WO2012164443A1 - Matériaux composites, leur production et leur utilisation dans des cellules électriques - Google Patents

Matériaux composites, leur production et leur utilisation dans des cellules électriques Download PDF

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Publication number
WO2012164443A1
WO2012164443A1 PCT/IB2012/052575 IB2012052575W WO2012164443A1 WO 2012164443 A1 WO2012164443 A1 WO 2012164443A1 IB 2012052575 W IB2012052575 W IB 2012052575W WO 2012164443 A1 WO2012164443 A1 WO 2012164443A1
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Prior art keywords
composite material
carbon
material according
sulfur
cyclic
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PCT/IB2012/052575
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German (de)
English (en)
Inventor
Nicole Janssen
Alexander Panchenko
Oliver Gronwald
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Basf Se
Basf (China) Company Limited
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Priority to KR1020137034459A priority Critical patent/KR20140035961A/ko
Priority to JP2014513281A priority patent/JP2014522435A/ja
Priority to CN201280022865.7A priority patent/CN103534303A/zh
Priority to EP12792642.6A priority patent/EP2714793A4/fr
Publication of WO2012164443A1 publication Critical patent/WO2012164443A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0688—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polyquinolines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/04—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 present invention relates to composite materials containing a reaction product of
  • the present invention relates to a method for producing composite materials according to the invention and the use of composite materials according to the invention.
  • Secondary batteries, accumulators, rechargeable batteries or "rechargeable batteries” are only a few embodiments for storing and using electrical energy after production because of their significantly better power density, they have recently deviated from the water-based secondary batteries and developed such batteries. where charge transport in the electrical cell is accomplished by lithium-ion.
  • lithium-ion secondary batteries having a carbon anode and a metal oxide-based cathode are limited in their energy density. New dimensions in energy density were opened by lithium-sulfur cells.
  • sulfur in the sulfur cathode is reduced via polysulfide ions to S 2_ , which are oxidized again during the loading of the cell to form sulfur-sulfur bonds.
  • the problem is the solubility of polysulfides, for example L12S4 and L12S6, which are soluble in the solvent and can migrate to the anode.
  • the consequences may include: loss of capacitance and deposition of electrically insulating material on the sulfur particles of the electrode.
  • the migration from cathode to anode can ultimately lead to a discharge of the affected cell and cell death in the battery.
  • This unwanted migration of polysulfide ions is also referred to in English as a "shuttle", a term that is also used as a shuttle in the context of the present invention.
  • the materials according to the invention are composite materials which in the context of the present invention are also called composite materials according to the invention.
  • Composite materials are materials which are solid mixtures which can not be separated manually and which have different properties than the individual components.
  • materials of the present invention are particulate composites.
  • Inventive composite material contains a reaction product of
  • Polymer (A) may be selected from any organic polymers and copolymers, preferably from polymers obtainable by anionic or free-radical (co) polymerization.
  • the organic polymers or copolymers consist of atoms of the elements carbon and hydrogen and optionally nitrogen, phosphorus, oxygen, sulfur and / or chlorine, in particular from the atoms of the elements carbon and hydrogen and optionally nitrogen, oxygen and / or chlorine, in particular nitrogen.
  • (co) polymerization means homopolymerization or copolymerization.
  • the term (co) polymer is a homopolymer or a copolymer.
  • polymer (A) can be selected from organic polyesters, in particular from aliphatic polyesters.
  • polymer (A) is selected from (co) polymers obtainable by anionic, catalytic or free radical (co) polymerization, in particular polyethylene, polypropylene polyacrylonitrile, polybutadiene, polystyrene, and copolymers of at least two comonomers selected from ethylene , Propylene, styrene, (meth) acrylonitrile, in particular acrylonitrile, and 1, 3-butadiene.
  • polyisoprene and polyacrylates are suitable. Particularly preferred is polyacrylonitrile, in the context of the present invention also called polyacrylonitrile (A).
