WO2017025926A1 - Method and device for production of graphene or graphene-like materials - Google Patents

Method and device for production of graphene or graphene-like materials Download PDF

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Publication number
WO2017025926A1
WO2017025926A1 PCT/IB2016/054848 IB2016054848W WO2017025926A1 WO 2017025926 A1 WO2017025926 A1 WO 2017025926A1 IB 2016054848 W IB2016054848 W IB 2016054848W WO 2017025926 A1 WO2017025926 A1 WO 2017025926A1
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previous
graphene
mixture
cavitation
high shear
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PCT/IB2016/054848
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English (en)
French (fr)
Inventor
Vitor Emanuel MARQUES ABRANTES
Bruno REIS FIGUEIREDO
Rui Pedro FONSECA FERREIRA DA SILVA
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Graphenest, S.A.
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Priority to EP16766385.5A priority Critical patent/EP3334686A1/en
Priority to US15/751,922 priority patent/US10843145B2/en
Priority to CA2995433A priority patent/CA2995433A1/en
Publication of WO2017025926A1 publication Critical patent/WO2017025926A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/27Mixers with stator-rotor systems, e.g. with intermeshing teeth or cylinders or having orifices
    • B01F27/271Mixers with stator-rotor systems, e.g. with intermeshing teeth or cylinders or having orifices with means for moving the materials to be mixed radially between the surfaces of the rotor and the stator
    • B01F27/2711Mixers with stator-rotor systems, e.g. with intermeshing teeth or cylinders or having orifices with means for moving the materials to be mixed radially between the surfaces of the rotor and the stator provided with intermeshing elements
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • C01B32/184Preparation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00Other mixers; Mixing plants; Combinations of mixers
    • B01F33/80Mixing plants; Combinations of mixers
    • B01F33/81Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053Details of the reactor
    • B01J19/0066Stirrers
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • C01B32/184Preparation
    • C01B32/19Preparation by exfoliation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • C01B32/194After-treatment
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/20Graphite
    • C01B32/21After-treatment
    • C01B32/22Intercalation
    • C01B32/225Expansion; Exfoliation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00Compounds of molybdenum
    • C01G39/06Sulfides
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/08Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds

Definitions

  • the present disclosure relates to a method and device for producing graphene sheets, graphene-like sheet materials, in particular metal dichalcogenides, oxides and carbides, or two-dimensional or few-layer nano-materials.
  • Graphene is a known two-dimensional material composed of an atomic-scale honeycomb lattice made of carbon atoms. It possesses distinct properties that makes of it a promising material for several applications. Specifically, its high conductivity capacity may encounter applicability in sensors, batteries, transistors, capacitors, among others. Since the production of graphene by mechanical exfoliation or peeling, a wide range of graphene synthesis techniques have emerged. Graphene production process can be currently achieved by one of the following methods.
  • the document CN102757035A describes a method to obtain high-purity graphene through the combination of a solvent, such as dimethylformamide, thermal treatment and microwave methods.
  • the obtaining process began with the preparation of a graphite solution that was heat-treated by microwave. Then, the solvent was removed and the resultant material was filtrated and washed, followed by a drying process. The performance rate of this method is about 10-15%. However, the method and device that is presently disclosed does not include any heat-treatment by microwave and has a much higher performance.
  • the document CN103632845A describes a method to obtain a graphene/organic thin film composite.
  • the procedure started with an uncontrolled ultrasonic dispersion of a graphite oxide/solvent mixture in order to obtain a liquid graphene oxide suspension.
  • the preferable solvents are deionized water, ethanol, isopropanol or n-butanol.
  • the pH of the solution is adjusted between values of 10 and 11 and a hydrazine hydrate solution is added to the suspension.
  • a graphene suspension is obtained and further used to coat an organic thin film.
  • the process of roller pressing is performed and repeated after the soaking of the mixed solution of acetone and isopropyl alcohol, so as to acquire the graphene/organic thin film composite.
