WO2017018855A1 - Plaque de graphène dopée d'un métal - Google Patents

Plaque de graphène dopée d'un métal Download PDF

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Publication number
WO2017018855A1
WO2017018855A1 PCT/KR2016/008374 KR2016008374W WO2017018855A1 WO 2017018855 A1 WO2017018855 A1 WO 2017018855A1 KR 2016008374 W KR2016008374 W KR 2016008374W WO 2017018855 A1 WO2017018855 A1 WO 2017018855A1
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WO
WIPO (PCT)
Prior art keywords
graphene
metal
graphene plate
graphite
plate
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PCT/KR2016/008374
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English (en)
Korean (ko)
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백종범
전인엽
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울산과학기술원
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Publication of WO2017018855A1 publication Critical patent/WO2017018855A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a graphene plate in which a metal is introduced, and more particularly, to a graphene plate in which a post-transition metal or metalloid is introduced into an edge of graphene.
  • Fuel cells have many advantages over batteries, such as energy safety, low operating costs, stable power generation, fuel selection, clean emissions and high power efficiency.
  • two major technical risks (manufacturing costs and reliability) have, to date, hindered commercialization.
  • ORR anodic oxygen reduction reaction
  • Platinum (Pt) based materials have been found to be the most efficient catalysts to date.
  • manufacturing costs are high, and fuel cells using them have various problems related to carbon monoxide poisoning, fuel selectivity, and long-term stability.
  • platinum substitutes including platinum based alloys, non-noble metal metal based catalysts, enzymatic electrochemical catalysts and hetero-doped carbon based materials.
  • hetero-doped carbonaceous materials such as carbon black, carbon nanoparticles, carbon nanotubes, and graphene have been studied as efficient metal free electrochemical catalysts for ORR.
  • Graphene is a carbon-based material composed of a single layer of sp 2 carbon having a two-dimensional honeycomb lattice layer, and has many specific properties including excellent electrical conductivity, large surface area, excellent mechanical flexibility, and high thermal / chemical stability.
  • boron Wang, S. et al. BCN graphene as efficient metal-free electrocatalyst for the oxygen reduction reaction. Angew. Chem. Int. Ed.
  • Korean Patent Publication No. 2013-009070 of the present applicant discloses a technique in which a functional group such as a carboxyl group is introduced at the edge of graphene.
  • a metal preferably post-transition metal or metalloid, is introduced at the edge part, based on the most optimized ball milling method.
  • the above object is achieved by a graphene plate in which a post-transition metal or metalloid is bonded with carbon at the edge portion.
  • the post-transition metal may be selected from the group consisting of aluminum, gallium, indium, tin, lead and bismuth.
  • the metalloid may be selected from the group consisting of silicon, germanium, arsenic and tellurium.
  • the total element content of the post-transition metal or metalloid in the graphene plate may be 0.1 element% to 5 element%.
  • the grain size of the graphene plate may be 0.1 to 100 ⁇ m.
  • the graphene plate may be prepared by mixing the metal or metalloid and graphite after the transition in a weight ratio of 1:10 to 10: 1, and then mechanically pulverizing. It can be achieved in a vacuum for 24 to 60 hours at a rate.
  • An object of the present invention is to prepare a mixture of graphite and a metal or post-transition metal in a weight ratio of 1:10 to 10: 1; Reacting the graphene with the metal by grinding with a ball mill under vacuum; Washing the reactants with a solvent to remove unreacted materials; And lyophilizing the reactant, thereby achieving a graphene plate having a metal bonded to carbon at an edge portion thereof.
  • the graphene plate according to the present invention provides a graphene plate into which a post-transition metal and a metalloid are introduced, which could not be manufactured by the conventional graphene manufacturing process. Since the graphene plate according to the present invention has excellent electrochemical activity and durability, it can be applied more quickly and easily in various fields and contribute to the commercialization of graphene.
  • Figure 1c is a natural graphite (a), CGnP (b), HGnP (c) before grinding SEM pictures of AlGnP (d), GaGnP (e), InGnP (f), GeGnP (g), SnGnP (h), PbGnP (i), AsGnP (j), SbGnP (k), BiGnP (l) Scale bar: 1 ⁇ m).
  • FIG. 2A illustrates an XPS spectra image of natural graphite
  • FIG. 2B is an enlarged view of an XPS spectra image of graphene (AlGnP) in which aluminum is introduced into a post-transition metal.
  • FIG. 3 shows an XPS spectra image of graphene (XGnP) into which post-transition metal is introduced.
  • FIG. 4 shows an XPS spectra image of graphene (XGnP) in which a metal is introduced.
  • FIG. 5a shows graphene (SbGnP) incorporating antimony
  • FIG. 5b shows graphene (AlGnP) incorporating aluminum
  • FIG. 5c shows graphene (InGnP) incorporating indium
  • FIG. Fin PbGnP
  • FIG. 5E shows an image of the atomic magnification transmission electron microscope of bismuth introduced graphene (BiGnP).
  • Figure 6 is a graph showing the electrochemical activity of graphite, commercial platinum catalyst and the graphene introduced antimony according to the present invention.
  • FIG. 7 is a graph comparing the stability of graphite, commercial platinum catalyst and graphene introduced antimony according to the present invention.