  • polyacrylonitrile is understood to mean not only polyacrylonitrile homopolymers, but also copolymers of acrylonitrile with 1,3-butadiene or styrene. Preference is given to polyacrylonitrile homopolymers.
  • polyacrylonitrile (A) is present after the reaction, ie in the composite material according to the invention, at least partially in the form of a cyclization product of the formula (I)
  • polyethylene is understood to mean not only homo-polyethylene, but also copolymers of ethylene which contain at least 50 mol% of ethylene and up to 50 mol% of at least one further comonomer, for example ⁇ -olefins such as Propylene, butylene (1-butene), 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-pentene, furthermore isobutene, vinylaromatics such as styrene, for example
  • ⁇ -olefins such as Propylene, butylene (1-butene), 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-pentene, furthermore isobutene, vinylaromatics such as styrene, for example
  • Polyethylene may be HDPE or LDPE.
  • polypropylene is understood to mean not only homo-polypropylene but also copolymers of propylene which contain at least 50 mol% of propylene polymerized and up to 50 mol% of at least one further comonomer, for example ethylene and ⁇ -propylene.
  • Olefins such as butylene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-pentene.
  • Polypropylene is preferably isotactic or substantially isotactic polypropylene.
  • polystyrene is understood to mean not only homopolymers of styrene, but also copolymers of styrene with acrylonitrile, 1,3-butadiene,
  • (Meth) acrylic acid Ci-Cio-alkyl esters of (meth) acrylic acid, divinylbenzene, 1, 2-diphenylethylene or ⁇ -methylstyrene, in particular with acrylonitrile or 1, 3-butadiene.
  • Another preferred polymer (A) is polybutadiene.
  • polymer (A) is selected from those which before the reaction have an average molecular weight M w in the range from 50,000 to 500,000 g / mol, preferably up to 250,000 g / mol.
  • polyacrylonitrile (A) is selected from those polyacrylonitriles having an average molecular weight M w in the range from 10,000 to 500,000 g / mol, in particular from 50,000 to 250,000 g / mol, before the reaction.
  • Polymer (A) may be crosslinked or uncrosslinked (co) polymers.
  • Sulfur (B) is known as such and in the context of the present invention may also be referred to briefly as sulfur.
  • the carbon (C) is an electrically conductive modification of carbon.
  • carbon (C) can be graphite.
  • % data refers to the total carbon (C) incorporated into the composite of the invention under chemically reactive conditions, including any impurities, and denotes percent by weight.
  • carbon (C) is carbon black.
  • Carbon black may, for example, be chosen from lampblack, furnace black, flame black, thermal black, acetylene black, carbon black and furnace carbon black.
  • Carbon black may contain impurities, for example hydrocarbons, in particular aromatic hydrocarbons, or oxygenated hydrocarbons. substance-containing compounds or oxygen-containing groups such as OH groups.
  • sulfur or iron-containing impurities in carbon black are possible.
  • carbon (C) is partially oxidized carbon black.
  • carbon (C) is carbon nanotubes.
  • Carbon nanotubes carbon nanotubes, short CNT or English carbon nanotubes
  • SW CNT single-walled carbon nanotubes
  • MW CNT multi-walled carbon nanotubes
  • carbon nanotubes have a diameter in the range of 0.4 to 50 nm, preferably 1 to 25 nm.
  • carbon nanotubes have a length in the range of 10 nm to 1 mm, preferably 100 nm to 500 nm.
  • Carbon nanotubes can be prepared by methods known per se. For example, one can use a volatile carbon-containing compound such as methane or carbon monoxide, acetylene or ethylene, or a mixture of volatile carbon-containing compounds such as synthesis gas in the presence of one or more reducing agents such as hydrogen and / or another gas such as nitrogen decompose. Another suitable gas mixture is a mixture of carbon monoxide with ethylene.
  • Suitable decomposition temperatures are, for example, in the range from 400 to 1000.degree. C., preferably from 500 to 800.degree.