  • the presently disclosed method and device do not have an uncontrolled ultrasonic dispersion of a graphite oxide/solvent mixture in order to obtain a liquid graphene oxide suspension.
  • the document US20130001068A1 discloses a combined production- functionalization process for the obtainment of chemically functionalized graphene material.
  • the disclosed method declares that is possible to obtain graphene by exfoliating pre-intercalated, oxidized, or halogenated graphite.
  • the graphite material may be selected from a group consisting of natural graphite, artificial graphite, highly oriented pyrolytic graphite, carbon fiber, graphite fiber, carbon nanofiber, graphitic nanofiber, meso-carbon micro- bead, graphitized coke, and combinations thereof.
  • the graphene production was initiated by the dispersion of the exfoliated graphite and an azide or bi-radical compound in a liquid medium to form a suspension. Then, this suspension was subjected to ultrasonic waves of a desired intensity for a period sufficient to produce nanographene platelets and to trigger a chemical reaction between the nanographene platelets and the azide, producing the wanted functionalized material.
  • this method uses an aqueous suspension with azide or bi-radical compounds that are going to react with the graphite nanoplatelets, unlike the presently disclosed method and device.
  • 3 - submit the mixture to a cavitation force containing cavitation bubbles; 4 - submit the mixture to high shear agitation in the range of 2000 to 35000 RPM;
  • Graphene-like materials may be defined as two-dimensional or few-layer nano- materials, in particular metal dichalcogenides, oxides and carbides.
  • the crystalline graphitic material used in the method for the production of graphene, graphene-like and other two-dimensional material is introduced with a quantity of 0.25 to 1.25 mg/mL.
  • the crystalline graphitic material used in the method for the production of graphene, graphene-like and other two-dimensional material is selected from the group composed by natural graphite, pyrolytic graphite, meso-carbon micro- bead carbon or graphite fiber, carbon or graphitic nano-fiber, soft carbon, hard carbon, and combinations thereof.
  • the solvent or surfactant used in the second step of the method for the production of graphene, graphene-like and other two-dimensional material is selected from at least one of the following: butyl alcohol, ethanol, acetone, petroleum ether, N-methylpyrrolidone, hydrogen peroxide and water.
  • the mixture in the third step of the method for the production of graphene, graphene-like and other two-dimensional material is subject to a cavitational force.
  • the cavitation bubbles used in the method for the production of graphene, graphene-like and other two-dimensional material comprise a radius size within a range of 0.2 to 18 ⁇ . This can be determined by the system operating conditions or through cavitation meters by measuring locally the energy of each bubble.
  • the fourth step of the method for the production of graphene, graphene-like and other two-dimensional material is made in at least two dispersion elements.
  • the dispersion elements of the method for the production of graphene, graphene-like and other two-dimensional material are a rotor and a stator.
  • the spray drying process used in the method for the production of graphene, graphene-like and other two-dimensional material is made on a spray drying chamber, a cyclone, a dehumidifier and an inert loop.
  • the fifth step of the method for the production of graphene, graphene-like and other two-dimensional material is made at temperatures comprised between 40 and 350°C.
  • the present application describes a method for producing graphene sheets, graphene-like materials and other two-dimensional materials that combines high shear thermomechanical exfoliation methods.
  • a modular equipment associates four distinct effects in the same enclosed vessel: chemical, thermal, mechanical and cavitational.
  • the cavitation is the governing effect being aided by one, at least, of the others.
  • the chemical and mechanical effects are of great importance to establish the best hydrodynamic properties and therefore reduce production time, what gives them an important role as cavitational-combinatorial effects.
  • This new method allows a much smaller production cost, higher control of defects in the structure of the material, less hazardous to human beings, animals and environment and feasibility to scale-up.
  • the production cost is significantly lower than conventional methods, like the modified Hummers method or the chemical vapor deposition (CVD) that usually are very ineffective and extensives.
