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WO2013008166A1 - Matériau d'électrode comprenant du sulfure de métal - Google Patents

Matériau d'électrode comprenant du sulfure de métal Download PDF

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Publication number
WO2013008166A1
WO2013008166A1 PCT/IB2012/053491 IB2012053491W WO2013008166A1 WO 2013008166 A1 WO2013008166 A1 WO 2013008166A1 IB 2012053491 W IB2012053491 W IB 2012053491W WO 2013008166 A1 WO2013008166 A1 WO 2013008166A1
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WO
WIPO (PCT)
Prior art keywords
electrode material
carbon
sulfur
electrical cell
weight
Prior art date
Application number
PCT/IB2012/053491
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English (en)
Inventor
Arnd Garsuch
Stefan Herzog
Lucas Montag
Andrea KREBS
Original Assignee
Basf Se
Basf (China) Company 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
Application filed by Basf Se, Basf (China) Company Limited filed Critical Basf Se
Priority to JP2014519665A priority Critical patent/JP2014523094A/ja
Priority to KR1020147003374A priority patent/KR20140063591A/ko
Priority to CN201280034109.6A priority patent/CN103650215A/zh
Priority to EP12810947.7A priority patent/EP2732492A4/fr
Publication of WO2013008166A1 publication Critical patent/WO2013008166A1/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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds 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
    • H01M4/58—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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • 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
    • 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

  • Electrode material comprising metal sulfide
  • the present invention relates to electrode material for an electrical ceil comprising as
  • component (A) at least one ion- and electron-conductive metal chalcogenide, as component (B) carbon in a polymorph comprising at least 60% sp 2 -hybridized carbon atoms, as component (C) at least one sulfur-containing component selected from the group consisting of elemental sulfur, a composite produced from elemental sulfur and at least one polymer, a polymer comprising divalent di- or polysulfide bridges and mixtures thereof, and as component (D) optionally at least one binder.
  • component (C) at least one sulfur-containing component selected from the group consisting of elemental sulfur, a composite produced from elemental sulfur and at least one polymer, a polymer comprising divalent di- or polysulfide bridges and mixtures thereof, and as component (D) optionally at least one binder.
  • the invention further relates to a rechargeable electrical cell comprising at least one electrode which has been produced from or using the inventive electrode material, to the use of the rechargeable electrical cell and to the use of an ion- and electron-conductive metal chalcogenide for production of an inventive rechargeable electrical cell.
  • Secondary batteries, accumulators or rechargeable batteries are just some embodiments by which electrical energy can be stored after generation and used when required. Owing to the significantly better power density, there has been a departure in recent times from the water- based secondary batteries toward development of batteries in which the charge transport in the electrical cell is accomplished by lithium ions.
  • lithium-sulfur cells sulfur in the sulfur cathode is reduced via polysulfide ions to S 2 -, which is reoxidized when the cell is charged to form sulfur-sulfur bonds.
  • the literature proposes, as described in Adv. Mater. 2002, 14, 963-965, the production and use of polymer-sulfur composites and sulfur- containing polymers as cathode materials in rechargeable lithium-sulfur batteries.
  • the known cathode materials are still unsatisfactory with regard to a combination of required properties such as capacity, cycling stability (lifetime), mechanical stability, resistance to chemicals (solvents, conductive salts), electrochemical corrosion stability and thermal stability, in the development of new cathode materials, the economic viability of the new material in terms of raw material and production costs is also a further important criterion.
  • an electrode material for an electrical cell comprising
  • (D) optionally at least one binder.
  • the proportion of the metal chalcogenide (A) is from 0.1 to 30% and especially from 5 to 20% by weight, the proportion of the carbon (B) from 19 to 50% and especially from 30 to 40% by weight and the proportion of the sulfur-containing component (C) from 20 to 80% and especially from 40 to 60% by weight, where the percentages by weight are each based on the total mass of components (A), (B) and (C).