  • Suitable pressure conditions for the decomposition are, for example, in the range of atmospheric pressure to 100 bar, preferably up to 10 bar.
  • Single- or multi-walled carbon nanotubes can be obtained, for example, by decomposition of carbon-containing compounds in the arc, in the presence or absence of a decomposition catalyst.
  • the decomposition of volatile carbon-containing compounds or carbon-containing compounds in the presence of a decomposition catalyst for example Fe, Co or preferably Ni.
  • the starting mixture for the preparation of the reaction product for the composite material according to the invention contains as component (D) 2 to 20% by weight, preferably 3 to 15% by weight, in particular in particular 4 to 10% by weight of a perfluorinated or partially fluorinated polymer (D) based on the total weight of the components (A), (B) and (C) used before the reaction.
  • Examples of perfluorinated or partially fluorinated polymers (D) may be fluorine-containing homo- or copolymers. Preference is given to choosing polymer (D) from the group of fluorine-containing polymers consisting of polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymers, vinylidene fluoride-hexafluoropropylene copolymers (PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymers, perfluoroalkylvinyl ether copolymers, ethylene Tetrafluoroethylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers and ethylene-chlorofluoroethylene copolymers.
  • fluorine-containing polymers consisting of polytetrafluoroethylene, polyvinyl fluoride, poly
  • the perfluorinated or partially fluorinated polymer (D) is preferably used in powder form. Particular preference is given to using a powder having an average particle size of 0.1 to 10 ⁇ m, in particular 0.5 to 2 ⁇ m.
  • polytetrafluoroethylene is understood to mean not only polytetrafluoroethylene homopolymers, but also copolymers of tetrafluoroethylene with hexafluoropropylene or vinylidene fluoride, and terpolymers consisting of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride.
  • the perfluorinated or partially fluorinated polymer (D) is polytetrafluoroethylene, in particular polytetrafluoroethylene homopolymer.
  • At least two of the abovementioned starting materials have chemically reacted with one another during the course of the production of composite material according to the invention, preferably polymer (A) and sulfur. It is not necessary that polymer (A) and sulfur enter into covalent bonds with each other. Thus, for example, it is possible that sulfur serves only as an oxidizing agent and is removed as H2S from the reaction medium.
  • polymer (A) and sulfur (B) have formed covalent bonds in the formation of composite material of the invention.
  • the composite material according to the invention also contains particles or domains which have sulfur (B) -filled carbon (C).
  • sulfur is preferably dispersed molecularly in carbon (C), for example in the form of sulfur rings or in the form of linear sulfur molecules, for example linear Ss molecules.
  • Such particles or domains can be detected for example by electron beam micro-area analysis.
  • the pores of carbon (C) are at least partially filled with sulfur (B).
  • Such particles or domains may have an average diameter in the range from 10 to 100 ⁇ m, preferably up to 70 ⁇ m.
  • such particles or domains contain carbon (C) and sulfur (B) in a weight ratio in the range of 2: 1 to 1:15, preferably 1: 1, 5 to 1:10.
  • the particles or domains described above are black to the human eye.
  • the above-described particles or domains contain not more than 5% by weight of polymer (A) or not more than 5% by weight of the above-described reaction product. In a specific embodiment of the present invention, neither the polymer (A) nor the above-described reaction product can be detected in the particles or domains described above.
  • Composite according to the invention can furthermore contain particles or domains which contain significant proportions of the above-described reaction product, for example at least 10% by weight.
  • the latter particles or domains may have a diameter in the range of 5 to 75 ⁇ m, preferably 10 to 50 ⁇ m. They are preferably smaller than the former particles or domains.
  • composite material in the range of 20 to 80 wt .-%, preferably 30 to 70 wt .-% of sulfur, determined by elemental analysis.
  • the composite material according to the invention contains in the range from 0.1 to 30% by weight carbon (C), preferably from 1 to 20% by weight.
