WO2014122465A1 - Procédé de production de graphène - Google Patents

Procédé de production de graphène Download PDF

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Publication number
WO2014122465A1
WO2014122465A1 PCT/GB2014/050348 GB2014050348W WO2014122465A1 WO 2014122465 A1 WO2014122465 A1 WO 2014122465A1 GB 2014050348 W GB2014050348 W GB 2014050348W WO 2014122465 A1 WO2014122465 A1 WO 2014122465A1
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WO
WIPO (PCT)
Prior art keywords
mixture
reactor
graphene
khz
frequency
Prior art date
Application number
PCT/GB2014/050348
Other languages
English (en)
Inventor
Iana TOULTCHINSKI
Original Assignee
Carbonlab Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Carbonlab Limited filed Critical Carbonlab Limited
Publication of WO2014122465A1 publication Critical patent/WO2014122465A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene

Definitions

  • This invention relates to a method for the production of graphene.
  • the invention also relates to graphene obtainable by such a method.
  • Graphene can be viewed as a two dimensional sheet composed of sp 2 carbons in a honeycomb structure.
  • Graphene layers are the building blocks for all the other graphitic carbon allotropes.
  • graphite (3-D) is composed of graphene layers stacked on top of each other with an interlayer spacing of approximately 3.4 Angstroms.
  • Carbon nanotubes on the other hand, can be viewed as graphene layers rolled into tubes.
  • Graphene has very attractive physical, optical and mechanical properties, including high charge carrier mobility, high thermal conductivity and stiffness. It can be used for a wide range of applications, for example, in the electronics industry as well as for an additive in polymer production.
  • graphene can be exfoliated from graphite using adhesive tape or obtained by reducing layers of graphite oxide.
  • Graphite can also be exfoliated in the liquid phase in an
  • the present invention also provides graphene obtained or obtainable by the above method.
  • Figure 1 is a schematic diagram of an apparatus that is suitable for carrying out a method according to one embodiment of the present invention.
  • the present invention provides a method for the production of graphene, said method comprising: a) providing a mixture of graphite in a solvent, b) subjecting the mixture to sonication at at least one frequency in the range of 15 to 30 kHz, and
  • the exfoliation of graphite may be improved.
  • the frequencies employed in step c) may be used to separate larger graphene particles (e.g. 20 to 100nm), while the frequencies employed in step b) may be used to separate smaller graphene particles (e.g. less than 20 microns, for example, less than 20 nanometres).
  • the mixture may also be circulated between steps b) and c) in a loop to optimise the process.
  • step b) of the method is performed by sonicating the mixture at 15 to 30 kHz.
  • the mixture is subjected to ultrasound at at least one frequency in the range of 20 to 25 kHz.
  • the ultrasound treatment occurs at a frequency of 18 to 22 kHz, for example, 20 kHz.
  • Step b) may be performed at a power of 300 to 2000 W, preferably 400 to 800 W, more preferably 400 to 500 W.
  • step c) the mixture is subjected to sonication at at least one frequency in the range of 50 to 250 kHz, for example, 50 to 100 or 100 to 250 kHz.
  • the ultrasound treatment in step c) occurs at a frequency of 50 to 100 kHz.
  • the ultrasound treatment occurs at a frequency of 55 to 90 kHz, preferably 55 to 80 kHz, for example 60 kHz.
  • the ultrasound treatment occurs at a frequency of 100 to 250 kHz, preferably 120 to 180 kHz, more preferably 140 to 160 kHz, for example, 150 kHz.
  • Step c) may be performed at a power of 500 to 4000W, preferably 3500 to 4000 W.
  • the volume of mixture that is treated may be subjected to a power of 300 to 700 W per litre, preferably 350 to 500 W per litre. In another embodiment, the volume of mixture that is treated may be subjected to a power of 25 to 200 W per litre, preferably 120 to 150 W per litre.
  • Steps b) and c) may be carried out in any order in the process.
  • step c) is carried out prior to step b).
  • the mixture is preferably circulated between steps b) and c).
  • a first reactor is provided for performing step b), while a second reactor is provided for performing step c).
  • the mixture may then be passed from the first reactor to the second reactor or vice- versa, or preferably circulated between the reactors using, for example, an appropriate piping or connection means.
  • the mixture may be passed from one reactor to another and thereafter to a holding tank.
  • the holding tank is positioned downstream of the second reactor, such that the mixture is introduced into the holding tank after treatment in both the first and second reactors.
  • the temperature and pressure of the mixture may be monitored and/or controlled, for example, by withdrawing a sample from the holding tank and, optionally, heating or cooling it as necessary.
  • the mixture is circulated through the first reactor, second reactor and holding tank.
  • the circulation of the mixture may be regulated through the use of pumps.