  • the sum of the proportions by weight of components (A), (B) and (C) is from 50 to 100%, preferably from 80 to 100% and especially from 90 to 100%, based on the total weight of the inventive electrode material.
  • the ion- and electron-conductive metal chalcogenide present in the inventive electrode material is also called metal chalcogenide (A) or component (A) for short in the context of the present invention.
  • the metal chalcogenide (A) is preferably selected from the group of compounds consisting of CoTe 2 , Cr 2 S 3 , HfS 2 , HfSe 2 , HfTe 2) lrTe 2 , MoS 2> MoSe 2 , MoTe 2 , NbS 2 , NbSe 2 , NbTe 2 , NiTe 2 , PtS 2 , PtSe 2 , PtTe 2 , SnS 2 , SnSSe, SnSe 2 , TaS 2 , TaSe 2 , TaTe 2 , TiS 2 , TiSe 2) TiTe 2 , VS 2 , VSe 2 , VTe 2 , WS 2 , WSe 2 , WTe 2
  • the metal chalcogenide (A) is TiS 2 .
  • the metal cha!cogenide (A) at room temperature has an ion and electron conductivity between 10 10 and 10 2 Ohrrr cm 1 .
  • the inventive electrode material for an electrical cell further comprises carbon in a polymorph comprising at least 60% sp z -hybridized carbon atoms, preferably from 75% to 100% sp 2 - hybridized carbon atoms.
  • this carbon is also called carbon (B) or component (B) for short, and is known as such.
  • the carbon (B) is an electrically conductive polymorph of carbon.
  • Carbon (B) can be selected, for example, from graphite, carbon black, carbon nanotubes, graphene or mixtures of at least two of the aforementioned substances.
  • Figures in % are based on all of the carbon (B) present in the electrode material together with metal chalcogenide (A) and component (C), including any impurities, and denote percent by weight.
  • carbon (B) is carbon black.
  • Carbon black may, for example, be selected from lamp black, furnace black, flame black, thermal black, acetylene black and industrial black.
  • Carbon black may comprise impurities, for example hydrocarbons, especially aromatic hydrocarbons, or oxygen-containing compounds or oxygen-containing groups, for example OH groups.
  • impurities for example hydrocarbons, especially aromatic hydrocarbons, or oxygen-containing compounds or oxygen-containing groups, for example OH groups.
  • sulfur- or iron-containing impurities are possible in carbon black.
  • carbon (B) is partially oxidized carbon black.
  • carbon (B) comprises carbon nanotubes.
  • Carbon nanotubes (CNTs for short), for example single-wall carbon nanotubes (SW CNTs) and preferably multiwall carbon nanotubes (MW CNTs), are known per se. A process for preparation thereof and some properties are described, for example, by A. Jess et al. in Chemie Ingenieurtechnik 2006, 78, 94 - 100.
  • carbon nanotubes have a diameter in the range from 0.4 to 50 nm, preferably 1 to 25 nm.
  • carbon nanotubes have a length in the range from 10 nm to 1 mm, preferably 00 nm to 500 nm.
  • Carbon nanotubes can be prepared by processes known per se.
  • a volatile carbon compound for example methane or carbon monoxide, acetylene or ethylene, or a mixture of volatile carbon compounds, for example synthesis gas
  • a suitable gas mixture is a mixture of carbon monoxide with ethylene.
  • Suitable temperatures for decomposition are, for example, in the range from 400 to 1000°C, preferably 500 to 800°C.
  • Suitable pressure conditions for the decomposition are, for example, in the range from standard pressure to 100 bar, preferably to 10 bar.
  • Single- or multiwall carbon nanotubes can be obtained, for example, by decomposition of carbon compounds in a light arc, specifically in the presence or absence of a decomposition catalyst.
  • the decomposition of volatile carbon compound(s) is performed in the presence of a decomposition catalyst, for example Fe, Co or preferably Ni.
  • a decomposition catalyst for example Fe, Co or preferably Ni.
  • graphene is understood to mean almost ideally or ideally two-dimensional hexagonal carbon crystals of analogous structure to single graphite layers.