  • This carbon is likewise determinable, for example, by elemental analysis, wherein it must be taken into account in the evaluation of the elemental analysis that polymer also comes into contact with polymer (A) in the composite material according to the invention.
  • the loss of sulfur employed by the reaction of the sulfur with hydrogen atoms of the polymer (A ) to form gaseous hydrogen sulfide is preferably in the range from 4.9 to 45% by weight.
  • the proportion of the component (B) before the reaction preferably in the range of 35 to 95 wt .-%, in particular 45 to 85 wt .-% and the proportion of the component (C) before implementation, preferably in the range of 0.1 to 20 wt .-%, in particular 5 to 15 wt .-%.
  • the composite material according to the invention may further comprise at least one binder (E).
  • Binder (E) is mainly used for the mechanical stabilization of composite material according to the invention.
  • binder (E) is selected from organic (co) polymers.
  • suitable organic (co) polymers may be halogenated or halogen-free.
  • PEO polyethylene oxide
  • cellulose carboxymethylcellulose
  • polyvinyl alcohol polyethylene
  • polypropylene polytetrafluoroethylene
  • polyacrylonitrile-methyl methacrylate copolymers polyethylene
  • polypropylene polytetrafluoroethylene
  • polyacrylonitrile-methyl methacrylate copolymers styrene-butadiene copolymers
  • tetrafluoroethylene-hexafluoropropylene copolymers vinylidene fluoride-hexafluoropropylene copolymers (PVdF-HFP)
  • Vinylidene fluoride-tetrafluoroethylene copolymers perfluoroalkyl vinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride-ch
  • Suitable binders are in particular polyvinyl alcohol and halogenated (co) polymers, for example polyvinyl chloride or polyvinylidene chloride, in particular fluorinated (co) polymers such as polyvinyl fluoride and in particular polyvinylidene fluoride and polytetrafluoroethylene.
  • the average molecular weight M w of binder (E) can be chosen within wide limits, suitable, for example, 20,000 g / mol to 1. 000,000 g / mol.
  • the composite material according to the invention preferably contains in the range from 0.1 to 10% by weight, particularly preferably 5 to 10% by weight and very particularly preferably 7 to 8% by weight. % Binder (E) based on the mass of the finished composite material.
  • Binder (E) can be incorporated into composite material according to the invention by various methods. For example, it is possible to dissolve soluble binders (E) such as polyvinyl alcohol in a suitable solvent or solvent mixture, for example, water / isopropanol is suitable for polyvinyl alcohol, and to produce a suspension with the other constituents of the cathode. After application to a suitable pad is the Solvent or solvent mixture removed, for example, evaporated, and obtained according to the invention composite material. Suitable solvent for polyvinylidene fluoride is NMP.
  • sparingly soluble polymers as binders (E), for example additional perfluorinated or partially fluorinated (co) polymers such as polytetrafluoroethylene or tetrafluoroethylene-hexafluoropropylene copolymers, a suspension of particles of the relevant binder (E) and the other constituents of the cathode is prepared and squeeze them under heat.
  • additional perfluorinated or partially fluorinated (co) polymers such as polytetrafluoroethylene or tetrafluoroethylene-hexafluoropropylene copolymers
  • the composite material additionally contains carbon that is incorporated into the composite under non-reactive conditions.
  • This additional carbon can be selected from the same materials as carbon (C). It may be the same or different from carbon (C), for example carbon (C) and additional carbon may be two different carbon blacks or graphites.
  • composite material according to the invention additionally contains carbon black which has not been reacted with organic polymer (A) or polyacrylonitrile (A) and sulfur (B).
  • composite material in the range of 0.1 to 10 wt .-% contains additional carbon, preferably additional carbon black, based on the mass of the finished composite material.
  • Composite materials according to the invention are particularly suitable as or for the production of electrodes, in particular for the production of electrodes of lithium-containing batteries.