  • graphene Since graphene is electrochemically inert, it is necessary to give electrochemical activity to graphene to expand its field of application. For this purpose, graphene using non-metal elements nitrogen (N), phosphorus (P), sulfur (S), selenium (Se), fluoro (F), chlorine (Cl), boron (Br), and iodine (I) A method of doping is known. However, when heterogeneous elements are introduced into graphene using the conventional chemical vapor deposition method or the oxidation method, the introduction itself is not good, and the excellent properties of the graphene itself are often weakened. Therefore, the graphene produced by the conventional method has a limit to exhibit the excellent characteristics of the graphene itself.
  • the present invention provides a graphene plate incorporating a metal into the edge portion of the graphene.
  • the present invention relates to a graphene plate in which a metal, such as a post-transition metal or a metalloid, is introduced at the edge of the graphene in order to impart electrochemical activity and stability to the electrochemically inactive graphene. Relates to a graphene plate in which the carbon of the edge of graphene and the metal are bonded.
  • the present invention provides graphene polarized by introducing heterogeneous elements, preferably metals, more preferably transition metals or metalloids, on the edges of graphene.
  • the metal after the transition may be selected from the group consisting of aluminum (Al), gallium (Ga), indium (In), tin (Sn), lead (Pb), and bismuth (Bi).
  • the metalloid may be selected from the group consisting of silicon, germanium, arsenic, and tellurium.
  • the method for preparing a graphene plate into which a metal is introduced according to the present invention includes the following steps:
  • the grinding process is preferably made for 24 to 60 hours at a speed of 100 to 10,000 rpm.
  • FIG. 1A schematically illustrates a manufacturing process of a graphene plate into which a metal (antimony) is introduced according to the present invention
  • FIG. 1B schematically illustrates a manufacturing process of a graphene plate into which a metal is introduced.
  • the graphite (C) located at the edge of the graphene plate is activated while the graphite is crushed into the graphene plate. And some of them combine with the metal.
  • the graphene plate has a grain size of 0.1 to 100 ⁇ m.
  • 1C shows natural graphite (a), CGnP (b), HGnP (c), AlGnP (d), GaGnP (e), InGnP (f), GeGnP (g), SnGnP (h), PbGnP before grinding into a ball mill. SEM pictures of (i), AsGnP (j), SbGnP (k) and BiGnP (l).
  • the size of natural graphite is about 150 ⁇ m, but the grain size of the graphene plate into which the metal according to the present invention is introduced is 1 ⁇ m or less (scale bar: 1 ⁇ m).
  • the natural graphite is ball milled together with a solid metal or a post-transition metal, thereby producing graphite having a multi-layered structure into a plurality of graphene plates, and introducing the metal into the edge portion to have a large surface area and pore volume.
  • Graphene plates can be provided. Graphene plates having this particular feature can contribute to the improvement of electrocatalyst performance.
  • FIGS. 2b and 3a The results are shown in FIGS. 2b and 3a. 2B and 3A, it can be seen that C-Al bonds formed by bonding C and Al of graphene are formed at the edges of the graphene. Compared with the natural graphite shown in FIG. 2, Al-introduced graphene showed O1s peaks and Al2p peaks in addition to the strong C1s peaks present in graphite, and it was confirmed that C-Al bonds were formed.
  • Atomic-resolution transmission electron microscopy (AR-TEM) photographs of AlGnP are shown in FIG. 5B.
  • 5B dark Al atoms are observed only along the edges of AlGnP. This confirms that Al is introduced only at the edge of the graphene plate.
  • the GaGnP spectrum of FIG. 3b was analyzed to calculate the element content (at.%) Of C, O, and Ga in the finally manufactured GaGnP, and is shown in Table 1 below.
  • FIG. 5C Atomic-resolution transmission electron microscopy (AR-TEM) photographs of InGnP are shown in FIG. 5C.
  • AR-TEM Atomic-resolution transmission electron microscopy
  • FIG. 5D Atomic-resolution transmission electron microscopy (AR-TEM) photographs of PbGnP are shown in FIG. 5D. 5D, dark colored Pb atoms are only observed along the edges of PbGnP. This confirmed that the Pb is introduced only at the edge of the graphene plate.
  • AR-TEM Atomic-resolution transmission electron microscopy
  • Si in the final manufactured SiGnP is shown in Table 1 below.
  • Ge in the final GeGnP produced is shown in Table 1 below.
  • FIG. 5A is an AR-TEM photograph obtained at the edge of SbGnP where dark colored Sb atoms are observed only along the edge of SbGnP. This confirmed that Sb is introduced only at the edge of the graphene plate.
  • Te in the final TeGnP produced is shown in Table 1 below.
  • the results are shown in FIG. 8 (a: CGnP, b: HGnP, c: GaGnP, d: SnGnP, e: SbGnP).
  • SEI solid-electrolyte interphase
  • the starting cathode peak near 0.5 V is associated with the insertion of Li + into the graphite layer, indicating that graphene is capable of lithium storage.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention concerne une plaque de graphène dopée d'un métal et, spécifiquement, concerne une plaque de graphène dans laquelle un métal post-transition ou un métalloïde est dopé au bord du graphène. La présente invention décrit la plaque de graphène, dans laquelle un métal post-transition ou un métalloïde, qui ne peut pas être produit par des procédés classiques de production de graphène, est dopé au bord du graphène, faisant ainsi preuve d'excellentes activité électrochimique et durabilité. Grâce à ces caractéristiques, la plaque de graphène selon la présente invention peut être appliquée plus rapidement et facilement à divers domaines, et peut contribuer à la commercialisation du graphène.
PCT/KR2016/008374 2015-07-29 2016-07-29 Plaque de graphène dopée d'un métal WO2017018855A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020150107277A KR101765672B1 (ko) 2015-07-29 2015-07-29 금속이 도입된 그래핀 플레이트
KR10-2015-0107277 2015-07-29