  • carbon (B) is selected from graphite, graphene, activated carbon and especially carbon black.
  • Carbon (B) may, for example, be in the form of particles having a diameter in the range from 0.1 to 00 ⁇ , preferably 2 to 20 pm.
  • the particle diameter is understood to mean the mean diameter of the secondary particles, determined as the volume average.
  • carbon (B) and especially carbon black has a BET surface area in the range from 20 to 1500 m 2 /g, measured to ISO 9277.
  • At least two, for example two or three, different kinds of carbon (B) are mixed.
  • Different kinds of carbon (B) may differ, for example, with regard to particle diameter or BET surface area or extent of contamination.
  • the carbon (B) selected Is a combination of two different carbon blacks.
  • inventive electrode material for an electrical cell comprises, as well as metal chalcogenide (A) and carbon (B), at least one sulfur-containing component selected from the group consisting of elemental sulfur, a composite produced from elemental sulfur and at least one polymer, a polymer comprising divalent di- or polysu!fide bridges and mixtures thereof.
  • the sulfur-containing component is also called component (C) for short in the context of the present invention.
  • Elemental sulfur is known as such.
  • Composites produced from elemental sulfur and at least one polymer, which find use as a constituent of electrode materials, are likewise known to those skilled in the art.
  • Adv. Funct. Mater. 2003, 13, 487 ff describes, for example, a reaction product of sulfur and polyacrylonitrile, which results from elimination of hydrogen from polyacrylonitrile with simultaneous formation of hydrogen sulfide.
  • Polymers comprising divalent di- or polysulfide bridges for example polyethylene tetrasulfide, are likewise known in principle to those skilled in the art. J. Electrochem. Soc, 1991 , 138, 1896 - 1901 and US 5,162,175 describe the replacement of pure sulfur with polymers comprising disulfide bridges. Polyorganodisulfides are used therein as materials for solid redox
  • polymerization electrodes in rechargeable cells together with polymeric electrolytes.
  • component (C) in the inventive electrode material is elemental sulfur.
  • component (A) in the inventive electrode material is TiS2, component (B) carbon black, and component (C) elemental sulfur.
  • the proportion of the TiS 2 is preferably from 0.1 to 30% and especialiy from 5 to 20% by weight, the proportion of the carbon black from 9 to 50% and especially from 30 to 40% by weight, and the proportion of the elemental sulfur from 20 to 80% and especially from 40 to 60% by weight, the percentages by weight each being based on the total mass of TiS 2 , carbon black and elemental sulfur.
  • the proportion of carbon black in the inventive electrode materia] is 30 to 40% by weight, based on the total mass of TiS 2 , carbon black and elemental sulfur, and the mass ratio of elemental sulfur to T1S2 is in the range from 60:40 to 95:5, even more preferably in the range from 70:30 to 90: 0 and especialiy in the range from 75:25 to 85:15.
  • the sum of the proportions by weight of TiS 2 , carbon black and elemental sulfur is from 50 to 100%, preferably 80 to 100%, especially 90 to 100%, based on the total weight of the inventive electrode material. This does not take into account the mass of an output conductor such as a metal foil, for example aluminum foil.
  • inventive electrode material for an electrical cell optionally comprises, as well as metal chalcogenide (A), carbon (B) and component (C), at least one binder, which is also referred to in the context of the present invention as binder (D) for short.
  • binder (D) serves principally for mechanical stabilization of inventive electrode material.
  • binder (D) is selected from organic (co) polymers.
  • suitable organic (co)polymers may be halogenated or halogen-free.