  • the present invention is the use of composite materials according to the invention as or for the production of electrodes for electrical cells.
  • Another object of the present invention are electrical cells containing at least one electrode which is made of or using at least one composite material according to the invention.
  • the respective electrode is the cathode, which may also be referred to as a sulfur cathode or an S-cathode.
  • that electrode is referred to as the cathode, which has a reducing effect during unloading (working).
  • composite material according to the invention is processed into electrodes, for example in the form of endless belts, which are processed by the battery manufacturer.
  • electrodes made of composite material according to the invention may have thicknesses in the range from 20 to 500 ⁇ m, preferably 40 to 200 ⁇ m. They may be, for example, rod-shaped, in the form of round, elliptical or square columns or cuboidal or as flat electrodes.
  • electrical cells according to the invention contain, in addition to the composite material according to the invention, at least one electrode which contains metallic zinc, metallic sodium or preferably metallic lithium.
  • electrical cells according to the invention contain, in addition to a composite material according to the invention and a further electrode, at least one nonaqueous solvent which may be liquid or solid at room temperature, preferably selected from polymers, cyclic or noncyclic ethers, cyclic or noncyclic Acetals, cyclic or non-cyclic organic carbonates and ionic liquids.
  • a nonaqueous solvent which may be liquid or solid at room temperature, preferably selected from polymers, cyclic or noncyclic ethers, cyclic or noncyclic Acetals, cyclic or non-cyclic organic carbonates and ionic liquids.
  • polymers are in particular polyalkylene glycols, preferably P0IV-C1-C4-alkylene glycols and in particular polyethylene glycols.
  • Polyethylene glycols may contain up to 20 mol% of one or more C 1 -C 4 -alkylene glycols in copolymerized form.
  • polyalkylene glycols are polyalkylene glycols double capped with methyl or ethyl.
  • the molecular weight M w of suitable polyalkylene glycols and especially of suitable polyethylene glycols may be at least 400 g / mol.
  • the molecular weight M w of suitable polyalkylene glycols and in particular of suitable polyethylene glycols may be up to 5,000,000 g / mol, preferably up to 2,000,000 g / mol
  • non-cyclic ethers are, for example, diisopropyl ether, di-n-butyl ether, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, preference is 1, 2-dimethoxyethane.
  • Suitable cyclic ethers are tetrahydrofuran and 1,4-dioxane.
  • non-cyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1,1-dimethoxyethane and 1,1-diethoxyethane.
  • Suitable cyclic acetals are 1, 3-dioxane and in particular 1, 3-dioxolane.
  • non-cyclic organic carbonates examples include dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.
  • suitable cyclic organic carbonates are compounds of the general formulas (II) and (III)
  • R 1 , R 2 and R 3 may be identical or different and selected from hydrogen and C 1 -C 4 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec. Butyl and tert-butyl, preferably R 2 and R 3 are not both tert-butyl.
  • R 1 is methyl and R 2 and R 3 are each hydrogen or R 1 , R 2 and R 3 are each hydrogen.
  • Another preferred cyclic organic carbonate is vinylene carbonate, formula (IV).
  • the solvent or solvents are used in the so-called anhydrous state, i. with a water content in the range of 1 ppm to 0.1 wt .-%, determined for example by Karl Fischer titration.
  • electrochemical cells according to the invention comprise one or more conductive salts, preference being given to lithium salts.
  • suitable lithium salts are LiPF 6, LiBF 4, LiCI0 4, LiAsF 6, L1CF3SO3, LiC (C n F 2n + IS02) 3, lithium imides such as LiN (C n F 2n + IS02) 2, where n is an integer in the range 1-20 LiN (SO 2 F) 2, Li 2 SiFe, LiSbF 6, LiAICU, and salts of the general formula (C n F 2n + i SO 2) m X Li, where m is defined as follows:
  • m 3 if X is chosen from carbon and silicon.
