WO2016096484A1 - Procédé de production de graphène - Google Patents

Procédé de production de graphène Download PDF

Info

Publication number
WO2016096484A1
WO2016096484A1 PCT/EP2015/078696 EP2015078696W WO2016096484A1 WO 2016096484 A1 WO2016096484 A1 WO 2016096484A1 EP 2015078696 W EP2015078696 W EP 2015078696W WO 2016096484 A1 WO2016096484 A1 WO 2016096484A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene
liquid
suspension
graphene precursor
surfactant
Prior art date
Application number
PCT/EP2015/078696
Other languages
English (en)
Inventor
Sivasambu BÖHM
Henagama Liyanage Mallika Böhm
Samson PATOLE
Kevin Victor GRAHAM
Digvijay THAKUR
Sai SHIVAREDDY
Original Assignee
Tata Steel Uk 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
Priority claimed from EP15020048.3A external-priority patent/EP3072851A1/fr
Application filed by Tata Steel Uk Limited filed Critical Tata Steel Uk Limited
Priority to EP15805465.0A priority Critical patent/EP3233726A1/fr
Publication of WO2016096484A1 publication Critical patent/WO2016096484A1/fr

Links

Classifications

    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer

Definitions

  • the invention relates to a method of producing graphene from a graphene precursor using mechanical treatment of the graphene precursor.
  • the top-down route is basically the exfoliation of a graphene precursor, wherein the graphene precursor comprises natural graphite or synthetic graphite.
  • the exfoliation method comprises chemical treatment of the graphene precursor, which often includes toxic chemicals.
  • the graphene precursor is first treated with strong oxidants resulting in the forming of graphene oxide.
  • Graphene oxide can be dispersed easily in solvents, including water, and is subsequently subjected to a reducing step by treating the graphene oxide again with chemicals, for instance with hydrazine.
  • This exfoliation method requires a number of subsequent processing steps which makes this also a time consuming method. If such a method is to be carried out on an industrial scale the chemicals needed would be substantial, requiring adequate safety and environmental measures.
  • the quality of the graphene resulting from this exfoliation method can be substantially less than the quality of the graphene resulting from the method according to the bottom-up route.
  • one or more of the objectives of the invention are realized by providing a method for producing graphene, which comprises the steps of:
  • the mechanical treatment comprises that the graphene precursor suspended in the liquid is subjected to at least two different mechanical treatments at the same time.
  • graphene precursor shall mean a solution or compound comprising natural graphite or synthetic graphite.
  • graphene shall refer to single layer graphene as well as to multilayer stacks of graphene comprising 20 layers or less of graphene, unless indicated differently.
  • the time needed to produce graphene is considerable reduced in comparison to the usual method wherein mechanical and chemical treatment steps are carried out subsequently.
  • milling times of 24 hours and more are necessary whereas with the method according the invention the time needed to carry out the method is less than 3 hours.
  • the graphene produced according to the method shows a high yield of single and bilayer graphene.
  • the mechanical treatment comprises a mixing operation and sonication operation.
  • the milling operation is a high shear mixing operation.
  • This milling operation is carried out with high shear mixers which operate at speeds in the order of 6000 - 9000 rpm.
  • the sonication operation is preferably a ultrasonication operation wherein the liquid with the graphene precursor in suspension is subjected to ultrasonic waves of 20 kHz and more.
  • the sound waves propagating through the liquid generate compression and rarefaction cycles, the rarefaction creating voids which collapse during compression.
  • the frequency of the ultrasonication is in the range of 30 - 60 kHz, more preferably in the range of 40 - 50 kHz.
  • the liquid with the graphene precursor in suspension is cooled.
  • the temperature of the liquid with the graphene precursor in suspension is cooled to a temperature below 100°C. More preferably the temperature of the liquid with the graphene precursor in suspension is kept in a range between 0 - 50°C, and even more preferably to about room temperature in a range between 15 - 35°C.