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WO2017018855A1 true WO2017018855A1 (fr) 2017-02-02

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ES2971746T3 (es) * 2018-11-09 2024-06-06 Lg Energy Solution Ltd Dispositivo formador de bolsas
KR102324367B1 (ko) * 2020-02-20 2021-11-09 원광대학교산학협력단 철 도핑 없이 질소가 도핑된 그래피틱 나노플레이트 및 이의 제조 방법

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
BHATTACHARJY A, DHRUBAJYOTI ET AL.: "Graphene Nanoplatelets with Selectively Functionalized Edges as Electrode Material for Electrochemical Energy Storage", LANGMUIR, vol. 31, no. 20, 5 May 2015 (2015-05-05), pages 5676 - 5683, XP055302979 *
CHANG, JUNGBO ET AL.: "Multilayered Si Nanoparticle/reduced Graphene Oxide Hybrid as High-performance Lithium-ion Battery Anode", ADVANCED MATERIALS, vol. 26, no. 5, 2014, pages 758 - 764, XP055353206 *
JEON, IN - YUP ET AL.: "Antimony-doped Graphene Nanoplatelets", NATURE COMMUNICATIONS, vol. 6, no. 7123, 22 May 2015 (2015-05-22), pages 1 - 8, XP055353208 *
JEON, IN - YUP ET AL.: "Edge-selectively Sulfurized Graphene Nanoplatelets as Efficient Metal-free Electrocatalysts for Oxygen Reduction Reaction: The Electron Spin Effect", ADVANCED MATERIALS, vol. 25, no. 42, 2013, pages 6138 - 6145, XP055353123 *
JEON, IN - YUP ET AL.: "Facile, Scalable Synthesis of Edge-halogenated Graphene Nanoplatelets as Efficient Metal-free Eletrocatalysts for Oxygen Reduction Reaction", SCIENTIFIC REPORTS, vol. 3, no. 1810, 2013, pages 1 - 7, XP055353209 *
RASHAD, MUHAMMAD ET AL.: "Effect of Graphene Nanoplatelets Addition on Mechanical Properties of Pure Aluminum Using a Semi-powder Method", PROGRESS IN NATURAL SCIENCE : MATERIALS INTERNATIONAL, vol. 24, no. 2, 2014, pages 101 - 108, XP028849827 *

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KR20170014252A (ko) 2017-02-08

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