  • Controlling the energy of the bubbles implosions generated by the cavitational effect permits to have a higher control of defects in the structure which turns also possible to obtain tailor-made materials according to the customers and market needs, which represents a great novelty.
  • the method now disclosed is environmentally friendly since it does not use strong oxides or acids, an important advantage in the modern World.
  • the present application discloses a method for the production of graphene, graphene-like and other two-dimensional materials, said method comprising the following steps:
  • cavitational force containing cavitation bubbles which can have a radius in the range of 0.2 to 18 microns; in order to achieve exfoliation of graphite until complete flatness and ultimately produce graphene a large number of implosions of controlled size and therefore energy is required to archive the desired effect;
  • the production method described above may be also applied for the production of other two-dimensional (2D) materials from the following group: boron nitride, germanene, silicene, stanene, phosphorene, molybdenum disulfide and tungsten disulfide, by replacing the crystalline graphitic material with the corresponding precursor material of the desired 2D material.
  • 2D two-dimensional
  • This description also relates to graphene obtained by such method, which has a much lower level of structural defects.
  • the cavitation step and the high shear agitation step are simultaneous, further in particular wherein the cavitation step and the high shear agitation step are simultaneous in the same enclosed vessel.
  • the crystalline graphitic material is provided at 0.25 to 25 mg/mL, in particular 0.25 to 15 mg/mL, further in particular 0.25 to 1.25 mg/mL.
  • the cavitation bubbles have a radius size within a range of 0.2 to 18 ⁇ , in particular 1.2 to 10.5 ⁇ , further in particular 2.4 to 6.8 ⁇ .
  • the cavitation force is modulated in working frequency of a 1-5% range, in particular 3%, of a sweep function.
  • the high shear agitation of the method is made by at least two mechanical dispersion elements.
  • the mechanical dispersion elements are a rotor and a stator.
  • the rotor and stator are arranged for creating a double toroidal vortex with shear stirring with doppler effect.
  • the high shear agitation is 5000 to 15000 RPM, in particular 6500 to 10500 RPM.
  • the crystalline graphitic material is selected from: natural graphite, pyrolytic graphite, meso-carbon micro-bead carbon or graphite fiber, carbon or graphitic nano-fiber, soft carbon, hard carbon, or combinations thereof.
  • the solvent or surfactant is selected from: butyl alcohol, ethanol, acetone, ketone, petroleum ether, N-methylpyrrolidone, hydrogen peroxide, water, or mixtures thereof.
  • the solvent or surfactant mixture has a Hildebrand solubility of at least of 23 MPa (1/2) .
  • the cavitation step and the high shear agitation step are carried out for 0.1 to 12 hours.
  • An embodiment comprises a subsequent step of submitting the mixture to an atomization nozzle and spray drying process.
  • the spray drying process is made on a spray drying chamber, a cyclone, a dehumidifier and an inert loop.
  • the atomization nozzle and spray drying process step is made at temperatures comprised between 40 and 350°C.
  • a device for the production of graphene or graphene-like material comprising a reactor having an enclosed vessel for receiving a solvent or surfactant mixture with dispersed particles of a crystalline graphitic material, said reactor being arranged for:
  • the reactor is configured for producing cavitation bubbles having a radius size of 0.2 to 18 ⁇ , in particular 1.2 to 10.5 ⁇ , further in particular 2.4 to 6.8 ⁇ .
  • An embodiment comprises two mechanical dispersion elements for high shear agitation.
  • the mechanical dispersion elements are a rotor and a stator.
  • the rotor and stator are arranged for creating a double toroidal vortex with shear stirring with doppler effect.
  • the high shear agitation is 5000 to 15000 RPM, in particular 6500 to 10500 RPM.
  • An embodiment comprises an atomization nozzle and spray drying stage for subsequent spray drying of the mixture.
