrix materials (utilizing laser that mixing raw material is processed) such as graphene oxide-pottery, graphene oxide-polymkeric substance, can also be used for pattern structure easily.
Graphene oxide paper described in the present invention is a kind of matrix material of stratiform, by graphene oxide by in the face and physics or the chemically crosslinked of interlayer form.The cost of this stacked structure is very low, but mechanics tensile strength and Young's modulus all are better than other paper shape material, therefore can with the compound and preparation high performance composite of materials such as polymkeric substance, glass, pottery, metal.Graphene oxide paper among 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 quick laser scanning heating and patterning processing, and diameter 10-20um controlled amount can be prepared by present method, thickness is less than 10 atomic shells, the high redox graphene microplate of electric conductivity; (2) directly use graphene oxide paper or composite system as the laser treatment object, preparation process does not relate to the complex reaction in the solution, thereby simplifies preparation process, and can control production environment more accurately; (3) utilize laser to scan fast, not only make the spatial resolution of local reduction more accurate, and establish the feasibility path for the big shape of preparation than Graphene microplate, finished product is showed high conductivity and intrinsic Graphene raman spectral characteristics; The microplate pattern is more smooth, and big shape is more more than structure distribution; The microplate number of plies and big I are regulated by the laser parameter segmentation; (4) creationary use LASER HEATING redox graphene and laser modified graphene composite material system make optimization preparation doped graphene structure and heterogeneous heterogeneous graphene composite material become possibility.
Description of drawings
Content of the present invention is easier to be expressly understood in order to make, and according to specific embodiment also by reference to the accompanying drawings, the present invention is further detailed explanation, wherein below
The graphene oxide target synoptic diagram of Fig. 1 a different structure and composition; The quick laser scanning reduction of Fig. 1 b preparation modified graphene microplate light path synoptic diagram.
The burnt micro Raman spectra of Fig. 2 copolymerization, corresponding (a) is without the graphene oxide paper of laser treatment; (b) redox graphene is heated in laser scanning fast.
Fig. 3 atomic force microscope shape appearance figure (rapping pattern), the big shape of the quick laser scanning reduction of corresponding diagram 3 (a) is than Graphene microplate; The Graphene micro sheet structure that Fig. 3 (b) metallic particles mixes.
The sem photograph of Fig. 4 LASER HEATING redox graphene.
Embodiment
(embodiment 1)
With substrate of glass or independently graphene oxide paper vertically stick on the support, put into silica tube.Sample apart from the distance of quartzy pipe end window about about 150mm.With mechanical pump and molecular pump extracting vacuum, be down to 10 to intraductal pressure
-2Pa; Close evacuating valve, feed and treated that it was full of boiler tube in a little high pure nitrogen 2-5 minute, close nitrogen valve then, reopen extraction valve, treat that intraductal pressure is down to 10 again
-2Pa feeds nitrogen again, after 2-3 time, vacuumizes continuously 2-3 hour so repeatedly, drops to the about 1x10 of the limit until pressure
-4Pa.Feed high-purity hydrogen (99.999%), negative pressure rises to-0.05Pa relatively in pipe.
2. install optical fiber laser, regulate its vertical height and level attitude, make the ejaculation laser beam just in time focus on sample surfaces.Guarantee that with the ruddiness pre-determined bit of system sample is placed in the beam flying scope.Draw with system's mapping software or AutoCAD and to set Graphene pattern (as structures such as square, circular, ring-types).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 experiment is finished, close hydrogen, open pressure lock.After waiting to manage inside and outside air pressure balance, open quartz tube furnace, take out sample, place in the drying receptacle and preserve.
3. the Graphene after Laser Experiments are finished (Dark grey) can be used as the sample of four point probe resistance test, and the spacing of four point probe probe is 5mm; The surperficial square resistance result that surveys is followed successively by: non-conductive (sample before the laser treatment), 35-50 Ω/mouth (laser reduction multilayer graphene oxide), 10-13 Ω/ (laser reduction mono-layer graphite oxide alkene).In addition, utilize micro Raman spectra to test preferred microcell, carry out the spectral signal collection; In the measuring process, set spectral range from 800 to 3500cm
-1In the atomic force microscope test, need the micro-Graphene of sampling to put into dehydrated alcohol and dilute, handle with ultrasonic again, almost do not see until naked eyes; The drop that takes a morsel drops on the quartz or mica substrate of cleaning, allows its diffusion come, and is placed on to be heated to liquid under the infrared lamp and to volatilize fully.The atomic force microscope pattern is collected and to be taked the pattern of rapping, and can scan earlier and be convenient to find sample on a large scale, carries out detail scans at single Graphene microplate again, obtains height and corner characteristics mutually.The test of scanning electronic microscope need be dispersed in the Graphene powder on the conductive resin of load sample base, puts into the Electronic Speculum chamber again and carries out the secondary electron imaging.