  • Preferred conducting salts are selected from LiC (CF 3 SO 2 ) 3 , LiN (CF 3 SO 2 ) 2 , LiPF 6 , LiBF 4 ,
  • electrochemical cells according to the invention contain one or more separators, by means of which the electrodes are mechanically separated.
  • Suitable separators are polymer films, in particular porous polymer films, which are unreactive with respect to metallic lithium and to lithium sulfides and lithium polysulfides.
  • Particularly suitable materials for separators are polyolefins, in particular film-shaped porous polyethylene and film-shaped porous polypropylene.
  • Polyolefin separators particularly polyethylene or polypropylene, may have a porosity in the range of 35 to 45%. Suitable pore diameters are for example in the range from 30 to 500 nm.
  • separators made of PET particles filled with inorganic particles may have a porosity in the range of 40 to 55%. Suitable pore diameters are for example in the range of 80 to 750 nm.
  • Inventive electrical cells are characterized by particularly high capacity, high performance even after repeated charging and greatly delayed cell death.
  • the shuttle can be suppressed very well.
  • Electric cells according to the invention are very well suited for use in automobiles, aircraft, ships or stationary energy storage. Such uses are a further subject of the present invention.
  • Another object of the present invention is a process for the preparation of composite materials according to the invention, which is also referred to in the context of the present invention as a manufacturing method according to the invention.
  • the production process according to the invention comprises at least one process step, which is characterized in that
  • organic polymer (A), sulfur (B), carbon (C) and perfluorinated or partially fluorinated polymer (D) are as defined above, in particular also with regard to preferred embodiments thereof.
  • organic polymer (A) is selected from polyethylene, polypropylene, polyacrylonitrile, polybutadiene, polystyrene and copolymers of at least two comonomers selected from Ethylene, propylene, styrene, acrylonitrile and 1, 3-butadiene, most preferably from polyacrylonitrile.
  • the components (A), (B), (C) and (D) are brought together before the thermal reaction in such proportions that the skilled person from the desired final composition after the thermal reaction and taking into account the potentially resulting in the thermal reaction , gaseous by-products, especially hydrogen sulfide, can easily calculate.
  • the preparation process according to the invention can be carried out in the presence of a solvent, for example toluene or ethanol. However, it is preferable to carry out the production process according to the invention without solvent.
  • a solvent for example toluene or ethanol.
  • the production process according to the invention is carried out without pressure, ie at normal pressure.
  • the inventive production process is carried out at elevated pressure, for example at 1, 1 to 100 bar.
  • the process according to the invention is carried out under autogenous pressure.
  • you can set any pressure for example, 10 bar or normal pressure, and performs the reaction in a pressure vessel, such as an autoclave.
  • the formation of gaseous by-products, in particular H 2 S may increase the pressure during the reaction, for example to pressures of up to 100 bar or even more. If it is desired to carry out the production process according to the invention under autogenous pressure, it is possible to use the pressure measurement to monitor the reaction.
  • the production process according to the invention can be carried out over a period in the range from 10 minutes to 100 hours, preferably from 2 to 24 hours.
  • H 2 S it is preferred, after completion of the reaction, to free the resultant composite material according to the invention from H 2 S, for example to degas it.
  • the degassing can be done for example by evacuation or by purging with an inert gas, for example with nitrogen or with a noble gas such as argon.
  • the composite according to the invention is obtained as a powder.
  • Another object of the present invention is a method for operating automobiles, aircraft, ships or stationary energy storage using at least one electrical cell according to the invention.
  • the invention is illustrated by the following, but not limiting examples of the invention.
  • electrochemical cells according to FIG. 1 were constructed.
  • the following components were used in addition to the cathodes produced in II.
  • Anode Li foil, 50 ⁇ thick,
  • Electrolyte 1 M LiTFSI (LiN (SO 2 CF 2) 2) in 1: 1 mixture of dioxolane and dimethoxyethane
  • FIG. 1 shows the schematic structure of a disassembled electrochemical cell for testing composite materials according to the invention.