  • the method includes the addition of a surfactant to the liquid with the graphene precursor.
  • the liquid is water and the surfactant is a water soluble surfactant.
  • the surfactant is a tetra butyl ammonium surfactant or an alkylol ammonium surfactant. Good results were obtained with ANTI-TERRA ® -250, a solution of an alkylol ammonium salt of a higher molecular weight acidic polymer, a surfactant supplied by BYK Chemie GmbH.
  • the surfactant is preferably added in a concentration of 0.1 - 10.0 mg/ml, preferably 0.2 - 5.0 mg/ml.
  • the method according to the invention is suitable to be carried out batch- wise, but it is also possible to carry out the method in a continuous or semi- continuous process.
  • fig.1 shows schematically a device to apply the method for producing graphene
  • fig.2 shows a Raman diagram of the produced graphene
  • fig.3 shows a TEM image and an electron diffraction diagram of the produced graphene.
  • a device for applying the method comprising a vessel with a cooling liquid and a pipe system 5 for the supply and drainage of the cooling liquid from the vessel.
  • the temperature of the cooling liquid is measured with a probe 1 and the temperature data is used to control the supply and drainage of the cooling liquid. With water as a cooling liquid the temperature can be controlled adequately.
  • a sample cup 6 is placed containing the liquid with the graphene precursor in suspension.
  • a high shear mixer 2 is provided extending with the shear generating element in the liquid with the graphene precursor in suspension.
  • the shear mixer is provided with a speed controller unit 3 with which the speed of the mixture can be adjusted.
  • a further temperature measuring probe 4 is immersed in the liquid with the graphene precursor in suspension and is also used to control the temperature of the cooling liquid contained in the vessel.
  • a ultrasonicator 7 is immersed in the cooling liquid. By operating the ultrasonicator the liquid with the graphene precursor in suspension in sample cup 6 is subjected to the sound waves propagating from ultrasonicator 7.
  • a Raman spectrum of a graphene sample obtained by the method according the invention was performed at room temperature with a Renishaw spectrometer at 514nm, with notch filters cutting at 100 cm-1 .
  • the vertical axis shows the intensity of the scattered Raman signal and the horizontal axis shows the Raman shift in cm-1 when excited by a laser radiation with a wavelength of 514 nm.
  • the principle peaks observed in the graphene Raman spectrum are the D, G and 2D peaks at 1350 cm-1 , 1580 cm-1 and 2700 cm-1 respectively.
  • the spectrum above indicates that the synthesized material contains a high content of monolayer graphene as indicated by the very symmetrical 2D peak with a Lorentzian profile centred at 2692 cm-1 .
  • the image to the left in fig. 3 shows a transmission electron micrograph of a graphene flake.
  • the image to the right is an electron diffraction pattern obtained from the same sample. It shows the typical six-fold symmetry expected for graphene and graphite.
  • the electron diffraction spots are labelled using Miller- Bravais indices (hkil). The ratio of identified peak intensities of 0th order and 1 st order spots is indicative of single or bilayer graphene depending on the area under the electron beam.
  • Ultraviolet visible absorption spectra of the test shows the concentration of final graphene based suspension (after sonication, centrifuging at l OOOrpm for 1 hr and separating the supernatant) in the range of 0.063 - 0.1 1 mg/ltr which is much higher than values reported in literature.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention concerne un procédé de production de graphène comprenant les étapes consistant à disperser un précurseur de graphène dans un liquide afin de créer une suspension du précurseur de graphène dans le liquide et à soumettre la suspension du précurseur de graphène dans le liquide à au moins deux traitements mécaniques différents en même temps.
PCT/EP2015/078696 2014-12-19 2015-12-04 Procédé de production de graphène WO2016096484A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP15805465.0A EP3233726A1 (fr) 2014-12-19 2015-12-04 Procédé de production de graphène