The property-modifying additive that present embodiment prepared graphene microplate 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 the support, put into silica tube.Sample apart from the distance of quartzy pipe end window about about 150mm.With mechanical pump and molecular pump extracting vacuum, be down to 10 to intraductal pressure
-2Pa; Close evacuating valve, feed and treated that it was full of boiler tube in a little high pure nitrogen 2-5 minute, close nitrogen valve then, reopen extraction valve, treat that intraductal pressure is down to 10 again
-2Pa feeds nitrogen again, after 2-3 time, vacuumizes continuously 2-3 hour so repeatedly, drops to the about 1x10 of the limit until pressure
-4Pa.Feed high-purity hydrogen (99.999%), negative pressure rises to-0.05Pa relatively in pipe.
2. install optical fiber laser, regulate its vertical height and level attitude, make the ejaculation laser beam just in time focus on sample surfaces.Guarantee that with the ruddiness pre-determined bit of system sample is placed in the beam flying scope.Draw with system's mapping software or AutoCAD and to set Graphene pattern (as structures such as square, circular, ring-types).Open laser apparatus and function software.Sweep velocity is arranged between the 2000-5000mm/s, frequency 30kHz, power 6W tests respectively and compares.The working lipe of laser reduction reaction was between 20 minutes.After experiment is finished, close hydrogen, open pressure lock.After waiting to manage inside and outside air pressure balance, open quartz tube furnace, take out sample, place in the drying receptacle and preserve.
3. the doped graphene structure after Laser Experiments are finished can be used as the sample of four point probe resistance test, and the spacing of four point probe probe is 5mm; Finished product electric conductivity after the laser treatment can significantly improve, and the surperficial square resistance result that surveys (can be with doping component and ratio and be slightly different by 10-35 Ω/).In addition, utilize micro Raman spectra to test preferred microcell, carry out the spectral signal collection; In the measuring process, set spectral range from 800 to 3500cm
-1In the atomic force microscope test, need the micro-Graphene of sampling to put into dehydrated alcohol and dilute, handle with ultrasonic again, almost do not see until naked eyes; The drop that takes a morsel drops on the quartz or mica substrate of cleaning, allows its diffusion come, and is placed on to be heated to liquid under the infrared lamp and to volatilize fully.The atomic force microscope pattern is collected and to be taked the pattern of rapping, and can scan earlier and be convenient to find sample on a large scale, carries out detail scans at single Graphene microplate again, obtains height and corner characteristics mutually.The test of scanning electronic microscope need be sprinkled upon the Graphene powder on the conductive resin of load sample base, puts into the Electronic Speculum chamber again and carries out the secondary electron imaging.
Metal or the semiconductor doping Graphene of present embodiment preparation, 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 that will comprise patterning and complex construction (as polymeric coating) vertically sticks on the support, puts into silica tube.Sample apart from the distance of quartzy pipe end window about about 150mm.With mechanical pump and molecular pump extracting vacuum, be down to 10 to intraductal pressure
-2Pa; Close evacuating valve, feed and treated that it was full of boiler tube in a little high pure nitrogen 2-5 minute, close nitrogen valve then, reopen extraction valve, treat that intraductal pressure is down to 10 again
-2Pa feeds nitrogen again, after 2-3 time, vacuumizes continuously 2-3 hour so repeatedly, drops to the about 1x10 of the limit until pressure
-4Pa.Feed high-purity hydrogen (99.999%), negative pressure rises to-0.05Pa relatively in pipe.
2. install optical fiber laser, regulate its vertical height and level attitude, make the ejaculation laser beam just in time focus on sample surfaces.Guarantee that with the ruddiness pre-determined bit of system sample is placed in the beam flying scope.Draw with system's mapping software or AutoCAD and to set Graphene pattern (as structures such as square, circular, ring-types).Open laser apparatus and function software.Sweep velocity is arranged between the 4800mm/s, frequency 45kHz, power 6W tests respectively and compares.The working lipe of laser reduction reaction was between 5-30 minute.After experiment is finished, close hydrogen, open pressure lock.After waiting to manage inside and outside air pressure balance, open quartz tube furnace, take out sample, place in the drying receptacle and preserve.