  • the reactors used in steps b) and/or c) may be continuous flow reactors.
  • a summary of the operation of the reactors is as follows. Acoustic energy with a working frequency between 15-30 kHz in the first reactor and 50-250 kHz or 100-250 kHz in the second may be transmitted from an ultrasonic generator to a
  • a waveguide may be attached to the magnetostrictive transducer.
  • the waveguide may be a concentrator with an amplification coefficient k of between 7 and 10, which produces axial and radial emission within the reactor.
  • the normal working displacement amplitude of the concentrator face may be 70-120 micron.
  • the waveguide may be adjacent to the bottom section of the reactor, to which the input nozzle for the working mixture may be attached.
  • the clearance between the waveguide and bottom section of the reactor may be equal to the amplitude of displacement of the waveguide face.
  • the waveguide and the bottom section of the reactor may together constitute a hydrodynamic valve, operating at the frequency of the magnetostrictor.
  • the static pressure in the region of cavitational emission may fluctuate between 0 and a set working pressure, P w , of the magnetostrictive transducer. This may generate supplementary vibrational energy within the cavitation zone, in addition to the acoustic energy. This process may be used to assist in the dispersion of solids.
  • Step b) may be carried out at a temperature of 0 to 200 degrees C, preferably 15 to 120 degrees C. In one embodiment, the temperature is 10 to 90 degrees C, for example, 10 to 20 degrees C. The temperature may be selected depending on the nature of the solvent. Step b) may also be carried out at a pressure of 0.01 to 0.97 MPa. In one embodiment, the pressure and/or temperature of the first reactor is controlled such that the reaction temperature and pressure are within the desired ranges.
  • Step c) may be carried out at a temperature of 0 to 200 degrees C, preferably 15 to 120 degrees C. In one embodiment, the temperature is 10 to 90 degrees C, for example, 10 to 20 degrees C. The temperature may be selected depending on the nature of the solvent. Step c) may also be carried out at a pressure of 0.01 to 0.97 MPa. In one embodiment, the pressure and/or temperature of the second reactor is controlled such that the reaction temperature and pressure are within the desired ranges.
  • the temperature and pressure conditions may be the same in both reactors.
  • the temperature of the holding tank may be maintained at a temperature of 15 to 90 degrees C, preferably 60 to 70 degrees C.
  • the pressure may be maintained at 0.01 to 0.97MPa.
  • a mixture e.g. slurry
  • graphite and solvent may be formed and mixed in the holding tank.
  • the concentration of graphite in the solvent can be varied to maintain the desired viscosity of the solution.
  • the concentration of graphite in the solvent may be from 5 to 18%.
  • the graphite is provided as a mixture in a solvent.
  • the graphite is provided as a dispersion in a solvent.
  • the mixture of graphite in a solvent may form a homogenized solution. Any suitable form of graphite may be used.
  • the graphite may be prepared by crushing (e.g. in a ball mill) prior to being added to the solvent.
  • Examples of suitable forms of graphite include graphite powder and graphite flakes.
  • graphite flakes are used having a high carbon content (e.g. above 99%, preferably 99.95%).
  • the flakes are preferably crushed (e.g. in a ball mill) into particles, for example, of 50 microns in size.
  • the graphite may be washed in a solvent prior to forming the mixture.
  • the solvent for used washing the graphite may be the same or different to the solvent used for forming the mixture.
  • Any suitable solvent may be employed.
  • suitable solvents include organic solvents and aqueous solvents, including water.
  • Suitable organic solvents include alcohols, such as C 2 to C 6 alcohols, and hydrocarbon solvents, such as alkanes.
  • Suitable alcohols include ethanol, propanol, butyl alcohol, pentanol and hexanol.
  • Suitable hydrocarbon solvents include C 5 to C 10 alkanes and mixtures thereof.
  • An example of a suitable alkane mixture is petroleum ether.
  • the present invention may be carried out using non-corrosive solvents. Specific examples include butyl alcohol, ethanol, petroleum ether and water. Without wishing to be bound by any theory, it is believed that the efficient exfoliation afforded by steps b) and c) of the present invention allows milder solvents to be used to achieve desirable results.
  • a surfactant may also be used in the mixture, particularly where aqueous solvents or water are used as the solvent.
  • An example of a suitable surfactant is sodium dodecyl sulphate.