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP14020118.7 2014-12-19
EP14020118 2014-12-19
EP15020048.3A EP3072851A1 (fr) 2015-03-27 2015-03-27 Procédé de fabrication de graphène
EP15020048.3 2015-03-27

Publications (1)

Publication Number Publication Date
WO2016096484A1 true WO2016096484A1 (fr) 2016-06-23

Family

ID=54834813

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2015/078696 WO2016096484A1 (fr) 2014-12-19 2015-12-04 Procédé de production de graphène

Country Status (2)

Country Link
EP (1) EP3233726A1 (fr)
WO (1) WO2016096484A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018051095A1 (fr) * 2016-09-15 2018-03-22 University Of Sunderland Procédé de formation de nanoplaquettes de graphène, nanoplaquettes de graphène ainsi obtenues et composites comprenant lesdites nanoplaquettes
CN110621809A (zh) * 2017-04-26 2019-12-27 烯克斯·索尼娅技术有限公司 半导体材料或导体材料的制备方法及其用途
WO2020012500A1 (fr) 2018-07-09 2020-01-16 Log 9 Materials Scientific Private Limited Système et procédé de synthèse en masse de graphène et de ses dérivés

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090026086A1 (en) * 2007-07-27 2009-01-29 Aruna Zhamu Electrochemical method of producing nano-scaled graphene platelets
US20110017585A1 (en) * 2009-07-27 2011-01-27 Aruna Zhamu Mass production of pristine nano graphene materials
FR2952049A1 (fr) * 2009-11-03 2011-05-06 Centre Nat Rech Scient Preparation de graphene par amincissement mecanique de materiaux graphitiques
WO2014122465A1 (fr) * 2013-02-07 2014-08-14 Carbonlab Limited Procédé de production de graphène
CN104058396A (zh) * 2014-07-14 2014-09-24 复旦大学 一种层数可控的大尺寸、高质量石墨烯制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090026086A1 (en) * 2007-07-27 2009-01-29 Aruna Zhamu Electrochemical method of producing nano-scaled graphene platelets
US20110017585A1 (en) * 2009-07-27 2011-01-27 Aruna Zhamu Mass production of pristine nano graphene materials
FR2952049A1 (fr) * 2009-11-03 2011-05-06 Centre Nat Rech Scient Preparation de graphene par amincissement mecanique de materiaux graphitiques
WO2014122465A1 (fr) * 2013-02-07 2014-08-14 Carbonlab Limited Procédé de production de graphène
CN104058396A (zh) * 2014-07-14 2014-09-24 复旦大学 一种层数可控的大尺寸、高质量石墨烯制备方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018051095A1 (fr) * 2016-09-15 2018-03-22 University Of Sunderland Procédé de formation de nanoplaquettes de graphène, nanoplaquettes de graphène ainsi obtenues et composites comprenant lesdites nanoplaquettes
CN110621809A (zh) * 2017-04-26 2019-12-27 烯克斯·索尼娅技术有限公司 半导体材料或导体材料的制备方法及其用途
CN110621809B (zh) * 2017-04-26 2022-09-13 烯克斯·索尼娅技术有限公司 半导体材料或导体材料的制备方法及其用途
WO2020012500A1 (fr) 2018-07-09 2020-01-16 Log 9 Materials Scientific Private Limited Système et procédé de synthèse en masse de graphène et de ses dérivés
CN112672978A (zh) * 2018-07-09 2021-04-16 对数9物质科学私人有限公司 大量合成石墨烯和衍生物的系统和方法
EP3820814A4 (fr) * 2018-07-09 2022-03-30 Log 9 Materials Scientific Private Limited Système et procédé de synthèse en masse de graphène et de ses dérivés

Also Published As

Publication number Publication date
EP3233726A1 (fr) 2017-10-25

Similar Documents

Publication Publication Date Title
Korepanov et al. Carbon structure in nanodiamonds elucidated from Raman spectroscopy
Malaki et al. MXenes and ultrasonication
Lin et al. Laser-ablation production of graphene oxide nanostructures: from ribbons to quantum dots
Arabpour et al. Preparation and optimization of novel graphene oxide and adsorption isotherm study of methylene blue
Ali et al. Effect of sonication conditions: solvent, time, temperature and reactor type on the preparation of micron sized vermiculite particles
WO2016096484A1 (fr) Procédé de production de graphène
Nebogatikova et al. Fluorinated graphene dielectric films obtained from functionalized graphene suspension: preparation and properties
Ding et al. Exploring the blue luminescence origin of nitrogen-doped carbon dots by controlling the water amount in synthesis
Zhang et al. Multifunctional Zn–Al layered double hydroxides for surface-enhanced Raman scattering and surface-enhanced infrared absorption
Gholizadeh et al. Facile synthesis of nanographene by a high-yield and scalable method
Rahaman et al. Understanding the effect of surfactants’ hydrophobicity on the growth of lanthanum sulfide nanospheres in water-in-oil microemulsions: A detailed dynamic light scattering, small angle X-ray scattering, and microscopy study
EP3072851A1 (fr) Procédé de fabrication de graphène
AU2017304275B2 (en) An improved method for the synthesis of graphene oxide
Lebedev et al. Microwave plasma in liquid n-heptane: a study of plasma-chemical reaction products
Neira‐Velázquez et al. Surface modification of nanoclays by plasma polymerization of ethylene
Ren et al. Engineering UV-emitting defects in h-BN nanodots by a top-down route
Jirásek et al. Hydroxylation and self-assembly of colloidal hydrogenated nanodiamonds by aqueous oxygen radicals from atmospheric pressure plasma jet
Pelletier et al. Influence of layer charge on the hydroxyl stretching of trioctahedral clay minerals: A vibrational study of synthetic Na-and K-saponites
Wang et al. Synthesis and structure of molybdenum diselenide nanosheets produced from MoO3 and Se powders
JP7090811B2 (ja) 気液物質移動による炭素材料のその場製造および機能化ならびのその使用
Machida et al. Expansion of orderly stacked metakaolinite layers and order destruction using a kaolinite-tetraphenylphosphonium chloride intercalation compound
Azadbakht et al. Synthesis and characterization of acrylic fibers with antibacterial silver nanoparticles
Pol’shchikov et al. Composite materials based on graphene nanoplatelets and polypropylene derived via in situ polymerization
EP3072852A1 (fr) Procédé de fabrication de graphène
EP3248939A1 (fr) Particules de silicone organofonctionnelle, son procede de fabrication et d'utilisation

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15805465

Country of ref document: EP

Kind code of ref document: A1

REEP Request for entry into the european phase

Ref document number: 2015805465

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE