WO2019196144A1 - Méthode de préparation de graphène par intercalation de métal alcalin - Google Patents

Méthode de préparation de graphène par intercalation de métal alcalin Download PDF

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Publication number
WO2019196144A1
WO2019196144A1 PCT/CN2018/085135 CN2018085135W WO2019196144A1 WO 2019196144 A1 WO2019196144 A1 WO 2019196144A1 CN 2018085135 W CN2018085135 W CN 2018085135W WO 2019196144 A1 WO2019196144 A1 WO 2019196144A1
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WO
WIPO (PCT)
Prior art keywords
graphite
alkali metal
graphene
composite material
intercalating
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PCT/CN2018/085135
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English (en)
Chinese (zh)
Inventor
李彬
杨树斌
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北京航空航天大学
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Publication of WO2019196144A1 publication Critical patent/WO2019196144A1/fr

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    • 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
    • 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
    • C01B2204/04—Specific amount of layers or specific thickness
    • 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
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/32—Size or surface area
    • 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
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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

Definitions

  • the invention belongs to the field of inorganic non-metal materials, and in particular relates to a method for preparing graphene.
  • Graphene has excellent material properties, including a large specific surface area, a high Young's modulus, electron mobility, and an extremely high thermal conductivity.
  • Graphene is composed of a single layer of sp 2 hybridized carbon atoms. It is the thinnest and hardest nano carbon material known at present, and it is almost completely transparent, light in weight, excellent in flexibility and superior thermal conductivity. It has a wide range of applications in the fields of energy storage, catalysis, and composite materials.
  • the production methods of graphene mainly include a top-down method and a bottom-up method.
  • Bottom-up growth methods such as traditional chemical vapor deposition methods, but chemical vapor deposition methods require graphene to grow in harsh environments, such as higher temperatures and high vacuum, and the addition of catalysts during the deposition process. Catalytic growth consumes a large amount of energy during the growth process. In addition, the growth rate of the method is slow and the production cost is greatly increased, which greatly limits the application fields of such grown graphene.
  • Top-down methods such as liquid phase stripping, starting from natural graphite, using a stripping method to prepare graphene oxide, and further reducing the preparation of graphene, such methods generally require higher energy or strong oxides in the preparation process. Pre-treatment, post-reduction method to prepare graphene, the graphene prepared by this method will cause many defects in the redox process, and the preparation cycle is also long.
  • the object of the present invention is to propose a high-efficiency method for preparing graphene by intercalating alkali metal, using graphite carbon material as raw material and metal lithium or other high active alkali metal as intercalation material.
  • the single-layer or oligo-layer graphene is obtained by expanding the intercalated metal based on metal intercalated graphite and rapidly reacting.
  • Another object of the present invention is to provide graphene obtained by the production method.
  • a method for preparing graphene by intercalating alkali metal comprising the following steps:
  • a graphite-based material and an alkali metal are mixed to obtain a uniformly mixed graphite-based carbon material-alkali metal composite material, and allowed to stand in an inert environment to cause a metal intercalation reaction until the composite material From black to golden yellow;
  • the obtained composite material is placed in a liquid medium capable of reacting therewith to carry out a reaction, the intercalation material is removed, and the graphene material is obtained by shaking, washing and separating.
  • the alkali metal is one or more of lithium, sodium and potassium
  • the graphite material may be natural graphite or artificial graphite, specifically graphite paper, graphite powder, flake graphite, expanded graphite, spherical graphite One or more of highly oriented pyrolytic graphite.
  • the mass ratio of the graphite material to the alkali metal in the step (1) is 1 to 10:1; the graphite material and the alkali metal are mixed and repeatedly folded and rolled until the mixture is uniformly mixed; or the alkali metal is melted by heating and then added. The graphite material is stirred and mixed evenly.
  • the inert environment is an argon atmosphere and/or a helium atmosphere, and is allowed to stand in an inert environment until the graphite turns golden yellow, generally 10 hours or more, and can be placed in an inert environment all the time. Further changes.
  • the liquid medium is one or more of water, methanol, ethanol, propanol, n-butanol, ethylene glycol, formic acid, acetic acid, propionic acid and hydrochloric acid.
  • the oscillation in the step (2) may be ultrasonic vibration.
  • the concentration of hydrochloric acid may be, but not limited to, 0.05 to 0.5 mol/L.
  • An optional technical solution of the present invention is that after the step (1), the operation is performed:
  • the non-inert environment is one or more of air, nitrogen, carbon dioxide, ammonia, water vapor, argon-organic acid mixture, and argon-organic alcohol mixture.
  • the operation is performed: the obtained composite material is placed in a container, and one of water vapor, argon-acetic acid mixed gas and argon-ethanol mixed gas is slowly introduced into the container. The golden yellow color of the composite material is completely removed, and the composite material is taken out, and the step (2) is carried out.
  • the mass ratio of acetic acid or ethanol in the mixed gas may be 1-20%.
  • the obtained graphene has the following features: the graphene layer has a thickness of 1-10 layers and a lateral dimension of 0.2-100 ⁇ m.
  • the graphene obtained by the method of the present invention is prepared.
  • the gold-yellow composite material after intercalation reaction of lithium or other high-activity alkali metal and graphite-based carbon material is used as a precursor, and the preparation of graphene in the later stage can be at room temperature. It is carried out under conditions of air and the like, and is suitable for the preparation of graphene on a large scale.
  • the preparation method of the present invention abandons the conventional high-pollution preparation method of the redox agent, and the high-energy preparation method such as mechanical shearing and arc discharge, and the method for processing the intercalated metal by intercalating reaction of lithium and graphite-based carbon materials
  • the high-quality graphene is obtained, the method has high yield of graphene, the obtained graphene product has high single layer rate, and the preparation method is fast and efficient, low in energy consumption and small in pollution, and is suitable for industrial large-scale production.
  • Figure 1 is an optical photograph of the graphite powder-lithium composite prepared in Example 1 after standing in an inert environment for 24 hours.
  • Example 2 is an XRD diffraction pattern of the graphite powder-lithium composite material prepared in Example 1 after standing in an inert environment for 24 hours.
  • Example 3 is a scanning electron micrograph of graphene obtained in Example 1.
  • Example 4 is a scanning electron micrograph of graphene obtained in Example 4.
  • Fig. 5 is an atomic force microscope photograph of graphene obtained in Example 1.
  • the XRD diffraction pattern of the material is shown in Fig. 2, and the gold-yellow material obtained by the analysis is an alkali metal intercalated graphite.
  • the graphene was examined by scanning electron microscopy to 10 layers with a lateral dimension of 10 microns (see Figure 3).
  • the graphene material obtained was examined by atomic force microscopy to obtain a graphene material having a thickness of 3.5 nm (see Fig. 5).
  • the composite material was placed in a different solvent such as ethanol, formic acid, acetic acid, water or dilute hydrochloric acid, and there was no significant difference in the severity of the reaction, but it was slightly slowed down as the acidity decreased.
  • a different solvent such as ethanol, formic acid, acetic acid, water or dilute hydrochloric acid
  • the invention provides a method for preparing graphene by intercalating an alkali metal.
  • a graphite-based material and an alkali metal in an inert environment to obtain a uniformly mixed graphite-based carbon material-alkali-metal composite material, and allowing to stand in an inert environment to cause a metal intercalation reaction,
  • the obtained composite material is placed in a liquid medium capable of reacting therewith to carry out a reaction, the intercalation material is removed, and the graphene material is obtained by shaking, washing and separating.
  • high-quality graphene is obtained by intercalating a lithium metal and a graphite-based carbon material to obtain a high-quality graphene, and the obtained graphene has high yield and obtained graphite.
  • the olefin product has a high single layer rate, and the preparation method is fast and efficient, low in energy consumption and small in pollution, and is suitable for industrial large-scale production, and has good economic value and application prospect.

