WO2013107798A1 - Utilisation d'un réticulat polymérique en tant matériau de cathode pour des batteries rechargeables - Google Patents

Utilisation d'un réticulat polymérique en tant matériau de cathode pour des batteries rechargeables Download PDF

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Publication number
WO2013107798A1
WO2013107798A1 PCT/EP2013/050796 EP2013050796W WO2013107798A1 WO 2013107798 A1 WO2013107798 A1 WO 2013107798A1 EP 2013050796 W EP2013050796 W EP 2013050796W WO 2013107798 A1 WO2013107798 A1 WO 2013107798A1
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WO
WIPO (PCT)
Prior art keywords
network
cathode material
cathode
use according
electrolyte
Prior art date
Application number
PCT/EP2013/050796
Other languages
German (de)
English (en)
Inventor
Ken SAKAUSHI
Jürgen Eckert
Georg NICKERL
Stefan Kaskel
Original Assignee
Leibniz-Institut Für Festkörper- Und Werkstoffforschung Dresden E.V.
Technische Universität Dresden
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 Leibniz-Institut Für Festkörper- Und Werkstoffforschung Dresden E.V., Technische Universität Dresden filed Critical Leibniz-Institut Für Festkörper- Und Werkstoffforschung Dresden E.V.
Publication of WO2013107798A1 publication Critical patent/WO2013107798A1/fr

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Classifications

    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the field of chemistry and energy technology, in particular the energy storage technology, and relates to the use of a polymer network as a cathode material, as it can be used in particular for organic rechargeable high-performance batteries.
  • Rechargeable batteries basically consist of at least the anode, cathode and an electrolyte.
  • amorphous covalent triazine-based networks (ACTF-1 - amorphous covalent triazine-based framework) are known.
  • the pores of the -1.5 nm network are surrounded by sheet-like structures.
  • These networks exist as a defined network of a layered structure, but without forming a three-dimensional regular network (Kuhn, P. et al: Macromolecules 42, 319-326 (2009)).
  • the object of the present invention is the use of a network as a cathode material for rechargeable batteries, by which the specific energy of the batteries is significantly increased.
  • a polymer network is used as the cathode material for rechargeable batteries, with the network used being an amorphous bipolar porous polymer network based on triazine as the cathode material.
  • triazine with nitrogen in positions 1, 3.5 in the 6-membered ring is used as the base material of the polymer network.
  • a polymer network is used as the cathode material, and both the anions of the electrolyte material and Li + ions or nations can be used as charge carriers in the discharge.
  • the network is used as cathode material and lithium or sodium in pure form or as alloy or compound as anode material, wherein still advantageously the network as cathode material and as anode material L ⁇ Ce, NaCö, LiTiO2, LiSn, LiAl, NaTiO2, or Na3 , 5 Sn is used.
  • salts and organic solvents are used as the electrolyte, more preferably as salts LiPF 6 , NaPF 6 , LiCI0 4 , NaCIO 4 , Li-trifluoromethanesulfonyl imide (Li-TFSI) or Na trifluoromethanesulfonyl imide (Na-TFSI) and as organic solvents propylene carbonate , Ethylene carbonate, diethyl carbonate, dimethyl carbonate or ethyl methyl carbonate.
  • Li-TFSI Li-trifluoromethanesulfonyl imide
  • Na-TFSI Na trifluoromethanesulfonyl imide
  • both the anions of the electrolyte or Li + ions or nations can be used as charge carriers for the transfer of the electrons from one electrode to the other electrode.
  • electrons are transported from the anode to the cathode this is the discharge process.
  • anions from the electrolyte and cations from the anode can be used as charge carriers.
  • LiC6, NaCo, LiTiO 2 , LiSn, LiAl, NaTiO 2 , or Na 3 can advantageously be used as anode materials. 5 Sn. Other metals, such as S or Al, or intercalation compounds can also be used.
  • electrolytes salts and organic solvents can advantageously be used.
  • Li-TFSI Li trifluoromethanesulfonyl imide
  • Na-TFSI Na trifluoromethanesulfonyl imide
  • organic solvents propylene carbonates, ethylene carbonates, diethyl carbonates, dimethyl carbonates or ethylmethylcarbonates.
  • the particular advantage of the solution according to the invention is that a material is used as the cathode material, which is bipolar, ie at the same time an n- and p-type material. As a result, the material can realize both a charging process and a discharging process.
  • C3N 3 + X can be used as the network material. Then the first reaction leads to:
  • C3N 3 + X can be used as the network material. Then the first reaction leads to:
  • the solution according to the invention exhibits a high mechanical stability, as well as a high specific capacity, a large working potential due to a fast ion transport and a large cathode surface.
  • a network consisting of triazine rings (C3N3) in an amorphous structure is processed into a cathode.
  • C3N3 triazine rings
  • 70% by weight of amorphous CTF-1 (ACTF-1), 20% by weight of carbon black as conductive additive and 10% by weight of carboxymethylcellulose are mixed as binder and coated with an aluminum foil as current collector.
  • the polymer network was prepared according to the known method of P. Kuhn et al: Angew. Chem. Int. Ed. 47, 3450-3453 (2008).
  • the ACTF-1 was synthesized by heating a mixture of p-dicyanobenzene and ZnC in a ratio of p-dicyanobenzene / ZnC ⁇ of 0.1 in a quartz vessel to 400 ° C.
  • An anode of commercial Li metal is electrically connected together with the cathode and incorporated into a swagelock cell to test the electrochemical properties.
  • the anode and cathode are positioned in the cell with 1 M LiPF 6 as the electrolyte in the volume ratio of ethylene carbonate: Dimetylencarbonat of 1: 1. Glass fibers separate the cathode from the anode.
  • the cell is transferred to a room with an Ar atmosphere and tested in a VMP3 (multiChannel potentiostatic-galvanostatic system).
  • the specific energy achieved is 1, 084 Wh kg “1 at a specific force of 13.238 W kg “ 1 based on the cathode mass. This is a significant improvement in specific energy over typical values of 600 Wh kg "1 and for the specific force of 500-2000 W kg " 1 for prior art cathode materials.
  • a network consisting of triazine rings (C3N3) in an amorphous structure is processed into a cathode.
  • C3N3 triazine rings
  • 70% by weight of amorphous CTF-1 (ACTF-1), 20% by weight of carbon black as conductive additive and 10% by weight of carboxymethylcellulose are mixed as binder and coated with an aluminum foil as current collector.
  • Na metal was used as anode and reference electrode.
  • 1 M NaCIO 4 in propylene carbonate was used as the electrolyte. It was measured with a three-electrode configuration in a beaker.
  • the specific energy achieved is 500 Wh kg "1 at a specific force of 1 0 kW kg " 1 based on the cathode mass. After 7000 cycles, the electrode shows 80% of its initial capacity in half-cells.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne l'utilisation d'un réticulat polymérique en tant matériau de cathode pour des batteries rechargeables. La présente invention se rapporte aux domaines de la chimie et de la technique énergétique, en particulier de la technique d'accumulation d'énergie, à l'utilisation d'un réticulat polymérique servant de cathode pour des batteries rechargeables constituées d'une cathode, d'une anode et d'un électrolyte. Un réticulat polymérique poreux bipolaire amorphe à base de triasine utilisé comme réticulat sert de matériau de cathode. L'utilisation d'un tel matériau de cathode permet d'augmenter considérablement l'énergie spécifique des batteries.
PCT/EP2013/050796 2012-01-20 2013-01-17 Utilisation d'un réticulat polymérique en tant matériau de cathode pour des batteries rechargeables WO2013107798A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012200827A DE102012200827A1 (de) 2012-01-20 2012-01-20 Verwendung eines Polymernetzwerkes als Kathodenmaterial für wiederaufladbare Batterien
DE102012200827.6 2012-01-20