  • An embodiment comprises a spray drying chamber, a cyclone, a dehumidifier and an inert loop.
  • Figure 1 Schematic representation of an embodiment of the disclosed reactor used in the method for the production of graphene, graphene-like and others two- dimensional materials.
  • the graphitic materials used in the first step of the above mentioned method are selected from the group composed by natural graphite, pyrolytic graphite, meso-carbon micro-bead carbon or graphite fiber, carbon or graphitic nano-fiber, soft carbon, hard carbon, and combinations thereof. These graphitic materials are introduced with a quantity of 0.25 to 1.25 mg/mL, preferably 0.5 mg/mL.
  • the solvent or surfactant used in the second step of the method is selected from at least one of the following: butyl alcohol, ethanol, acetone, petroleum ether, N-methylpyrrolidone, hydrogen peroxide and water.
  • the intention is to lower the surface tension and Hildebrand solubility parameter during the process in order to enhance the thermomechanical system and decrease the energy of the colloidal dispersion.
  • the energetic cost of the exfoliation goes lower as soon as we have a Hildebrand solubility of 23 MPa (1 2) , which means, a surface tension of 40 mJ/m 2 .
  • the mixture is subject to a cavitational force, a very well-known phenomenon that generates vapour cavities in the liquid medium or liquid-cavitation-free zones where the rapid change of pressure cause the formation of said cavities because the pressure in that zone is relatively lower.
  • the cavities are also called cavitation bubbles, implosion bubbles or voids and in this application the bubbles comprise a radius size within a range of 0.2 to 18 ⁇ .
  • cavitation bubbles also called non-inertial cavitation
  • the bubbles oscillates in size, storing energy until it is released in the form of a jet and shock wave.
  • the energy jets that occur near the particle surface allow a smooth break of the van der Waals bonds between graphite layers.
  • the generated bubbles implodes or collapses on themselves creating local conditions of 5000 degrees Celsius and 50 MPa of pressure. Due to the boundary layer effect, large sized bubbles are not allowed to form close enough to the convoluted surface, which due to their high energy characteristic have a destructive structural impact generating defects on the produced graphene. However, smaller cavitation bubbles are able to penetrate the interlayers surface enabling the peeling of each layer without damaging the graphene structure, nor adding defects.
  • a noteworthy aspect of the disclosed method is that the doppler effect of the high shear stirring, enha nced the performance in particle movement or particle momentum, which also uniforms the wave interference through the particle flow, thus enabling further control and optimization of the graphene production.
  • This third step is made in about 0.1 to 12h.
  • the fourth step of the method it may be used at least two dispersion elements, a rotor and a stator, mounted in a pivot.
  • the rotor or impeller is used in combination with the stationary component known as a stator to create a shear force that generates a double toroidal vortex to achieve the desired results.
  • the latter promotes a high mechanical stress in the material, breaking it down into small particles or microparticles.
  • the stirred method will be able to create a double flow vortex that split or break the bigger particles, with at least 200 ⁇ , into small ones within a range of 10 to 30 ⁇ .
  • the combination (simultaneous) of high shear agitation and cavitation force, described in the third step helps improving the production efficiency by reducing the time-cycle, homogenizing the mixture or lower range of particle size and avoid standing waves in the liquid medium.
  • the mixture is then submitted to an atomization nozzle and spray drying process on a spray drying chamber, a cyclone, a dehumidifier and an inert loop.
  • the spray drying process transforms a pumpable fluid feed into a dried product in a single operation, separating solids and gases.
  • the fluid is atomized using a rotating wheel or a nozzle where the spray of droplets immediately comes into contact with a flow of hot drying medium, usually air.
  • the resulting rapid evaporation maintains a low droplet temperature so that high drying air temperatures can be applied without affecting the material.
  • the evaporation rate is usually about 6 kg/h for water (only one atomizer) and is considerably more for organic solvents where a gain of 50% may be achieved.