  • PEO polyethylene oxide
  • cellulose carboxymethylceilulose
  • polyvinyl alcohol polyethylene
  • polypropylene polytetrafluoroethylene
  • polyacryionitrile-methyl methacrylate copolymers polyethylene
  • polypropylene polytetrafluoroethylene
  • polyacryionitrile-methyl methacrylate copolymers styrene-butadiene copolymers, tetrafluoroethylene-hexafluoropropyiene copolymers, vinylidene fluoride-hexafluoropropylene copolymers (PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymers, perfluoroalkyl vinyl ether copolymers, ethylene-tetrafluoroethylene copolymers,
  • copolymers ethylene-acrylic acid copolymers, optionally at least partially neutralized with a!kaii metal salt or ammonia, ethylene-methacrylic acid copolymers, optionally at least partially neutralized with alkali metal salt or ammonia, ethylene-(meth)acrylic ester copolymers, poiyimides and polyisobutene.
  • Suitable binders are especially polyvinyl alcohol and halogenated (co)polymers, for example polyvinyl chloride or polyvinylidene chloride, especially fluorinated (co)polymers such as polyvinyl fluoride and especially polyvinylidene fluoride and polytetrafluoroethyiene.
  • the mean molecular weight w of binder (D) may be selected within wide limits, suitable examples being 20 000 g/mol to 1 000 000 g/mol.
  • the inventive electrode material comprises in the range from 0.1 to 10% by weight of binder, preferably 1 to 8% by weight and more preferably 3 to 6% by weight, based on the total mass of components (A), (B), (C) and (D).
  • Binder (D) can be incorporated into inventive electrode material by various processes. For example, it is possible to dissolve soluble binders (D) such as polyvinyl alcohol in a suitable solvent or solvent mixture, water/isopropanol for example being suitable for polyvinyl alcohol, and to prepare a suspension with the further constituents of the electrode material. After application to a suitable substrate, the solvent or solvent mixture is removed, for example evaporated, to obtain an electrode composed of the inventive electrode material.
  • a suitable solvent for polyvinylidene fluoride is NMP.
  • the components (A), (B), (C) and optionally (D) present in the inventive electrode material may, for example, be in a homogeneous mixture with one another.
  • the inventive cathode material may also have a layered structure, in which case at least two layers differ from one another in terms of composition.
  • the inventive cathode material may be composed of a first layer consisting of a homogeneous mixture of components (B), (C) and (D), and of a second layer consisting of a homogeneous mixture of components (A) and (D) or of a homogeneous mixture of components (A), (B) and (D).
  • Inventive electrode materials are particularly suitable as or for production of electrodes, especially for production of electrodes of lithium-containing batteries, especially rechargeable batteries.
  • the present invention provides for the use of inventive electrode materials as or for production of electrodes for rechargeable electrical ceils.
  • the present invention further provides rechargeable electrical cells comprising at least one electrode which has been produced from or using an inventive electrode material as described above.
  • the electrode in question is the cathode.
  • the electrode referred to as the cathode is that which has reducing action on discharge (operation).
  • inventive electrode material is processed to give electrodes, for example in the form of continuous belts which are processed by the battery manufacturer.
  • Electrodes produced from inventive electrode material may, for example, have thicknesses in the range from 20 to 500 ⁇ , preferably 40 to 200 ⁇ . They may, for example, have a rod- shaped configuration, or be configured in the form of round, elliptical or square columns or in cuboidal form, or as flat electrodes.
  • the electrodes produced with the inventive electrode material may have further constituents customary per se, for example an output conductor, which may be configured in the form of a metal wire, metal grid, metal mesh, expanded metal, metal sheet or a metal foil. Suitable metal foils are especially aluminum foils. A flat output conductor, such as an aluminum foil, can be coated on one side or on both sides with the inventive electrode material.
  • an output conductor which may be configured in the form of a metal wire, metal grid, metal mesh, expanded metal, metal sheet or a metal foil.
  • Suitable metal foils are especially aluminum foils.
  • a flat output conductor, such as an aluminum foil can be coated on one side or on both sides with the inventive electrode material.
  • a cathode may comprise the inventive electrode material in a layered structure, in which case, for example, an aluminum foil as the output conductor is first coated on one or both sides with a mixture of sulfur, carbon black and binder, and then the first layer applied is sealed with a second layer consisting of titanium sulfide and binder or consisting of titanium sulfide, carbon black and binder.