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WO2013107798A1 true WO2013107798A1 (fr) 2013-07-25

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WO (1) WO2013107798A1 (fr)

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Publication number Priority date Publication date Assignee Title
DE102019110450B3 (de) 2019-04-23 2020-06-10 Humboldt-Universität Zu Berlin Anode und Verfahren zu ihrer Herstellung

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2911723A1 (fr) * 2007-01-19 2008-07-25 Arkema France Electrode comprenant au moins un polynitroxyde triazinique

Family Cites Families (2)

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Publication number Priority date Publication date Assignee Title
CA1202072A (fr) * 1981-12-28 1986-03-18 Yoram S. Papir Batteries renfermant des polymeres electroactifs
CA1341507C (fr) * 1989-09-01 2006-06-13 Michel Gauthier Generateur a l'etat solide fonctionnant par polymerisation redox

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2911723A1 (fr) * 2007-01-19 2008-07-25 Arkema France Electrode comprenant au moins un polynitroxyde triazinique

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
BARPANDA, P. ET AL., NATURE MATER., vol. 10, 2011, pages 772 - 779
KUHN, P. ET AL., MACROMOLECULES, vol. 42, 2009, pages 319 - 326
MIZUSHIMA, K. ET AL., MATER. RES. BULL., vol. 15, 1980, pages 783 - 789
NIGREY, P. J. ET AL., J. ELECTROCHEM. SOC., vol. 128, 1981, pages 1651 - 1654
NISHIDE, H. ET AL., ELECTROCHIM. ACTA, vol. 50, 2004, pages 827 - 831
P. KUHN ET AL., ANGEW. CHEM. INT. ED., vol. 47, 2008, pages 3450 - 3453
PIERRE KUHN ET AL: "Ionothermalsynthese von porösen kovalenten Triazin- Polymernetzwerken", ANGEWANDTE CHEMIE (INTERNATIONAL ED. IN ENGLISH), vol. 120, no. 18, 21 April 2008 (2008-04-21), pages 3499 - 3502, XP055064091, ISSN: 0044-8249, DOI: 10.1002/ange.200705710 *
PIERRE KUHN ET AL: "Toward Tailorable Porous Organic Polymer Networks: A High-Temperature Dynamic Polymerization Scheme Based on Aromatic Nitriles", MACROMOLECULES, vol. 42, no. 1, 13 January 2009 (2009-01-13), pages 319 - 326, XP055064197, ISSN: 0024-9297, DOI: 10.1021/ma802322j *
WHITTINGHAM, M. S. ET AL., SCIENCE, vol. 192, 1976, pages 1126 - 1127

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