  • the droplets drying time is very short in comparison with most other drying processes. Low product-temperature and short drying-time allow spray drying of very heat-sensitive materials like graphene.
  • the solvent/graphene mixture obtained with the described method is pumped with air from the reactor vessel for exfoliation of graphitic materials (1) using a high pressure two fluid nozzle and injected into the spray drying chamber (2) that converts the mixture and the air gas into a cloud of droplets that contact the hot drying gases.
  • the feed ratio with higher flow volume of gas comprised in range between 50 to 90%, generally produces smaller average particle sizes.
  • the cyclone (3) removes the finest particulates from an air, gas or liquid stream, without the use of filters, through vortex separation. Then, the final solid product drops to the finish product collector (5) and the gases separated. Specifically, water is separated by the dehumidifier (6) and tra nsferred to a proper water collector (7) while the inert loop (8) condensates the gases that are transferred into a different solvent collector (9).
  • the carrier gas flow to treat the evaporation of about 6 kg/h of water shall be about 80 kg/h.
  • the final product is held and the condensed fluids may be reused on the next production batch.
  • the temperature for submitting the mixture to an atomization nozzle and spray drying process on a spray drying chamber, a cyclone, a dehumidifier and an inert loop is comprised between 40 and 350?C
  • Fig. 1 illustrates an embodiment of the reactor used in the method for the production of graphene, graphene-like and other two-dimensional materials, where the following are represented: 1 - Reactor vessel for exfoliation of graphitic materials; 2 - Spray drying chamber; 3 - Cyclone; 4 - Large particles collector; 5 - Finish product collector; 6 - Dehumidifier; 7 - Water collector; 8 - Inert loop; 9 - Solvent collector; 10 - Exhaust air with particle filter.
  • the reaction mixture has been prepared by dispersing 100 grams of natural graphite flakes, with average particle size of at least 200 ⁇ , in 5 liters of ketone/water mixture with a molar ratio 75/25.
  • the mixture is submitted to a cavitation force with an implosion bubble radius size of 1.33 ⁇ and modulated in working frequency of a 3% range by a 'sweep' function, during 30 minutes and with a temperature of 40 degrees Celsius.
  • the power intensity is established in the value of 30 watt/liter.
  • the mixture is submitted to a high shear agitation of 7500 RPM.
  • the mixture is submitted to a spray drying process during two hours, until complete drying and separation of the graphene sheets from the mixture. The solvents are recovered and able to use in new production batch.
PCT/IB2016/054848 2015-08-11 2016-08-11 Method and device for production of graphene or graphene-like materials WO2017025926A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP16766385.5A EP3334686A1 (en) 2015-08-11 2016-08-11 Method and device for production of graphene or graphene-like materials
US15/751,922 US10843145B2 (en) 2015-08-11 2016-08-11 Method and device for production of graphene or graphene-like materials
CA2995433A CA2995433A1 (en) 2015-08-11 2016-08-11 Method and device for production of graphene or graphene-like materials

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PT108765 2015-08-11
PT10876515 2015-08-11

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GB2575827A (en) * 2018-07-24 2020-01-29 Npl Management Ltd Method of an apparatus for producing nanomaterials