  • inventive rechargeable electrical cells comprise, as well as inventive electrode material, at least one electrode comprising metallic magnesium, metallic aluminum, metallic zinc, metallic sodium or preferably metallic lithium.
  • inventive rechargeable eiectrical cells comprise, as well as inventive electrode material, a liquid electrolyte comprising a lithium-containing conductive salt.
  • inventive rechargeable electrical cells comprise, in addition to inventive electrode material and a further electrode, especially an electrode comprising metallic lithium, at least one nonaqueous solvent which may be liquid or solid at room temperature, and is preferably liquid at room temperature, and which is preferably selected from polymers, cyclic and noncyclic ethers, cyclic and noncyclic acetals, cyclic and noncyclic organic carbonates and ionic liquids.
  • suitable polymers are especially polyaikylene glycols, preferably poly-C C4- alkylene glycols and especially polyethylene glycols. These polyethylene glycols may comprise up to 20 mol% of one or more Ci-C4-alkylene glycols in copo!ymerized form.
  • the polyaikylene glycols are preferably polyaikylene glycols double-capped by methyl or ethyl.
  • the molecular weight M w of suitable polyaikylene glycols and especially of suitable polyethylene glycols may be at least 400 g/mol.
  • the molecular weight w of suitable polyaikylene glycols and especially of suitable polyethylene glycols may be up to 5 000 000 g/mol, preferably up to 2 000 000 g/mol.
  • noncyclic ethers are, for example, diisopropyl ether, di-n-butyl ether, 1 ,2-d ' imethoxyethane, 1 ,2-diethoxyethane, preference being given to 1 ,2-dimethoxyethane.
  • Suitable cyclic ethers are tetrahydrofuran and 1,4-dioxane.
  • noncyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1 , 1 -dimethoxyethane and 1 , 1 -diethoxyethane.
  • Suitable cyclic acetals are 1 ,3-dioxane and especially 1 ,3-dioxolane.
  • noncyclic organic carbonates examples include dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.
  • Suitable cyclic organic carbonates are compounds of the general formulae (X) and
  • R 1 , R 2 and R 3 may be the same or different and are selected from hydrogen and Ci-C 4 - alky!, for example methyl, ethyl, n-propyl, isopropyi, n-butyl, isobutyl, sec-butyl and tert-butyl, where R 2 and R 3 are preferably 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 (XII).
  • the solvent(s) is (are) preferably used in what is known as the anhydrous state, i.e. with a water content in the range from 1 ppm to 0.1% by weight, determinable, for example, by Karl Fischer titration.
  • inventive rechargeable electrochemical cells comprise one or more conductive salts, preference being given to lithium salts.
  • suitable lithium salts are LiPF 6 , LiBF 4 , LiCI0 4) LiAsF 6 , LiCF 3 S0 3 , LiC(C n F2n + iS0 2 )3, lithium imides such as LiN(C n F2n+iS02)2, where n is an integer in the range from 1 to 20, LiN(S0 2 F)2, Li 2 SiFB, LiSbF 6 , LiAICI 4) and salts of the general formula (C n F2n+iS02) m XLi, where m is defined as follows:
  • m 3 when X is selected from carbon and silicon.
  • Preferred conductive salts are selected from LiC(CF 3 S0 2 )3, LiN(CF 3 S0 2 )2, LiPF 6 , LiBF 4 , LiCI0 4 , particular preference being given to LiPF 6 and LiN(CF 3 S0 2 ) 2 .
  • inventive rechargeable electrochemical cells comprise one or more separators by which the electrodes are mechanically separated.
  • Suitable separators are polymer films, especially porous polymer films, which are unreactive toward metallic lithium and toward lithium sulfides and lithium polysulfides.
  • Particularly suitable materials for separators are polyolefins, especially porous polyethylene in film form and porous polypropylene in film form.
  • Separators made from polyolefin, especially made from polyethylene or polypropylene, may have a porosity in the range from 35 to 45%. Suitable pore diameters are, for example, in the range from 30 to 500 nm.