  • the graphene produced from the method of the present invention may be separated using any suitable method. Examples include decanting, centrifugation and filtration (e.g. membrane filtration). To separate the graphene, a portion of the mixture may be removed from the process, for example, after a particular reaction time. In one embodiment, the sample may be continuously withdrawn from the process, for example, via a holding tank. The reaction time of the process can be controlled to determine the particle size of the graphene produced. Generally speaking, the longer the reaction time, the thinner the graphene particle size. In one embodiment, the reaction time for a single cycle is 60 minutes. More than one cycle may be carried out, for example to obtain thinner graphene. The specific choice of solvent may also affect the graphene particle size. [0028] Following separation, the graphene produced from the method of the present invention may be dried using any suitable method. An example of a suitable drying method is vacuum drying.
  • the graphene produced from the method of the present invention may be separated from the mixture by decanting and centrifugation, followed by vacuum drying.
  • the graphene produced may have an average particle size of 100 nm or less, preferably 80 nm or less, more preferably 60 nm or less, for example, 20 nm or less.
  • particle size it is meant the thickness of the graphene particles rather than diameter.
  • the particle size (thickness) is 1 to 15 nm, preferably 1 to 10 nm, for example, 1 to 5 nm or 5 to 10 nm.
  • the diameter of the particles may range from 5 to 20 microns, for example, 5 to 10 microns.
  • the graphene particles produced have an average particle size (thickness) of 1 to 5 nm and a diameter of 5 to 7 microns.
  • the graphene particles produced have an average particle size (thickness) of 1 to 10 nm and a diameter of 5 to 15 microns.
  • the graphene produced or obtainable by the method of the present invention includes single layer graphene as well as few-layer graphene of, for example, up to 10 layers of graphene thick.
  • graphene as used in relation to the present invention covers graphene flakes and graphite nanoplatelets, and nanographite materials. The number of layers of graphene in nanographite materials is dependent on the time and parameters used. In one embodiment, the nanographite material comprises between 5 and 10 layers of graphene.
  • Particle size may be measured using any known method. For example, an electron dual beam microscopy or scanning probe microscopy may be used. Raman spectroscopy, X-ray diffraction or an atomic force microscope may also be used to measure the particle size. The resulting thickness of the graphene is determined by treatment time and type of solvent.
  • a prevelance (up to 98%) of the particles have an average particle size (thickness) of 1 to 5 nm. In one embodiment, the effective particle diameter is 3 to 5 microns.
  • the graphene produced or obtainable using the method of the present invention may be used for a wide range of applications.
  • the graphene may be used as an additive for polymers, such as polyethylene and polystyrene.
  • the graphene may also be used for electrical or electronic applications, such as an electrode additive for, for example, lithium accumulators, or in the manufacture of supercapacitors.
  • the graphene may also be formulated into inks and coatings to achieve desired thermal and electrical properties.
  • Graphene materials obtained using described method may also be used in a thermal interface material, such as a thermal grease.
  • the thermal conductivity of the thermal grease may be in the range of up to 300 Wm ' V '1 .
  • the method of the present invention may allow graphene to be produced in high yield in a relatively time and cost efficient process.
  • the specific surface area of the graphene produced may range from 200 to 2400 m 2 /g. In one embodiment, the specific surface area of the grapheme produced is from 200 to 1000 m 2 /g.
  • Figure 1 depicts an apparatus for performing a method according to one embodiment of the present invention.
  • the apparatus comprises a first reactor 10, a second reactor 20 and a holding tank 30.
  • the apparatus also comprises a control unit 40 for monitoring the temperature and pressure of liquid in the holding tank 30.
  • a mixture 50 of graphite in a solvent of, for example, butyl alcohol is circulated through the apparatus.
  • the mixture 50 is treated in the first reactor 10 where it is subjected to sonication at a frequency in the range of 15 to 30 kHz.
  • the mixture is then introduced into the second reactor 20 where it is subjected to sonication at a frequency in the range of 50 to 250 kHz, for example, 50 to 100 kHz or 100 to 250 kHz.
  • the mixture 50 is introduced into the holding tank 30, where it is circulated through the control unit 40 via pump 60 to monitor its pressure and temperature. From the holding tank 30, the mixture 50 is also recycled to the first reactor via pump 70.
  • Graphene may be separated from a sample of the mixture 50 withdrawn (not shown), for example, from the holding tank after a predetermined period of treatment.
  • the temperature of the first reactor 10, second reactor 20 and cooling tank 30 may be controlled, for example, through the use of a circulating heat control medium 80.
  • Reactor 1 frequency 22.5 kHz; power density 2.1 W/cm 3
  • Reactor 2 frequency 190 kHz; power density 6.2 W/cm 3
  • Reactor 1 frequency 25 kHz; power density 3 W/cm 3