Abstract

L'invention concerne une méthode de préparation de graphène par intercalation d'un métal alcalin, comprenant les étapes suivantes : (1) dans un environnement inerte, mélanger un matériau à base de graphite avec un métal alcalin pour acquérir un matériau carboné à base de graphite-matériau composite de métal alcalin uniformément mélangé, se trouvant dans l'environnement inerte, et mettre en œuvre une réaction d'intercalation de métal ; (2) retirer le matériau d'intercalation en plaçant le matériau composite obtenu dans un milieu à l'état liquide capable de réagir avec celui-ci et faire réagir, et acquérir un matériau de graphène au moyen d'oscillations, de lavage et de séparation. L'invention concerne également un graphène préparé à l'aide la présente méthode. La méthode utilise un matériau composite jaune doré obtenu en mélangeant du lithium ou un autre métal alcalin à forte activité et un matériau carboné à base de graphite et en mettant en œuvre une réaction d'intercalation en tant que précurseur, et la préparation ultérieure de graphène peut être réalisée dans des conditions de température et d'air ambiants, convenant pour la préparation à grande échelle de graphène.
PCT/CN2018/085135 2018-04-09 2018-04-28 Méthode de préparation de graphène par intercalation de métal alcalin WO2019196144A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810312337.4 2018-04-09
CN201810312337.4A CN110357081A (zh) 2018-04-09 2018-04-09 一种碱金属插层制备石墨烯的方法

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WO2019196144A1 true WO2019196144A1 (fr) 2019-10-17

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CN114408916B (zh) * 2021-12-16 2023-07-07 广东邦普循环科技有限公司 一种膨胀石墨及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103626165A (zh) * 2012-08-28 2014-03-12 海洋王照明科技股份有限公司 石墨烯的制备方法
CN104003372A (zh) * 2013-02-21 2014-08-27 海洋王照明科技股份有限公司 一种石墨烯材料及其制备方法
CN107416809A (zh) * 2017-06-01 2017-12-01 黄凯 一种制备石墨烯的方法

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CN102815694A (zh) * 2012-03-13 2012-12-12 华东理工大学 一种石墨烯的制备方法和使用该方法制备的石墨烯

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103626165A (zh) * 2012-08-28 2014-03-12 海洋王照明科技股份有限公司 石墨烯的制备方法
CN104003372A (zh) * 2013-02-21 2014-08-27 海洋王照明科技股份有限公司 一种石墨烯材料及其制备方法
CN107416809A (zh) * 2017-06-01 2017-12-01 黄凯 一种制备石墨烯的方法

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