  • FIG. 1 The explanations in FIG. 1 mean:

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Abstract

L'invention concerne des matériaux composites contenant un produit de réaction contenant (A) au moins un polymère organique, (B) du soufre, (C) du carbone dans une modification comprenant au moins 60% d'atomes de C hybridés sp2 et (D) 2 à 20% en poids d'un polymère perfluoré ou partiellement fluoré, rapporté au poids total des composés (A), (B) et (C) utilisés pour la réaction. L'invention concerne en outre un procédé pour produire des matériaux composites selon l'invention ainsi que l'utilisation de matériaux composites selon l'invention.
PCT/IB2012/052575 2011-05-27 2012-05-23 Matériaux composites, leur production et leur utilisation dans des cellules électriques WO2012164443A1 (fr)

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KR1020137034459A KR20140035961A (ko) 2011-05-27 2012-05-23 복합 재료, 이의 제조 방법 및 전지에서 이의 용도
JP2014513281A JP2014522435A (ja) 2011-05-27 2012-05-23 複合材料、その製造及び電池におけるその使用方法
CN201280022865.7A CN103534303A (zh) 2011-05-27 2012-05-23 复合材料、其制备及其在电池中的用途
EP12792642.6A EP2714793A4 (fr) 2011-05-27 2012-05-23 Matériaux composites, leur production et leur utilisation dans des cellules électriques

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JP2015115270A (ja) * 2013-12-13 2015-06-22 株式会社アルバック リチウム硫黄二次電池
EP3319099A1 (fr) * 2016-11-02 2018-05-09 Robert Bosch GmbH Cellule de batterie et une batterie avec polymères électroactifs

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WO2009117460A1 (fr) * 2008-03-19 2009-09-24 E. I. Du Pont De Nemours And Company Compositions de polymère électriquement conductrices, et films réalisés à partir de celles-ci
WO2009143405A2 (fr) * 2008-05-22 2009-11-26 The University Of North Carolina At Chapel Hill Synthèse de feuillets de graphène et composites nanoparticulaires en comprenant
WO2011148357A1 (fr) * 2010-05-28 2011-12-01 Basf Se Matériaux composites, leur fabrication et leur utilisation dans des piles voltaïques

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US20070007679A1 (en) * 2004-03-18 2007-01-11 Hitoshi Hashizume Composite material, composite carbon material and method for producing those
WO2011028804A2 (fr) * 2009-09-02 2011-03-10 Ut-Battelle, Llc Nanocomposites soufre-carbone et leur application en tant que matériaux de cathode dans des batteries lithium-soufre

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WO2009117460A1 (fr) * 2008-03-19 2009-09-24 E. I. Du Pont De Nemours And Company Compositions de polymère électriquement conductrices, et films réalisés à partir de celles-ci
WO2009143405A2 (fr) * 2008-05-22 2009-11-26 The University Of North Carolina At Chapel Hill Synthèse de feuillets de graphène et composites nanoparticulaires en comprenant
WO2011148357A1 (fr) * 2010-05-28 2011-12-01 Basf Se Matériaux composites, leur fabrication et leur utilisation dans des piles voltaïques

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015115270A (ja) * 2013-12-13 2015-06-22 株式会社アルバック リチウム硫黄二次電池
EP3319099A1 (fr) * 2016-11-02 2018-05-09 Robert Bosch GmbH Cellule de batterie et une batterie avec polymères électroactifs
US10665853B2 (en) 2016-11-02 2020-05-26 Robert Bosch Gmbh Battery cell and battery including electroactive material

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JP2014522435A (ja) 2014-09-04
KR20140035961A (ko) 2014-03-24
CN103534303A (zh) 2014-01-22
EP2714793A1 (fr) 2014-04-09
EP2714793A4 (fr) 2015-01-14

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