  • the separators selected may be separators made from PET nonwovens filled with inorganic particles. Such separators may have a porosity in the range from 40 to 55%. Suitable pore diameters are, for example, in the range from 80 to 750 nm.
  • Inventive rechargeable electrical cells are notable for particularly high capacities, high performance even after repeated charging, even under the action of mechanical stress on the cell, and significantly delayed cell death.
  • Inventive rechargeable electrical cells are very suitable for use in automobiles, aircraft, bicycles operated by electric motor, for example pedelecs, ships or stationary energy stores. Such uses form a further part of the subject matter of the present invention.
  • the present invention also provides for the use of an ion- and electron-conductive metal chalcogenide for production of a rechargeable electrical cell as described above.
  • the ion- and electron-conductive metal chalcogenide is processed together with carbon in a polymorph comprising at least 60% sp 2 -hybrtdized carbon atoms and at least one sulfur-containing component selected from the group consisting of elemental sulfur, a composite produced from elemental sulfur and at least one polymer, a polymer comprising divalent di- or polysulfide bridges, and mixtures thereof, and optionally further constituents to give an electrode, which is used as a component for production of a rechargeable electrical cell.
  • aqueous formulations of electrode materials (E1 , E2, E3, C-E4 and C-E5) obtainable from example !. were each used as follows for production of electrodes.
  • the respective ink was sprayed by means of an airbrush method onto aluminum foil (thickness: 30 ⁇ ) on a vacuum table (temperature: 75°C). Nitrogen was used for spraying. A solids loading of 4 mg/cm 2 was achieved. Thereafter, the aluminum foil coated on one side was cautiously laminated between two rubber rollers. A low applied pressure was selected, in order that the coating remained porous. Subsequently, the aluminum foil coated on one side was treated thermally in a drying cabinet at a temperature of 40°C.
  • inventive electrode materials E1 , E2 and E3 were used to produce the inventive cathodes K1 , K2 and K3, and the comparative electrode materials C-E4 and C-E5 to produce the comparative cathodes C-K4 and C-K5.
  • electrochemical cells according to figure 1 were constructed.
  • the following components were used in each case:
  • Anode Li foil, thickness 50 ⁇ ,
  • Electrolyte 8% by weight of LiTFSI (LiN(S0 2 CF 3 )2), 2% by weight of LiN0 3 , 45% by weight of
  • inventive cathodes K1 , K2 and K3 were used to produce inventive cells Z1 , Z2 and Z3, and comparative electrodes C-K4 and C-K5 to produce comparative cells C-Z4 and C-Z5.
  • Figure 1 shows the schematic structure of a dismantled electrochemical cell for testing of inventive and noninventive electrode materials.
  • the % by weight are based on the sum of the masses of S, TiS 2 and C used in the electrode material production, without taking into account any further constituents, for example binder or solvent residue.

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Abstract

La présente invention concerne un matériau d'électrode pour un élément électrique comprenant comme composant (A) au moins un chalcogénure de métal conducteur d'ions et d'électrons, comme composant (B) du carbone dans un polymorphe comprenant au moins 60 % d'atomes de carbone hybridés sp2, comme composant (C) au moins un composant contenant du soufre choisi dans le groupe constitué par le soufre élémentaire, un composite produit à partir de soufre élémentaire et d'au moins un polymère, un polymère comprenant des ponts disulfure ou polysulfure divalents et des mélanges de ceux-ci, et comme composant (D) éventuellement au moins un liant. L'invention concerne en outre un élément électrique rechargeable comprenant au moins une électrode ayant été produite à partir ou au moyen du matériau d'électrode selon l'invention, ainsi que l'utilisation de cet élément électrique rechargeable et l'utilisation d'un chalcogénure de métal conducteur d'ions et d'électrons pour la production d'un élément électrique rechargeable selon l'invention.