3. the graphene composite material body after Laser Experiments are finished can be used as the sample of four point probe resistance test, and the spacing of four point probe probe is 5mm; Because Graphene is taken place simultaneously by laser modified by thermal reduction and other composition, reaction is comparatively complicated, and matrix material surface square resistance result can have significant change with test zone is different.In addition, utilize micro Raman spectra to test preferred domain structure, carry out the spectral signal collection; In the measuring process, set spectral range from 800 to 3500cm
-1In the atomic force microscope test, need the micro-Graphene of sampling to put into dehydrated alcohol and dilute, handle with ultrasonic again, almost do not see until naked eyes; The drop that takes a morsel drops on the quartz or mica substrate of cleaning, allows its diffusion come, and is placed on to be heated to liquid under the infrared lamp and to volatilize fully.The atomic force microscope pattern is collected and to be taked the pattern of rapping, and can scan earlier and be convenient to find sample on a large scale, carries out detail scans at single Graphene microplate again, obtains height and corner characteristics mutually.The test of scanning electronic microscope need be sprinkled upon the Graphene powder on the conductive resin of load sample base, puts into the Electronic Speculum chamber again and carries out the secondary electron imaging.
Polymkeric substance described in the present embodiment comprises polyolefine, ethene, propene polymer, trevira, polymeric amide, polyurethane, Resins, epoxy rubber etc.The graphene composite material of preparation may be used on fields such as electromagnetic protection material, antistatic coating, electrically conducting coating.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. an oversized shape is than the preparation method of Graphene microplate; Be specially following steps: (1) is positioned over graphene oxide paper or its matrix material in the vitreosil pipe; Adopt laser apparatus that sample is scanned fast and add thermal reduction; (2) test product.
2. oversized shape according to claim 1 is characterized in that than the preparation method of Graphene microplate: described step (1) is put into silica tube for graphene oxide paper or its matrix material are bonded on the support, and extracting vacuum also feeds high-purity hydrogen immediately; Open laser apparatus, and allow laser focusing at graphene oxide paper or its composite material surface, utilize numerical control software that sample is scanned and patterned process fast.
3. oversized shape according to claim 1 is than the preparation method of Graphene microplate, it is characterized in that: described step (2) becomes Dark grey for patterned surfaces graphene oxide paper or its matrix material behind laser marking to be seen by black, take out finished product, observe respectively with four point probe tester, Raman spectrum and microscope, these test purposes are inspection after construction, Graphene microplate or the target combination product of screening high-quality.
According to claim 1 or 2 or 3 described oversized shape than the preparation method of Graphene microplate, it is characterized in that: a kind of in the graphene oxide paper that described graphene oxide paper composites is metal or semiconductor doping, graphene oxide-ceramic composite, the graphene oxide-polymer composites.
5. oversized shape according to claim 2 is characterized in that than the preparation method of Graphene microplate: described high-purity hydrogen purity is 99.999%, when feeding high-purity hydrogen when silica tube in relatively pressure be-stop feeding during 0.05Pa.
6. oversized shape according to claim 2 is characterized in that than the preparation method of Graphene microplate: 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.
7. the big shape of the described method preparation of claim 1-6 is than Graphene microplate, it is characterized in that: the average atom number of plies of the Graphene microplate that makes is at the 6-8 layer, and thickness is between 2.0-3.0nm, and the microplate diameter surpasses 10 μ m, maximum is near 20 μ m, and the shape ratio is that diameter can be near 10000 with the thickness ratio.
One kind as the big shape of method preparation as described in the claim 1-7 than Graphene microplate purposes, it is characterized in that: in functional paint, property-modifying additive, electrically conductive ink, ultracapacitor, lithium-ion-power cell Application for Field.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103077766A (en) * | 2013-02-06 | 2013-05-01 | 青岛中科昊泰新材料科技有限公司 | Graphene conducting film and application of graphene conducting film to electrochemical capacitor |
-
2013
- 2013-06-27 CN CN201310260669.XA patent/CN103318878B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103077766A (en) * | 2013-02-06 | 2013-05-01 | 青岛中科昊泰新材料科技有限公司 | Graphene conducting film and application of graphene conducting film to electrochemical capacitor |
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| 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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