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention porte sur un procédé pour la production de graphène, ledit procédé comprenant : l'utilisation d'un mélange de graphite dans un solvant, l'opération consistant à soumettre le mélange à des ultrasons à au moins une fréquence dans la plage de 15 à 30 kHz et l'opération consistant à soumettre le mélange à des ultrasons à au moins une fréquence dans la plage de 50 à 250 kHz.
PCT/GB2014/050348 2013-02-07 2014-02-06 Procédé de production de graphène WO2014122465A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1302149.8 2013-02-07
GBGB1302149.8A GB201302149D0 (en) 2013-02-07 2013-02-07 Graphene production method

Publications (1)

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WO2014122465A1 true WO2014122465A1 (fr) 2014-08-14

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016096484A1 (fr) * 2014-12-19 2016-06-23 Tata Steel Uk Limited Procédé de production de graphène
EP3072851A1 (fr) * 2015-03-27 2016-09-28 Tata Steel UK Ltd Procédé de fabrication de graphène
WO2017025973A1 (fr) * 2015-08-13 2017-02-16 B.G. Negev Technologies And Applications Ltd., At Ben-Gurion University Procédé de fabrication de graphène
WO2018199512A1 (fr) * 2017-04-28 2018-11-01 주식회사 엘지화학 Procédé de fabrication de graphène
CN114314571A (zh) * 2020-10-10 2022-04-12 吴国明 一种石墨烯微晶片的制备方法

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US20110046289A1 (en) * 2009-08-20 2011-02-24 Aruna Zhamu Pristine nano graphene-modified tires

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GB2483288A (en) * 2010-09-03 2012-03-07 Trinity College Dublin Exfoliation process for forming semiconducting nanoflakes
EP2734468B1 (fr) * 2011-07-19 2020-09-09 Flex-G Pty Ltd Exfoliation de matériau laminaire par ultrasonication dans un tensioactif
CN102557023A (zh) * 2012-03-12 2012-07-11 大连丽昌新材料有限公司 一种石墨烯的制备方法

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US20090022649A1 (en) * 2007-07-19 2009-01-22 Aruna Zhamu Method for producing ultra-thin nano-scaled graphene platelets
US20100028681A1 (en) * 2008-07-25 2010-02-04 The Board Of Trustees Of The Leland Stanford Junior University Pristine and Functionalized Graphene Materials
US20110046289A1 (en) * 2009-08-20 2011-02-24 Aruna Zhamu Pristine nano graphene-modified tires

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LONGXIU ZHU ET AL: "High-quality production of graphene by liquid-phase exfoliation of expanded graphite", MATERIALS CHEMISTRY AND PHYSICS, vol. 137, no. 3, 1 January 2013 (2013-01-01), pages 984 - 990, XP055123996, ISSN: 0254-0584, DOI: 10.1016/j.matchemphys.2012.11.012 *
VÁCLAV STENGL: "Preparation of Graphene by Using an Intense Cavitation Field in a Pressurized Ultrasonic Reactor", CHEMISTRY - A EUROPEAN JOURNAL, vol. 18, no. 44, 29 October 2012 (2012-10-29), pages 14047 - 14054, XP055124011, ISSN: 0947-6539, DOI: 10.1002/chem.201201411 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016096484A1 (fr) * 2014-12-19 2016-06-23 Tata Steel Uk Limited Procédé de production de graphène
EP3072851A1 (fr) * 2015-03-27 2016-09-28 Tata Steel UK Ltd Procédé de fabrication de graphène
WO2017025973A1 (fr) * 2015-08-13 2017-02-16 B.G. Negev Technologies And Applications Ltd., At Ben-Gurion University Procédé de fabrication de graphène
WO2018199512A1 (fr) * 2017-04-28 2018-11-01 주식회사 엘지화학 Procédé de fabrication de graphène
KR20180121209A (ko) * 2017-04-28 2018-11-07 주식회사 엘지화학 그래핀 제조방법
KR102176629B1 (ko) 2017-04-28 2020-11-09 주식회사 엘지화학 그래핀 제조방법
US11254576B2 (en) 2017-04-28 2022-02-22 Lg Energy Solution, Ltd. Method of preparing graphene
CN114314571A (zh) * 2020-10-10 2022-04-12 吴国明 一种石墨烯微晶片的制备方法

Also Published As

Publication number Publication date
GB201402044D0 (en) 2014-03-26
GB2512711B (en) 2016-09-14
GB2512711A (en) 2014-10-08
GB201302149D0 (en) 2013-03-27

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