PCT/IB2012/053491 2011-07-11 2012-07-09 Matériau d'électrode comprenant du sulfure de métal WO2013008166A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2014519665A JP2014523094A (ja) 2011-07-11 2012-07-09 金属硫化物を含む電極材料
KR1020147003374A KR20140063591A (ko) 2011-07-11 2012-07-09 금속 황화물을 포함하는 전극 물질
CN201280034109.6A CN103650215A (zh) 2011-07-11 2012-07-09 包含金属硫化物的电极材料
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EP3121877A1 (fr) * 2015-07-24 2017-01-25 Basf Se Particules coeur-écorce comprenant du soufre élémentaire et du dioxyde de manganèse pour des cathodes des cellules de soufre de lithium et synthèse de ces particules
CN107919464A (zh) * 2017-10-27 2018-04-17 长江大学 一种锂离子电池碲化钼阳极材料及其制备方法
EP3457483A4 (fr) * 2016-11-28 2019-05-15 LG Chem, Ltd. Matériau actif de cathode pour pile lithium-soufre, comportant des nanoparticules de sulfure métallique, et son procédé de fabrication
US11417884B2 (en) 2017-12-20 2022-08-16 Cornell University Titanium disulfide-sulfur composites
US11631898B2 (en) 2015-12-08 2023-04-18 Lg Energy Solution, Ltd. Electrolyte for lithium secondary battery and lithium secondary battery comprising same

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CN107732010B (zh) * 2017-09-29 2020-07-10 华中科技大学 一种选通管器件及其制备方法
CN109326780B (zh) * 2018-09-18 2021-05-14 昆明理工大学 一种二硫化钨负极材料包覆硫复合材料制备方法
CN112038589A (zh) * 2019-06-04 2020-12-04 中国科学院物理研究所 高能量密度铝二次电池及其正极材料和制备方法
WO2021124522A1 (fr) * 2019-12-19 2021-06-24 株式会社Adeka Matériau actif d'électrode, son procédé de production, composition pour former une couche de mélange d'électrode, électrode pour batteries secondaires à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux
CN113839044B (zh) * 2021-11-29 2022-03-18 广东工业大学 一种锂硫电池正极及其制备方法和锂硫电池
CN114388274B (zh) * 2021-12-30 2024-02-02 浙江浙能中科储能科技有限公司 一种离子和电子复合导通的电极及其原位制备方法
CN115101357B (zh) * 2022-06-14 2024-01-26 中国工程物理研究院激光聚变研究中心 一种三元镍钴钨碲化物复合材料的制备方法及应用
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CN104091927A (zh) * 2014-07-17 2014-10-08 浙江大学 Ws2带孔纳米片/石墨烯电化学贮镁复合电极及制备方法
EP3121877A1 (fr) * 2015-07-24 2017-01-25 Basf Se Particules coeur-écorce comprenant du soufre élémentaire et du dioxyde de manganèse pour des cathodes des cellules de soufre de lithium et synthèse de ces particules
CN104992843A (zh) * 2015-08-01 2015-10-21 大连理工大学 一种二硫化钛纳米片/石墨烯复合材料对电极及其制备方法
CN104992843B (zh) * 2015-08-01 2017-06-27 大连理工大学 一种二硫化钛纳米片/石墨烯复合材料对电极及其制备方法
US11631898B2 (en) 2015-12-08 2023-04-18 Lg Energy Solution, Ltd. Electrolyte for lithium secondary battery and lithium secondary battery comprising same
EP3457483A4 (fr) * 2016-11-28 2019-05-15 LG Chem, Ltd. Matériau actif de cathode pour pile lithium-soufre, comportant des nanoparticules de sulfure métallique, et son procédé de fabrication
US10770727B2 (en) 2016-11-28 2020-09-08 Lg Chem, Ltd. Cathode active material for lithium-sulfur battery, comprising metal sulfide nanoparticles, and method for producing same
CN107919464A (zh) * 2017-10-27 2018-04-17 长江大学 一种锂离子电池碲化钼阳极材料及其制备方法
CN107919464B (zh) * 2017-10-27 2018-08-17 长江大学 一种锂离子电池碲化钼阳极材料及其制备方法
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