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GB2593243A (en) * 2020-03-16 2021-09-22 Vozyakov Igor Flaking method and apparatus for monomolecular layers
WO2021204946A1 (en) 2020-04-09 2021-10-14 2D Fab Ab Manufacture of two-dimensional matter

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090005587A1 (en) * 2007-06-27 2009-01-01 H R D Corporation Method of making phthalic acid diesters
CN102757035A (zh) 2011-04-26 2012-10-31 海洋王照明科技股份有限公司 一种石墨烯的制备方法
US20130001068A1 (en) 2009-07-27 2013-01-03 Aruna Zhamu Production process for chemically functionalized nano graphene materials
CN103632845A (zh) 2012-08-24 2014-03-12 海洋王照明科技股份有限公司 石墨烯/有机薄膜复合集流体、其制备方法、电化学电极及电化学电池或电容器
CN103754864A (zh) 2014-01-02 2014-04-30 上海理工大学 一种石墨烯薄膜的制备方法
US20140242275A1 (en) * 2013-02-25 2014-08-28 Aruna Zhamu Process for producing unitary graphene materials
WO2014140324A1 (en) * 2013-03-14 2014-09-18 The Provost, Fellows, Foundation Scholars, And The Other Members Of Board, Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth, Near Dublin A scalable process for producing exfoliated defect-free, non-oxidised 2-dimensional materials in large quantities

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH064482B2 (ja) 1988-06-08 1994-01-19 三井鉱山株式会社 葉片状黒鉛粉末及びその製造方法
CN102020270B (zh) * 2009-09-09 2013-08-21 中国科学院金属研究所 一种大尺寸石墨烯的宏量制备方法
CN101671015B (zh) * 2009-10-13 2011-07-20 南昌航空大学 一种石墨烯材料的生产方法
CN102583332B (zh) 2012-01-17 2013-11-06 北京航空航天大学 一种在液相中制备石墨烯所用溶液的制备工艺及方法
CN103553030A (zh) 2013-11-05 2014-02-05 中国石油大学(北京) 一种少层石墨烯的制备方法
CN104058393B (zh) * 2014-06-30 2016-06-01 上海交通大学 一种剥离层状三维材料得到片层二维材料的方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090005587A1 (en) * 2007-06-27 2009-01-01 H R D Corporation Method of making phthalic acid diesters
US20130001068A1 (en) 2009-07-27 2013-01-03 Aruna Zhamu Production process for chemically functionalized nano graphene materials
CN102757035A (zh) 2011-04-26 2012-10-31 海洋王照明科技股份有限公司 一种石墨烯的制备方法
CN103632845A (zh) 2012-08-24 2014-03-12 海洋王照明科技股份有限公司 石墨烯/有机薄膜复合集流体、其制备方法、电化学电极及电化学电池或电容器
US20140242275A1 (en) * 2013-02-25 2014-08-28 Aruna Zhamu Process for producing unitary graphene materials
WO2014140324A1 (en) * 2013-03-14 2014-09-18 The Provost, Fellows, Foundation Scholars, And The Other Members Of Board, Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth, Near Dublin A scalable process for producing exfoliated defect-free, non-oxidised 2-dimensional materials in large quantities
CN103754864A (zh) 2014-01-02 2014-04-30 上海理工大学 一种石墨烯薄膜的制备方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107723828A (zh) * 2017-10-13 2018-02-23 江苏双良低碳产业技术研究院有限公司 一种高分散性石墨烯/尼龙6复合纤维的制备方法及纺丝方法
GB2575827A (en) * 2018-07-24 2020-01-29 Npl Management Ltd Method of an apparatus for producing nanomaterials
RU2720684C1 (ru) * 2019-03-13 2020-05-12 Федеральное государственное бюджетное образовательное учреждение высшего образования "Тамбовский государственный технический университет" (ФГБОУ ВО "ТГТУ") Способ получения графеносодержащих суспензий и устройство для его реализации
RU2737925C1 (ru) * 2019-12-12 2020-12-04 Федеральное государственное бюджетное образовательное учреждение высшего образования "Тамбовский государственный технический университет" (ФГБОУ ВО "ТГТУ") Способ получения графеносодержащих суспензий эксфолиацией графита и устройство для его реализации
GB2593243A (en) * 2020-03-16 2021-09-22 Vozyakov Igor Flaking method and apparatus for monomolecular layers
GB2593243B (en) * 2020-03-16 2023-11-29 Vozyakov Igor Flaking method and apparatus for monomolecular layers
WO2021204946A1 (en) 2020-04-09 2021-10-14 2D Fab Ab Manufacture of two-dimensional matter

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